Patent Grant
9871145
The present invention relates to an object, a method, or a manufacturing method. In addition, the present invention relates to a process, a machine, manufacture, or a composition of matter. In particular, the present invention relates to, for example, a semiconductor device, a display device, a light-emitting device, a power storage device, an imaging device, a driving method thereof, or a manufacturing method thereof. In particular, one embodiment of the present invention relates to a semiconductor device or a method for manufacturing the semiconductor device.
In this specification and the like, a semiconductor device generally means a device that can function by utilizing semiconductor characteristics. A transistor and a semiconductor circuit are embodiments of semiconductor devices. In some cases, a memory device, a display device, or an electronic device includes a semiconductor device.
A technique by which a transistor is formed using a semiconductor film formed over a substrate having an insulating surface has been attracting attention. The transistor is used in a wide range of electronic devices such as an integrated circuit (IC) or an image display device (display device). A silicon-based semiconductor material is widely known as a material for a semiconductor thin film that can be used for a transistor. As another material, an oxide semiconductor has been attracting attention.
For example, a transistor whose active layer includes an amorphous oxide semiconductor layer containing indium (In), gallium (Ga), and zinc (Zn) is disclosed in Patent Document 1.
Manufacturing of semiconductor devices with highly integrated transistors requires miniaturization of transistors. However, in miniaturization of transistors, an increase in the parasitic capacitance of transistors is a problem.
In the case where parasitic capacitance exists in a channel of a transistor and the vicinity of the channel (e.g., between a source electrode and a drain electrode), for example, a time for charging the parasitic capacitance is needed in the transistor operation. Thus, not only the responsiveness of the transistor but also the responsiveness of a semiconductor device is lowered.
Furthermore, it becomes more difficult to control the shapes of transistors as the miniaturization of transistors advances. Variations due to a manufacturing process significantly affect transistor characteristics and reliability.
Thus, an object of one embodiment of the present invention is to reduce the parasitic capacitance of a transistor. Another object is to provide a semiconductor device capable of high-speed operation. Another object is to provide a semiconductor device with favorable electrical characteristics. Another object is to provide a semiconductor device with high reliability. Another object is to reduce variations in characteristics of a transistor or a semiconductor device that are caused by a manufacturing process. Another object is to provide a semiconductor device including an oxide semiconductor layer having few oxygen vacancies. Another object is to provide a semiconductor device that can be manufactured in a simple process. Another object is to provide a semiconductor device with a structure in which the density of interface state at the interface with an oxide semiconductor layer can be reduced. Another object is to provide a semiconductor device with low power consumption. Another object is to provide a novel semiconductor device or the like. Another object is to provide a manufacturing method of the semiconductor device.
Note that the description of these objects does not disturb the existence of other objects. In one embodiment of the present invention, there is no need to achieve all the objects. Other objects will be apparent from and can be derived from the description of the specification, the drawings, the claims, and the like.
(1) One embodiment of the present invention is a semiconductor device including a first insulating layer over a substrate, a first metal oxide layer over the first insulating layer, an oxide semiconductor layer over the first metal oxide layer, a second metal oxide layer over the oxide semiconductor layer, a gate insulating layer over the second metal oxide layer, and a gate electrode layer over the gate insulating layer. The oxide semiconductor layer includes a first region, a second region, and a third region. The first region and the second region each include a region overlapping with the gate electrode layer. The second region is between the first region and the third region. The second region includes a region with lower resistance than the first region. The third region includes a region with lower resistance than the second region. The second region and the third region each include a region containing an element N (N is phosphorus, argon, or xenon).
(2) Another embodiment of the present invention is a semiconductor device including a first insulating layer over a substrate, a first metal oxide layer over the first insulating layer, an oxide semiconductor layer over the first metal oxide layer, a second metal oxide layer over the first insulating layer and the oxide semiconductor layer, a first gate insulating layer over the second metal oxide layer, and a gate electrode layer over the first gate insulating layer. The second metal oxide layer and the first gate insulating layer each include a region facing side surfaces of the first metal oxide layer and the oxide semiconductor layer. The oxide semiconductor layer includes a first region, a second region, and a third region. The first region and the second region each include a region overlapping with the gate electrode layer. The second region is between the first region and the third region. The second region includes a region with lower resistance than the first region. The third region includes a region with lower resistance than the second region. The second region and the third region each include a region containing an element N (N is phosphorus, argon, or xenon).
(3) Another embodiment of the present invention is the semiconductor device described in (2), in which a second gate insulating layer is between the first gate insulating layer and the gate electrode layer.
(4) Another embodiment of the present invention is the semiconductor device described in any one of (1) to (3), in which the second region includes a region containing the element N at a higher concentration than that in the first region, and the third region includes a region containing the element N at a higher concentration than that in the second region.
(5) Another embodiment of the present invention is the semiconductor device described in any one of (1) to (4), in which the third region includes a region containing the element N at a concentration higher than or equal to 1×1018 atoms/cm3 and lower than or equal to 1×1022 atoms/cm3.
(6) One embodiment of the present invention is a semiconductor device including a first insulating layer over a substrate, a first metal oxide layer over the first insulating layer, an oxide semiconductor layer over the first metal oxide layer, a second metal oxide layer over the oxide semiconductor layer, a gate insulating layer over the second metal oxide layer, a second insulating layer over the second metal oxide layer, and a gate electrode layer over the gate insulating layer. The gate insulating layer includes a region in contact with a side surface of the gate electrode layer. The second insulating layer includes a region in contact with the gate insulating layer. The oxide semiconductor layer includes a first region, a second region, and a third region. The first region includes a region overlapping with the gate electrode layer. The second region includes a region overlapping with the gate insulating layer or the second insulating layer. The second region is between the first region and the third region. The second region and the third region each include a region containing an element N (N is phosphorus, argon, or xenon).
(7) Another embodiment of the present invention is the semiconductor device described in (6), in which the second region includes a region with lower resistance than the first region, and the third region includes a region with lower resistance than the second region.
(8) Another embodiment of the present invention is the semiconductor device described in (6) or (7) including a region where an angle between a bottom surface of the substrate and a tangent of a side surface of the gate electrode layer is greater than or equal to 60° and less than or equal to 85°.
(9) Another embodiment of the present invention is a method for manufacturing a semiconductor device. In the method, a first insulating layer is formed over a substrate, a stack including a first metal oxide layer and a first oxide semiconductor layer is formed over the first insulating layer, the stack including the first metal oxide layer and the first oxide semiconductor layer is etched into an island shape using a first mask to form a second metal oxide layer and a second oxide semiconductor layer, a third metal oxide layer is formed over the second oxide semiconductor layer and the first insulating layer, a second insulating layer is formed over the third metal oxide layer, the second insulating layer is subjected to planarization treatment to form a third insulating layer, part of the third insulating layer is etched using a second mask to form a fourth insulating layer with a groove portion that reaches the third metal oxide layer, a fifth insulating layer is formed over the fourth insulating layer and the third metal oxide layer, a first conductive layer is formed over the fifth insulating layer, the first conductive layer and the fifth insulating layer are subjected to planarization treatment until the fourth insulating layer is exposed to form a gate electrode layer and a sixth insulating layer, the fourth insulating layer and the sixth insulating layer are etched using the gate electrode layer as a mask so that a gate insulating layer is formed, and an ion is added to the second oxide semiconductor layer using the gate electrode layer as a mask to form a source region and a drain region.
(10) Another embodiment of the present invention is a method for manufacturing a semiconductor device. In the method, a first insulating layer is formed over a substrate, a stack including a first metal oxide layer and a first oxide semiconductor layer is formed over the first insulating layer, the stack including the first metal oxide layer and the first oxide semiconductor layer is etched into an island shape using a first mask to form a second metal oxide layer and a second oxide semiconductor layer, a third metal oxide layer is formed over the second oxide semiconductor layer and the first insulating layer, a first gate insulating layer is formed over the third metal oxide layer, a second insulating layer is formed over the first gate insulating layer, the second insulating layer is subjected to planarization treatment to form a third insulating layer, part of the third insulating layer is etched using a second mask to form a fourth insulating layer with a groove portion that reaches the first gate insulating layer, a first conductive layer is formed over the fourth insulating layer and the first gate insulating layer, the first conductive layer is subjected to planarization treatment until the fourth insulating layer is exposed to form a gate electrode layer, the fourth insulating layer is etched using the gate electrode layer as a mask to provide a region where the first gate insulating layer is exposed, the first gate insulating layer is etched using the gate electrode layer as a mask so that a second gate insulating layer is formed, and an ion is added to the second oxide semiconductor layer to form a source region and a drain region.
(11) Another embodiment of the present invention is a method for manufacturing a semiconductor device. In the method, a first insulating layer is formed over a substrate, a stack including a first metal oxide layer and a first oxide semiconductor layer is formed over the first insulating layer, the stack including the first metal oxide layer and the first oxide semiconductor layer is etched into an island shape using a first mask to form a second metal oxide layer and a second oxide semiconductor layer, a third metal oxide layer is formed over the second oxide semiconductor layer and the first insulating layer, a first gate insulating layer is formed over the third metal oxide layer, a second insulating layer is formed over the first gate insulating layer, the second insulating layer is subjected to planarization treatment to form a third insulating layer, part of the third insulating layer is etched using a second mask to form a fourth insulating layer with a groove portion that reaches the first gate insulating layer, a fifth insulating layer is formed over the fourth insulating layer and the first gate insulating layer, a first conductive layer is formed over the fifth insulating layer, the first conductive layer and the fifth insulating layer are subjected to planarization treatment until the fourth insulating layer is exposed to form a gate electrode layer and a sixth insulating layer, the fourth insulating layer and the sixth insulating layer are etched using the gate electrode layer as a mask to provide a region where the first gate insulating layer is exposed, and an ion is added to the second oxide semiconductor layer to form a source region and a drain region.
(12) Another embodiment of the present invention is the method for manufacturing a semiconductor device described in any one of (9) to (11), in which phosphorus, argon, or xenon is added as the ion.
(13) Another embodiment of the present invention is the method for manufacturing a semiconductor device described in any one of (9) to (12), in which a dose of the ion added is greater than or equal to 1×1014 ions/cm2 and less than or equal to 5×1016 ions/cm2.
(14) Another embodiment of the present invention is a method for manufacturing a semiconductor device. In the method, a first insulating layer is formed over a substrate, a stack including a first metal oxide layer and a first oxide semiconductor layer is formed over the first insulating layer, the stack including the first metal oxide layer and the first oxide semiconductor layer is etched into an island shape using a first mask to form a second metal oxide layer and a second oxide semiconductor layer, a third metal oxide layer is formed over the second oxide semiconductor layer and the first insulating layer, a second insulating layer is formed over the third metal oxide layer, the second insulating layer is subjected to planarization treatment to form a third insulating layer, part of the third insulating layer is etched using a second mask to form a fourth insulating layer with a groove portion that reaches the third metal oxide layer, a fifth insulating layer is formed over the fourth insulating layer and the third metal oxide layer, a first conductive layer is formed over the fifth insulating layer, the first conductive layer and the fifth insulating layer are subjected to planarization treatment until the fourth insulating layer is exposed to form a gate electrode layer and a sixth insulating layer, the fourth insulating layer and the sixth insulating layer are etched using the gate electrode layer as a mask to form a gate insulating layer including a region in contact with a side surface of the gate electrode layer and a seventh insulating layer including a region in contact with the gate insulating layer, and an ion is added to the second oxide semiconductor layer to form a source region and a drain region.
(15) Another embodiment of the present invention is the method for manufacturing a semiconductor device described in (14), in which phosphorus, argon, or xenon is added as the ion.
(16) Another embodiment of the present invention is the method for manufacturing a semiconductor device described in (14) or (15), in which a dose of the ion added is greater than or equal to 1×1014 ions/cm2 and less than or equal to 5×1016 ions/cm2.
(17) Another embodiment of the present invention is the method for manufacturing a semiconductor device described in any one of (14) to (16), in which the semiconductor device includes a region where an angle between a tangent of the side surface of the gate electrode layer and a bottom surface of the substrate is greater than or equal to 60° and less than or equal to 85°.
(18) Another embodiment of the present invention is an electronic device including the semiconductor device described in any one of (1) to (8), a housing, and a speaker.
According to one embodiment of the present invention, the parasitic capacitance of a transistor can be reduced, and a semiconductor device capable of high-speed operation can be provided. Alternatively, a semiconductor device with favorable electrical characteristics can be provided. Alternatively, a semiconductor device with high reliability can be provided. Alternatively, variations in characteristics of a transistor or a semiconductor device that are caused by a manufacturing process can be reduced. Alternatively, a semiconductor device including an oxide semiconductor layer having few oxygen vacancies can be provided. Alternatively, a semiconductor device that can be manufactured in a simple process can be provided. Alternatively, a semiconductor device with a structure in which the density of interface state at the interface with an oxide semiconductor layer can be reduced can be provided. Alternatively, a semiconductor device with low power consumption can be provided. Alternatively, a novel semiconductor device or the like can be provided. Alternatively, a manufacturing method of the semiconductor device can be provided.
Note that the description of these effects does not disturb the existence of other effects. One embodiment of the present invention does not necessarily have all the effects listed above. Other effects will be apparent from and can be derived from the description of the specification, the drawings, the claims, and the like.
Embodiments will be described in detail with reference to the drawings. Note that the present invention is not limited to the following description. It will be readily appreciated by those skilled in the art that modes and details of the present invention can be modified in various ways without departing from the spirit and scope of the present invention. The present invention therefore should not be construed as being limited to the following description of the embodiments. In structures of the invention described below, the same portions or portions having similar functions are denoted by the same reference numerals in different drawings, and the description thereof is not repeated in some cases. The same components are denoted by different hatching patterns in different drawings, or the hatching patterns are omitted in some cases.
For example, in this specification and the like, an explicit description “X and Y are connected” means that X and Y are electrically connected, X and Y are functionally connected, and X and Y are directly connected. Accordingly, without being limited to a predetermined connection relationship, for example, a connection relationship shown in drawings or texts, another connection relationship is included in the drawings or the texts.
Here, each of X and Y denotes an object (e.g., a device, an element, a circuit, a wiring, an electrode, a terminal, a conductive film, or a layer).
Examples of the case where X and Y are directly connected include the case where an element that enables electrical connection between X and Y (e.g., a switch, a transistor, a capacitor, an inductor, a resistor, a diode, a display element, a light-emitting element, or a load) is not connected between X and Y, and the case where X and Y are connected without the element that enables electrical connection between X and Y provided therebetween.
For example, in the case where X and Y are electrically connected, one or more elements that enable electrical connection between X and Y (e.g., a switch, a transistor, a capacitor, an inductor, a resistor, a diode, a display element, a light-emitting element, or a load) can be connected between X and Y. Note that the switch is controlled to be turned on or off. That is, the switch is conducting or not conducting (is turned on or off) to determine whether current flows therethrough or not. Alternatively, the switch has a function of selecting and changing a current path. Note that the case where X and Y are electrically connected includes the case where X and Y are directly connected.
For example, in the case where X and Y are functionally connected, one or more circuits that enable functional connection between X and Y (e.g., a logic circuit such as an inverter, a NAND circuit, or a NOR circuit; a signal converter circuit such as a D/A converter circuit, an A/D converter circuit, or a gamma correction circuit; a potential level converter circuit such as a power supply circuit (e.g., a step-up circuit or a step-down circuit) or a level shifter circuit for changing the potential level of a signal; a voltage source; a current source; a switching circuit; an amplifier circuit such as a circuit that can increase signal amplitude, the amount of current, or the like, an operational amplifier, a differential amplifier circuit, a source follower circuit, or a buffer circuit; a signal generation circuit; a memory circuit; or a control circuit) can be connected between X and Y. Note that for example, in the case where a signal output from X is transmitted to Y even when another circuit is provided between X and Y, X and Y are functionally connected. The case where X and Y are functionally connected includes the case where X and Y are directly connected and X and Y are electrically connected.
Note that in this specification and the like, an explicit description “X and Y are electrically connected” means that X and Y are electrically connected (i.e., the case where X and Y are connected with another element or another circuit provided therebetween), X and Y are functionally connected (i.e., the case where X and Y are functionally connected with another circuit provided therebetween), and X and Y are directly connected (i.e., the case where X and Y are connected without another element or another circuit provided therebetween). That is, in this specification and the like, the explicit description “X and Y are electrically connected” is the same as the explicit description “X and Y are connected.”
For example, the case where a source (or a first terminal or the like) of a transistor is electrically connected to X through (or not through) Z1 and a drain (or a second terminal or the like) of the transistor is electrically connected to Y through (or not through) Z2, or the case where a source (or a first terminal or the like) of a transistor is directly connected to part of Z1 and another part of Z1 is directly connected to X while a drain (or a second terminal or the like) of the transistor is directly connected to part of Z2 and another part of Z2 is directly connected to Y, can be expressed by using any of the following expressions.
The expressions include, for example, “X, Y, a source (or a first terminal or the like) of a transistor, and a drain (or a second terminal or the like) of the transistor are electrically connected to each other, and X, the source (or the first terminal or the like) of the transistor, the drain (or the second terminal or the like) of the transistor, and Y are electrically connected to each other in that order,” “a source (or a first terminal or the like) of a transistor is electrically connected to X, a drain (or a second terminal or the like) of the transistor is electrically connected to Y, and X, the source (or the first terminal or the like) of the transistor, the drain (or the second terminal or the like) of the transistor, and Y are electrically connected to each other in that order,” and “X is electrically connected to Y through a source (or a first terminal or the like) and a drain (or a second terminal or the like) of a transistor, and X, the source (or the first terminal or the like) of the transistor, the drain (or the second terminal or the like) of the transistor, and Y are connected in that order.” When the connection order in a circuit structure is defined by an expression similar to the above examples, a source (or a first terminal or the like) and a drain (or a second terminal or the like) of a transistor can be distinguished from each other to specify the technical scope.
Other examples of the expressions include “a source (or a first terminal or the like) of a transistor is electrically connected to X through at least a first connection path, the first connection path does not include a second connection path, the second connection path is a path between the source (or the first terminal or the like) of the transistor and a drain (or a second terminal or the like) of the transistor, Z1 is on the first connection path, the drain (or the second terminal or the like) of the transistor is electrically connected to Y through at least a third connection path, the third connection path does not include the second connection path, and Z2 is on the third connection path.” It is also possible to use the expression “a source (or a first terminal or the like) of a transistor is electrically connected to X through at least Z1 on a first connection path, the first connection path does not include a second connection path, the second connection path includes a connection path through the transistor, a drain (or a second terminal or the like) of the transistor is electrically connected to Y through at least Z2 on a third connection path, and the third connection path does not include the second connection path.” Still another example of the expressions is “a source (or a first terminal or the like) of a transistor is electrically connected to X through at least Z1 on a first electrical path, the first electrical path does not include a second electrical path, the second electrical path is an electrical path from the source (or the first terminal or the like) of the transistor to a drain (or a second terminal or the like) of the transistor, the drain (or the second terminal or the like) of the transistor is electrically connected to Y through at least Z2 on a third electrical path, the third electrical path does not include a fourth electrical path, and the fourth electrical path is an electrical path from the drain (or the second terminal or the like) of the transistor to the source (or the first terminal or the like) of the transistor.” When the connection path in a circuit structure is defined by an expression similar to the above examples, a source (or a first terminal or the like) and a drain (or a second terminal or the like) of a transistor can be distinguished from each other to specify the technical scope.
Note that these expressions are examples and there is no limitation on the expressions. Here, X, Y, Z1, and Z2 each denote an object (e.g., a device, an element, a circuit, a wiring, an electrode, a terminal, a conductive film, or a layer).
Even when independent components are electrically connected to each other in a circuit diagram, one component has functions of a plurality of components in some cases. For example, when part of a wiring also functions as an electrode, one conductive film functions as the wiring and the electrode. Thus, the term “electrical connection” in this specification also means such a case where one conductive film has functions of a plurality of components.
<Notes on Description for Drawings>
In this specification, terms for describing arrangement, such as “over” and “under,” are used for convenience to describe a positional relation between components with reference to drawings. Furthermore, the positional relation between components is changed as appropriate in accordance with a direction in which each component is described. Thus, there is no limitation on terms used in this specification, and description can be made appropriately depending on the situation.
The term “over” or “under” does not necessarily mean that a component is placed directly over or directly under and directly in contact with another component. For example, the expression “electrode B over insulating layer A” does not necessarily mean that the electrode B is over and in direct contact with the insulating layer A and can mean the case where another component is provided between the insulating layer A and the electrode B.
In this specification, the term “parallel” indicates that the angle formed between two straight lines is greater than or equal to −10° and less than or equal to 10°, and accordingly also includes the case where the angle is greater than or equal to −5° and less than or equal to 5°. The term “substantially parallel” indicates that the angle formed between two straight lines is greater than or equal to −30° and less than or equal to 30°. The term “perpendicular” indicates that the angle formed between two straight lines is greater than or equal to 80° and less than or equal to 100°, and accordingly includes the case where the angle is greater than or equal to 85° and less than or equal to 95°. The term “substantially perpendicular” indicates that the angle formed between two straight lines is greater than or equal to 60° and less than or equal to 120°.
In this specification, trigonal and rhombohedral crystal systems are included in a hexagonal crystal system.
In drawings, the size, the layer thickness, or the region is determined arbitrarily for description convenience. Therefore, the size, the layer thickness, or the region is not limited to the illustrated scale. Note that the drawings are schematically shown for clarity, and embodiments of the present invention are not limited to shapes or values shown in the drawings.
In drawings such as a top view (also referred to as a plan view or a layout view) and a perspective view, some of components might not be illustrated for clarity of the drawings.
The expression “being the same” may refer to having the same area or having the same shape. In addition, the expression “being the same” include a case of “being substantially the same” because a manufacturing process might cause some differences.
<Notes on Expressions that can be Rephrased>
In this specification and the like, in describing connections of a transistor, expressions “one of a source and a drain” (or a first electrode or a first terminal) and “the other of the source and the drain” (or a second electrode or a second terminal) are used. This is because a source and a drain of a transistor are interchangeable depending on the structure, operation conditions, or the like of the transistor. Note that the source or the drain of the transistor can also be referred to as a source (or drain) terminal, a source (or drain) electrode, or the like as appropriate depending on the situation.
In addition, in this specification and the like, the term such as an “electrode” or a “wiring” does not limit a function of the component. For example, an “electrode” is used as part of a “wiring” in some cases, and vice versa. Further, the term “electrode” or “wiring” can also mean a combination of a plurality of “electrodes” and “wirings” formed in an integrated manner.
In this specification and the like, a transistor is an element having at least three terminals: a gate, a drain, and a source. The transistor has a channel region between the drain (a drain terminal, a drain region, or a drain electrode) and the source (a source terminal, a source region, or a source electrode), and current can flow through the drain, the channel region, and the source.
Since the source and the drain of the transistor change depending on the structure, operating conditions, and the like of the transistor, it is difficult to define which is a source or a drain. Thus, a portion that functions as a source or a portion that functions as a drain is not referred to as a source or a drain in some cases. In that case, one of the source and the drain might be referred to as a first electrode, and the other of the source and the drain might be referred to as a second electrode.
In this specification, ordinal numbers such as first, second, and third are used to avoid confusion among components, and thus do not limit the number of the components.
In this specification and the like, a structure in which a flexible printed circuit (FPC), a tape carrier package (TCP), or the like is attached to a substrate of a display panel, or a structure in which an integrated circuit (IC) is directly mounted on a substrate by a chip on glass (COG) method is referred to as a display device in some cases.
Note that the terms “film” and “layer” can be interchanged with each other depending on the case or circumstances. For example, the term “conductive layer” can be changed into the term “conductive film” in some cases. In addition, the term “insulating film” can be changed into the term “insulating layer” in some cases.
<Notes on Definitions of Terms>
The following are definitions of the terms in this specification and the like.
In this specification, the term “trench” or “groove” refers to a depression with a narrow belt shape.
<Connection>
In this specification, when it is described that “A and B are connected to each other,” the case where A and B are electrically connected to each other is included in addition to the case where A and B are directly connected to each other. Here, the expression “A and B are electrically connected” means the case where electric signals can be transmitted and received between A and B when an object having any electric action exists between A and B.
Note that a content (or part thereof) described in one embodiment can be applied to, combined with, or replaced by a different content (or part thereof) described in the embodiment and/or a content (or part thereof) described in one or a plurality of different embodiments.
Note that in each embodiment, a content described in the embodiment is a content described with reference to a variety of diagrams or a content described with a text described in this specification.
Note that by combining a diagram (or part thereof) described in one embodiment with another part of the diagram, a different diagram (or part thereof) described in the embodiment, and/or a diagram (or part thereof) described in one or a plurality of different embodiments, much more diagrams can be formed.
In this embodiment, a semiconductor device of one embodiment of the present invention and a manufacturing method of the semiconductor device will be described with reference to drawings.
<Structure of Transistor 10>
The transistor 10 includes a substrate 100, an insulating layer 110, a metal oxide layer 121, an oxide semiconductor layer 122, a metal oxide layer 123, a low-resistance region 125, a gate insulating layer 150, a gate electrode layer 160, an insulating layer 180, a conductive layer 190, and a conductive layer 195.
The insulating layer 110 is provided over the substrate 100.
The metal oxide layer 121 is provided over the insulating layer 110.
The oxide semiconductor layer 122 is provided over the metal oxide layer 121. The oxide semiconductor layer 122 includes the low-resistance region 125. The low-resistance region contains one or more of hydrogen, nitrogen, helium, neon, argon, krypton, xenon, boron, phosphorus, tungsten, and aluminum. The low-resistance region 125 functions as a source or a drain.
The metal oxide layer 123 is provided over the oxide semiconductor layer 122.
The gate insulating layer 150 is provided over the metal oxide layer 123.
The gate electrode layer 160 is provided over the gate insulating layer 150. Note that the gate electrode layer 160, the gate insulating layer 150, the metal oxide layer 123, and the oxide semiconductor layer 122 overlap with each other.
The insulating layer 180 is provided over the insulating layer 110.
The conductive layer 190 is provided over the low-resistance region 125. The conductive layer 190 includes a region electrically connected to the low-resistance region 125.
The conductive layer 195 is provided over the conductive layer 190.
Part of the low-resistance region 125 can be below the gate electrode layer 160. When a channel region overlapping with the gate electrode layer 160, a part of the low-resistance region 125 which overlaps with the gate electrode layer 160 and to which an ion is diffused, and a low-resistance region not overlapping with the gate electrode layer 160 are a first region, a second region, and a third region, respectively, the second region includes a region with lower resistance than the first region and the third region includes a region with lower resistance than the second region. The resistance can be obtained by the resistance (e.g., sheet resistance) measurement and can be controlled by the impurity concentration. Furthermore, the third region includes a region where the concentration of the above-described element is greater than or equal to 1×1018 atoms/cm3 and less than or equal to 1×1022 atoms/cm3.
<Metal Oxide Layer>
A metal oxide layer (e.g., the metal oxide layer 121 or 123) refers to a layer which basically has an insulating property and in which current can flow through the interface with a semiconductor and the vicinity thereof when a gate electric field or a drain electric field is increased.
The above structure enables gate-source parasitic capacitance or gate-drain parasitic capacitance to be low. As a result, the transistor can operate at high speed; for example, cutoff frequency characteristics of the transistor 10 can be improved.
In addition, the gate, the source, and the drain of the transistor 10 can be formed in a self-aligned manner; thus, the alignment can be facilitated. Accordingly, a miniaturized transistor can be easily manufactured.
In the transistor 10, in the channel width direction, the gate electrode layer 160 includes a region that faces the side surfaces of the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 with the gate insulating layer 150 provided therebetween as illustrated in the cross-sectional view in
Here, the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 are collectively referred to as an oxide. When the transistor 10 is in an on state, a channel is formed in the entire oxide (bulk), so that the on-state current increases. When the transistor is in an off state, the channel region formed in the oxide semiconductor layer 122 with a wide band gap serves as a potential barrier; as a result, the off-state current can be further reduced.
<Channel Length>
Note that the channel length of a transistor refers to, for example, a distance between a source (a source region or a source electrode) and a drain (a drain region or a drain electrode) in a region where a semiconductor (or a portion where current flows in a semiconductor when the transistor is on) and a gate electrode overlap with each other or a region where a channel is formed in a top view of the transistor. In one transistor, channel lengths in all regions do not necessarily have the same value. In other words, the channel length of one transistor is not fixed to one value in some cases. Therefore, in this specification, the channel length is any one of values, the maximum value, the minimum value, or the average value in a region where a channel is formed.
<Channel Width>
Note that the channel width refers to, for example, the length of a region where a semiconductor (or a portion where current flows in a semiconductor when a transistor is on) and a gate electrode overlap with each other. In one transistor, channel widths in all regions do not necessarily have the same value. In other words, the channel width of one transistor is not fixed to one value in some cases. Therefore, in this specification, the channel width is any one of values, the maximum value, the minimum value, or the average value in a region where a channel is formed.
Note that depending on the transistor structure, a channel width in a region where a channel is actually formed (hereinafter referred to as an effective channel width) is different from a channel width shown in a top view of a transistor (hereinafter referred to as an apparent channel width) in some cases. For example, in a transistor having a three-dimensional structure, an effective channel width is larger than an apparent channel width shown in a top view of the transistor, and its influence cannot be ignored in some cases. For example, in a miniaturized transistor having a three-dimensional structure, the proportion of a channel region formed in a side surface of a semiconductor is high in some cases. In that case, an effective channel width obtained when a channel is actually formed is greater than an apparent channel width shown in the top view.
In a transistor having a three-dimensional structure, an effective channel width is difficult to measure in some cases. For example, estimation of an effective channel width from a design value requires an assumption that the shape of a semiconductor is known. Therefore, without accurate information on the shape of a semiconductor, it is difficult to measure an effective channel width accurately.
<SCW>
Therefore, in this specification, in a top view of a transistor, an apparent channel width in a region where a semiconductor and a gate electrode overlap with each other is referred to as a surrounded channel width (SCW) in some cases. Further, in this specification, in the case where the term “channel width” is simply used, it may denote a surrounded channel width or an apparent channel width. Alternatively, in this specification, in the case where the term “channel width” is simply used, it may denote an effective channel width in some cases. Note that the values of a channel length, a channel width, an effective channel width, an apparent channel width, a surrounded channel width, and the like can be determined by obtaining and analyzing a cross-sectional TEM image and the like.
Note that in the case where field-effect mobility, a current value per channel width, and the like of a transistor are obtained by calculation, a surrounded channel width may be used for the calculation. In that case, a value different from the value obtained by calculation using an effective channel width is obtained in some cases.
<Improvement of Characteristics in Miniaturization>
High integration of a semiconductor device requires miniaturization of a transistor. However, it is known that miniaturization of a transistor causes deterioration of electrical characteristics of the transistor. A decrease in channel width causes a reduction in on-state current.
In the transistor of one embodiment of the present invention illustrated in
In the transistor of one embodiment of the present invention, the gate electrode layer 160 is formed to electrically surround the oxide semiconductor layer 122, which is to be a channel, in the channel width direction; accordingly, a gate electric field is applied to the oxide semiconductor layer 122 in the side surface direction in addition to the perpendicular direction. In other words, a gate electric field is applied to the oxide semiconductor layer 122 entirely, so that current flows in the whole of the oxide semiconductor layer 122, leading to a further increase in on-state current.
The transistor of one embodiment of the present invention has an effect of, for example, making an interface state less likely to be formed because the metal oxide layer 123 is formed over the metal oxide layer 121 and the oxide semiconductor layer 122. In addition, entry of impurities into the oxide semiconductor layer 122 from above and below can be prevented because the oxide semiconductor layer 122 is positioned between the metal oxide layer 121 and the metal oxide layer 123. Therefore, the transistor can achieve not only the increase in the on-state current but also stabilization of the threshold voltage and a reduction in the S value (subthreshold value). Thus, Icut (current when gate voltage VG) is 0 V can be reduced and power consumption can be reduced. Furthermore, since the threshold voltage of the transistor becomes stable, long-term reliability of the semiconductor device can be improved.
In the transistor of one embodiment of the present invention, the gate electrode layer 160 is formed to electrically surround the oxide semiconductor layer 122, which is to be a channel, in the channel width direction; accordingly, a gate electric field is applied to the oxide semiconductor layer 122 in the side surface direction in addition to the perpendicular direction. That is, a gate electric field is applied to the entire oxide semiconductor layer 122, so that the influence of a drain electric field can be reduced and a short-channel effect can be significantly suppressed. Therefore, the transistor can have favorable characteristics even when miniaturized.
Alternatively, when the transistor of one embodiment of the present invention includes a wide band gap material as the oxide semiconductor layer 122, which is to be the channel, the transistor can have high source-drain breakdown voltage and stable electrical characteristics in various temperature environments.
Although an example where a channel or the like is formed in an oxide semiconductor layer or the like is described in this embodiment, one embodiment of the present invention is not limited thereto. For example, depending on circumstances or conditions, a channel, the vicinity of the channel, a source region, a drain region, or the like may be formed using a material containing silicon (including strained silicon), germanium, silicon germanium, silicon carbide, gallium arsenide, aluminum gallium arsenide, indium phosphide, gallium nitride, an organic semiconductor, or the like.
<Components of Transistor>
Components of a transistor of this embodiment will be described below.
<<Substrate 100>>
A glass substrate, a ceramic substrate, a quartz substrate, a sapphire substrate, or the like can be used as the substrate 100. Alternatively, a single crystal semiconductor substrate or a polycrystalline semiconductor substrate of silicon or silicon carbide, a compound semiconductor substrate of silicon germanium, a silicon on insulator (SOI) substrate, or the like can be used. Still alternatively, any of these substrates provided with a semiconductor element may be used. The substrate 100 is not limited to a simple supporting substrate, and may be a substrate where a device such as a transistor is formed. In that case, at least one of the gate, the source, and the drain of the transistor may be electrically connected to the device.
Alternatively, a flexible substrate may be used as the substrate 100. As a method for providing the transistor over a flexible substrate, there is a method in which the transistor is formed over a non-flexible substrate and then the transistor is separated and transferred to the substrate 100 that is a flexible substrate. In that case, a separation layer is preferably provided between the non-flexible substrate and the transistor. As the substrate 100, a sheet, a film, or a foil containing a fiber may be used, for example. The substrate 100 may have elasticity. The substrate 100 may have a property of returning to its original shape when bending or pulling is stopped. Alternatively, the substrate 100 may have a property of not returning to its original shape. The thickness of the substrate 100 is, for example, greater than or equal to 5 μm and less than or equal to 700 μm, preferably greater than or equal to 10 μm and less than or equal to 500 μm, and further preferably greater than or equal to 15 μm and less than or equal to 300 μm. When the substrate 100 has a small thickness, the weight of the semiconductor device can be reduced. When the substrate 100 has a small thickness, even in the case of using glass or the like, the substrate 100 might have elasticity or a property of returning to its original shape when bending or pulling is stopped. Therefore, an impact applied to the semiconductor device over the substrate 100, which is caused by dropping or the like, can be reduced. That is, a durable semiconductor device can be provided.
For the substrate 100 which is a flexible substrate, metal, an alloy, resin, glass, or fiber thereof can be used, for example. The flexible substrate 100 preferably has a lower coefficient of linear expansion because deformation due to an environment is suppressed. The flexible substrate 100 is formed using, for example, a material whose coefficient of linear expansion is lower than or equal to 1×10−3/K, lower than or equal to 5×10−5/K, or lower than or equal to 1×10−5/K. Examples of the resin include polyester, polyolefin, polyamide (e.g., nylon or aramid), polyimide, polycarbonate, acrylic, and polytetrafluoroethylene (PTFE). In particular, aramid is preferably used for the flexible substrate 100 because of its low coefficient of linear expansion.
<<Insulating Layer 110>>
As the insulating layer 110, an insulating film containing one or more of silicon (Si), nitrogen (N), oxygen (O), fluorine (F), hydrogen (H), aluminum (Al), gallium (Ga), germanium (Ge), yttrium (Y), zirconium (Zr), lanthanum (La), neodymium (Nd), hafnium (Hf), and tantalum (Ta) can be used.
The insulating layer 110 can have a function of supplying oxygen to the oxide semiconductor layer 122 (or the metal oxide layer 121 or 123) as well as a function of preventing diffusion of impurities from the substrate 100. For this reason, the insulating layer 110 is preferably an insulating film containing oxygen, and further preferably an insulating film having an oxygen content higher than that in the stoichiometric composition. For example, the insulating layer 110 is a film in which the amount of released oxygen converted into oxygen atoms is 1.0×1019 atoms/cm3 or more in TDS analysis. Note that the temperature of the film surface in the TDS analysis is preferably higher than or equal to 100° C. and lower than or equal to 700° C., or higher than or equal to 100° C. and lower than or equal to 500° C. In the case where the substrate 100 is provided with another device as described above, the insulating layer 110 also has a function of an interlayer insulating film. In that case, the insulating layer 110 is preferably subjected to planarization treatment such as chemical mechanical polishing (CMP) treatment so as to have a flat surface.
When the insulating layer 110 contains fluorine, fluorine gasified from the insulating layer can stabilize an oxygen vacancy in the oxide semiconductor layer 122.
<<Metal Oxide Layer 121, Oxide Semiconductor Layer 122, Metal Oxide Layer 123>>
The metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 are oxide semiconductor films containing In or Zn and typically contain an In—Ga oxide, an In—Zn oxide, an In—Mg oxide, a Zn—Mg oxide, or an In-M-Zn oxide (M is Al, Ti, Ga, Y, Sn, Zr, La, Ce, Mg, Hf, or Nd).
An oxide that can be used for each of the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 preferably contains at least indium (In) or zinc (Zn). Alternatively, both In and Zn are preferably contained. In order to reduce variations in electrical characteristics of the transistors including the oxide semiconductor layer, the oxide preferably contains a stabilizer in addition to In and Zn.
As examples of a stabilizer, gallium (Ga), tin (Sn), hafnium (Hf), aluminum (Al), zirconium (Zr), and the like can be given. As another example of stabilizer, lanthanoid such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), or lutetium (Lu) can be given.
The indium and gallium contents in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 can be compared with each other by time-of-flight secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectrometry (XPS), or inductively coupled plasma mass spectrometry (ICP-MS).
Since the oxide semiconductor layer 122 has an energy gap of 2 eV or more, preferably 2.5 eV or more, and further preferably 3 eV or more, the off-state current of the transistor 10 can be low.
The thickness of the oxide semiconductor layer 122 is greater than or equal to 3 nm and less than or equal to 200 nm, preferably greater than or equal to 3 nm and less than or equal to 100 nm, and further preferably greater than or equal to 3 nm and less than or equal to 50 nm.
The thickness of the oxide semiconductor layer 122 may be larger than, equal to, or smaller than that of at least the metal oxide layer 121. If the thickness of the oxide semiconductor layer 122 is large, the on-state current of the transistor can be increased. The thickness of the metal oxide layer 121 may be determined as appropriate as long as formation of an interface state at the interface with the oxide semiconductor layer 122 can be suppressed. For example, the thickness of the oxide semiconductor layer 122 is larger than that of the metal oxide layer 121, preferably 2 or more times, further preferably 4 or more times, and still further preferably 6 or more times as large as that of the metal oxide layer 121. In the case where there is no need to increase the on-state current of the transistor, the thickness of the metal oxide layer 121 may be larger than or equal to that of the oxide semiconductor layer 122. If oxygen is added to the insulating layer 110 or the insulating layer 180, oxygen vacancies in the oxide semiconductor layer 122 can be reduced by heat treatment, which leads to stabilization of electrical characteristics of the semiconductor device.
In the case where the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 have different compositions from one another, the interfaces thereof can be observed with a scanning transmission electron microscope (STEM) in some cases.
The indium content in the oxide semiconductor layer 122 is preferably higher than those in the metal oxide layers 121 and 123. In an oxide semiconductor, the s orbital of heavy metal mainly contributes to carrier transfer, and when the proportion of In in the oxide semiconductor layer is increased, overlap of the s orbitals is likely to be increased. Therefore, an oxide having a composition in which the proportion of In is higher than that of M has higher mobility than an oxide having a composition in which the proportion of In is equal to or lower than that of M. Thus, with the use of an oxide having a high indium content for the oxide semiconductor layer 122, a transistor having high field-effect mobility can be obtained.
In the case where the oxide semiconductor layer 122 is an In-M-Zn oxide (M is Al, Ti, Ga, Y, Sn, Zr, La, Ce, Mg, Hf, or Nd) and a target having the atomic ratio of metal elements of In:M:Zn=x2:y2:z2 is used for forming the oxide semiconductor layer 122 by a sputtering method, x2/(x2+y2+z2) is preferably greater than or equal to ⅓. The oxide semiconductor layer 122 has the atomic ratio of metal elements similar to that of the target. Furthermore, x2/y2 is preferably greater than or equal to ⅓ and less than or equal to 6 and further preferably greater than or equal to 1 and less than or equal to 6, and z2/y2 is preferably greater than or equal to ⅓ and less than or equal to 6 and further preferably greater than or equal to 1 and less than or equal to 6. In this manner, a c-axis aligned crystalline oxide semiconductor (CAAC-OS) film is easily formed as the oxide semiconductor layer 122. Typical examples of the atomic ratio of metal elements of the target include In:M:Zn=1:1:1, 1:1:1.2, 2:1:1.5, 2:1:2.3, 2:1:3, 3:1:2, 4:2:3, and 4:2:4.1.
When the atomic ratio of Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, Hf, or Nd is higher than that of In in each of the metal oxide layer 121 and the metal oxide layer 123, any of the following effects might be obtained.
(1) The energy gap of each of the metal oxide layer 121 and the metal oxide layer 123 is widened.
(2) The electron affinity of each of the metal oxide layers 121 and 123 is reduced.
(3) Impurities from the outside are blocked.
(4) An insulating property of each of the metal oxide layers 121 and 123 is higher than that of the oxide semiconductor layer 122.
(5) Oxygen vacancies are less likely to be generated in the metal oxide layers 121 and 123 because Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, Hf, and Nd are metal elements that can be strongly bonded to oxygen.
The metal oxide layer 121 and the metal oxide layer 123 each contain one or more elements contained in the oxide semiconductor layer 122. Thus, interface scattering is unlikely to occur at the interfaces between the oxide semiconductor layer 122 and the metal oxide layer 121 and between the oxide semiconductor layer 122 and the metal oxide layer 123. The movement of carriers is not hindered at the interfaces and accordingly, the transistor 10 can have high field-effect mobility.
Each of the metal oxide layers 121 and 123 is typically an In—Ga oxide, an In—Zn oxide, an In—Mg oxide, a Ga—Zn oxide, a Zn—Mg oxide, or an In-M-Zn oxide (M is Al, Ti, Ga, Y, Sn, Zr, La, Ce, Mg, Hf, or Nd), and has the conduction band minimum that is closer to a vacuum level than the conduction band minimum of the oxide semiconductor layer 122 is. Typically, a difference between the conduction band minimum of the oxide semiconductor layer 122 and the conduction band minimum of each of the metal oxide layers 121 and 123 is greater than or equal to 0.05 eV, greater than or equal to 0.07 eV, greater than or equal to 0.1 eV, or greater than or equal to 0.2 eV and also less than or equal to 2 eV, less than or equal to 1 eV, less than or equal to 0.5 eV, or less than or equal to 0.4 eV. That is, the difference between the electron affinity of the oxide semiconductor layer 122 and the electron affinity of each of the metal oxide layers 121 and 123 is greater than or equal to 0.05 eV, greater than or equal to 0.07 eV, greater than or equal to 0.1 eV, or greater than or equal to 0.2 eV and also less than or equal to 2 eV, less than or equal to 1 eV, less than or equal to 0.5 eV, or less than or equal to 0.4 eV. Note that the electron affinity refers to a difference between the vacuum level and the conduction band minimum.
In the case where the metal oxide layer 121 and the metal oxide layer 123 are In-M-Zn oxides (M is Al, Ti, Ga, Y, Sn, Zr, La, Ce, Mg, Hf, or Nd), the metal oxide layer 121 and the metal oxide layer 123 have a higher atomic ratio of M (Al, Ti, Ga, Y, Zr, Sn, La, Ce, Mg, Hf, or Nd) than the oxide semiconductor layer 122 formed by a sputtering method, and the element represented by M is more strongly bonded to oxygen than indium is; thus, generation of oxygen vacancies in the metal oxide layer 121 and the metal oxide layer 123 can be suppressed. That is, the metal oxide layer 121 and the metal oxide layer 123 are oxide semiconductor films in which oxygen vacancies are less likely to be generated than in the oxide semiconductor layer 122. Each of the metal oxide layer 121 and the metal oxide layer 123 has the atomic ratio of metal elements similar to that of the target.
In the case where the metal oxide layer 121 is an In-M-Zn oxide (M is Al, Ti, Ga, Y, Sn, Zr, La, Ce, Mg, Hf, or Nd) and a target having the atomic ratio of metal elements of In:M:Zn=x1:y1:z1 is used for forming the metal oxide layer 121, x1/y1 is preferably less than z1/y1, and z1/y1 is preferably greater than or equal to 1/10 and less than or equal to 6 and further preferably greater than or equal to 0.2 and less than or equal to 3.
Since the metal oxide layers 121 and 123 can have higher insulating properties than the oxide semiconductor layer 122, they each have a function of a gate insulating layer.
Alternatively, the metal oxide layer 123 can be metal oxide, such as aluminum oxide, gallium oxide, hafnium oxide, silicon oxide, germanium oxide, or zirconia oxide; or the metal oxide may be provided over the metal oxide layer 123.
The thickness of the metal oxide layer 123 may be determined as appropriate as long as formation of an interface state at the interface with the oxide semiconductor layer 122 is inhibited. For example, the thickness of the metal oxide layer 123 may be set smaller than or equal to that of the metal oxide layer 121. If the thickness of the metal oxide layer 123 is large, it might become difficult for the electric field from the gate electrode layer 160 to reach the oxide semiconductor layer 122. For this reason, the thickness of the metal oxide layer 123 is preferably small. For example, the thickness of the metal oxide layer 123 is smaller than that of the oxide semiconductor layer 122. Note that the thickness of the metal oxide layer 123 is not limited to the above, and may be determined as appropriate in accordance with the driving voltage of the transistor in consideration of the withstand voltage of the gate insulating layer 150.
For example, the thickness of the metal oxide layer 123 is preferably greater than or equal to 1 nm and less than or equal to 20 nm or greater than or equal to 3 nm and less than or equal to 10 nm.
In the case where the metal oxide layer 121 and the metal oxide layer 123 are each an In-M-Zn oxide (M is Al, Ti, Ga, Y, Sn, Zr, La, Ce, Mg, Hf, or Nd) and a target having the atomic ratio of metal elements of In:M:Zn=x3:y3:z3 is used for forming the metal oxide layer 121 and the metal oxide layer 123, x3/y3 is preferably less than x2/y2, and z3/y3 is preferably greater than or equal to ⅓ and less than or equal to 6 and further preferably greater than or equal to 1 and less than or equal to 6. Note that when z3/y3 is greater than or equal to 1 and less than or equal to 6, CAAC-OS films are easily formed as the metal oxide layer 121 and the metal oxide layer 123. Typical examples of the atomic ratio of metal elements of the target include In:M:Zn=1:3:2, 1:3:4, 1:3:6, 1:3:8, 1:4:4, 1:4:5, 1:4:6, 1:4:7, 1:4:8, 1:5:5, 1:5:6, 1:5:7, 1:5:8, 1:6:8, 1:6:4, and 1:9:6. The atomic ratio is not limited to the above and may be appropriately set in accordance with needed semiconductor characteristics.
In each of the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, the proportion of each atom in the above-described atomic ratio varies within a range of ±40% as an error in some cases.
For example, when an oxide semiconductor film to be the oxide semiconductor layer 122 is formed using a target in which the atomic ratio of the metal elements is In:Ga:Zn=1:1:1, the atomic ratio of the metal elements of the oxide semiconductor film is approximately In:Ga:Zn=1:1:0.6, which means that the atomic ratio of zinc is not changed or reduced in some cases. Therefore, the atomic ratio described in this specification includes the atomic ratio in vicinity thereof.
<Hydrogen Concentration>
Hydrogen contained in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 reacts with oxygen bonded to a metal atom to be water, and in addition, an oxygen vacancy is formed in a lattice from which oxygen is released (or a portion from which oxygen is released). An electron serving as a carrier can be generated due to entry of hydrogen into the oxygen vacancy or due to bonding of part of hydrogen to oxygen bonded to a metal atom. Thus, a transistor including an oxide semiconductor layer which contains hydrogen is likely to be normally on.
Accordingly, it is preferable that hydrogen as well as the oxygen vacancies be reduced as much as possible in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 and at the interfaces between the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123. The concentrations of hydrogen in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 and at the interfaces between the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, which are obtained by secondary ion mass spectrometry (SIMS), are desirably higher than or equal to 1×1016 atoms/cm3 and lower than or equal to 2×1020 atoms/cm3, preferably higher than or equal to 1×1016 atoms/cm3 and lower than or equal to 5×1019 atoms/cm3, further preferably higher than or equal to 1×1016 atoms/cm3 and lower than or equal to 1×1019 atoms/cm3, and still further preferably higher than or equal to 1×1016 atoms/cm3 and lower than or equal to 5×1018 atoms/cm3. As a result, the transistor 10 can have positive threshold voltage (normally-off characteristics).
<Concentrations of Carbon and Silicon>
When silicon and carbon, which are elements belonging to Group 14, are contained in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 and at the interfaces between the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, oxygen vacancies are increased and an n-type region is formed in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123. It is therefore preferable to reduce the concentrations of silicon and carbon in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 and at the interfaces between the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123. The concentrations of silicon and carbon in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 and at the interfaces between the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, which are obtained by SIMS, are desirably higher than or equal to 1×1016 atoms/cm3 and lower than or equal to 1×1019 atoms/cm3, preferably higher than or equal to 1×1016 atoms/cm3 and lower than or equal to 5×1018 atoms/cm3, and further preferably higher than or equal to 1×1016 atoms/cm3 and lower than or equal to 2×1018 atoms/cm3. As a result, the transistor 10 can have positive threshold voltage.
<Concentration of Alkali Metal and Alkaline Earth Metal>
Alkali metal and alkaline earth metal can generate carriers when bonded to an oxide semiconductor, which can increase the off-state current of the transistor. It is thus preferable to reduce the concentrations of alkali metal and alkaline earth metal in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 and at the interfaces between the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123. For example, the concentrations of alkali metal and alkaline earth metal in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 and at the interfaces between the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, which are obtained by SIMS, are desirably lower than or equal to 1×1018 atoms/cm3, preferably lower than or equal to 2×1016 atoms/cm3. As a result, the transistor 10 can have positive threshold voltage.
<Concentration of Nitrogen>
When nitrogen is contained in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 and at the interfaces between the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, an electron serving as a carrier is generated and accordingly carrier density is increased, so that n-type regions are formed. Thus, a transistor including an oxide semiconductor layer which contains nitrogen is likely to be normally on. Thus, it is preferable that nitrogen be reduced as much as possible in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 and at the interfaces between the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123. For example, the concentrations of nitrogen in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 and at the interfaces between the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, which are obtained by SIMS, are preferably higher than or equal to 1×1015 atoms/cm3 and lower than or equal to 5×1019 atoms/cm3, further preferably higher than or equal to 1×1015 atoms/cm3 and lower than or equal to 5×1018 atoms/cm3, still further preferably higher than or equal to 1×1015 atoms/cm3 and lower than or equal to 1×1018 atoms/cm3, and yet still further preferably higher than or equal to 1×1015 atoms/cm3 and lower than or equal to 5×1017 atoms/cm3. As a result, the transistor 10 can have positive threshold voltage.
However, in the case where excess zinc exists in the oxide semiconductor layer 122, the concentrations of nitrogen are not limited to the above range. Excess zinc might cause oxygen vacancies in the oxide semiconductor layer 122, and when the oxide semiconductor layer 122 containing excess zinc also contains nitrogen at 0.001 atomic % to 3 atomic %, the oxygen vacancies caused by the excess zinc can be inactivated in some cases. Therefore, the nitrogen can reduce variations in transistor characteristics and can improve the reliability.
<Carrier Density>
The carrier densities of the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 can be lowered by reduction in impurities in the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123. The carrier densities of the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 are 1×1015/cm3 or less, preferably 1×1013/cm3 or less, further preferably less than 8×1011/cm3, still further preferably less than 1×1011/cm3, and most preferably less than 1×1010/cm3 and 1×10−9/cm3 or more.
When an oxide semiconductor film having a low impurity concentration and a low density of defect states is used as each of the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, the transistor can have more excellent electrical characteristics. Here, the state in which the impurity concentration is low and the density of defect states is low (the amount of oxygen vacancies is small) is described as “highly purified intrinsic” or “substantially highly purified intrinsic.” A highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor layer has few carrier generation sources, and thus has a low carrier density in some cases. Thus, a transistor including the oxide semiconductor layer in which a channel region is formed is likely to have positive threshold voltage. A highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor layer has a low density of defect states and accordingly has a low density of trap states in some cases. Furthermore, a transistor using a highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor layer has extremely low off-state current; the off-state current can be lower than or equal to the measurement limit of a semiconductor parameter analyzer, i.e., lower than or equal to 1×10−13 A, at a voltage between a source electrode and a drain electrode (drain voltage) of from 1 V to 10 V. Thus, the transistor whose channel region is formed in the oxide semiconductor layer has a small variation in electrical characteristics and high reliability in some cases.
A transistor in which a highly purified oxide semiconductor layer is used for a channel formation region exhibits extremely low off-state current. For example, in the case where the voltage between the source and the drain is set to approximately 0.1 V, 5 V, or 10 V, the off-state current standardized on the channel width of the transistor can be as low as several yoctoamperes per micrometer to several zeptoamperes per micrometer.
The metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 may have a non-single crystal structure, for example. The non-single crystal structure includes a CAAC-OS which will be described later, a polycrystalline structure, a microcrystalline structure, or an amorphous structure, for example. Among the non-single crystal structures, the amorphous structure has the highest density of defect states, whereas the CAAC-OS has the lowest density of defect states.
The metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 may have a microcrystalline structure, for example. The metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 which have the microcrystalline structure each include a microcrystal with a size greater than or equal to 1 nm and less than 10 nm, for example. Alternatively, the oxide films and the oxide semiconductor film which have the microcrystalline structure each have a mixed phase structure where crystal parts (each of which is greater than or equal to 1 nm and less than 10 nm in size) are distributed in an amorphous phase, for example.
The metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 may have an amorphous structure, for example. The metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 which have the amorphous structure each have disordered atomic arrangement and no crystalline component, for example. Alternatively, the oxide films and the oxide semiconductor film which have the amorphous structure each have, for example, an absolutely amorphous structure and no crystal part.
Note that the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 may each be a mixed film including regions having two or more of the following structures: a CAAC-OS, a microcrystalline structure, and an amorphous structure. The mixed film, for example, has a single-layer structure including a region having an amorphous structure, a region having a microcrystalline structure, and a region of a CAAC-OS. Alternatively, the mixed film may have a stacked-layer structure including a region having an amorphous structure, a region having a microcrystalline structure, and a region of a CAAC-OS, for example.
Note that the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 may have a single-crystal structure, for example.
By providing an oxide film in which oxygen vacancies are less likely to be generated than in the oxide semiconductor layer 122, over and under and in contact with the oxide semiconductor layer 122, oxygen vacancies in the oxide semiconductor layer 122 can be reduced. Further, since the oxide semiconductor layer 122 is in contact with the metal oxide layers 121 and 123 containing one or more metal elements forming the oxide semiconductor layer 122, the density of interface states at the interface between the metal oxide layer 121 and the oxide semiconductor layer 122 and at the interface between the oxide semiconductor layer 122 and the metal oxide layer 123 is extremely low. For example, after oxygen is added to the metal oxide layer 121, the metal oxide layer 123, the gate insulating layer 150, the insulating layer 110, and the insulating layer 180, the oxygen is transferred through the metal oxide layers 121 and 123 to the oxide semiconductor layer 122 by heat treatment; however, the oxygen is hardly trapped by the interface states at this time, and the oxygen in the metal oxide layer 121 or 123 can be efficiently transferred to the oxide semiconductor layer 122. Accordingly, oxygen vacancies in the oxide semiconductor layer 122 can be reduced. Since oxygen is added to the metal oxide layer 121 or 123, oxygen vacancies in the metal oxide layers 121 and 123 can be reduced. In other words, the density of localized states of at least the oxide semiconductor layer 122 can be reduced.
In addition, when the oxide semiconductor layer 122 is in contact with an insulating film including a different constituent element (e.g., a gate insulating layer including a silicon oxide film), an interface state is sometimes formed and the interface state forms a channel. At this time, a second transistor having a different threshold voltage appears, so that an apparent threshold voltage of the transistor is varied. However, since the metal oxide layers 121 and 123 containing one or more kinds of metal elements forming the oxide semiconductor layer 122 are in contact with the oxide semiconductor layer 122, an interface state is not easily formed at the interface between the metal oxide layer 121 and the oxide semiconductor layer 122 and the interface between the metal oxide layer 123 and the oxide semiconductor layer 122.
The metal oxide layers 121 and 123 function as barrier films that prevent constituent elements of the insulating layer 110 and the gate insulating layer 150 from entering the oxide semiconductor layer 122 and forming an impurity state.
For example, in the case of using a silicon-containing insulating film as the insulating layer 110 or the gate insulating layer 150, silicon in the gate insulating layer 150 or carbon which might be contained in the insulating layer 110 or the gate insulating layer 150 enters the metal oxide layer 121 or 123 to a depth of several nanometers from the interface in some cases. An impurity, such as silicon or carbon, entering the oxide semiconductor layer 122 forms an impurity state. The impurity state serves as a donor to generate an electron; thus, the oxide semiconductor layer 122 might become n-type.
However, when each thickness of the metal oxide layers 121 and 123 is larger than several nanometers, the impurity such as silicon or carbon does not reach the oxide semiconductor layer 122, so that the influence of impurity states is reduced.
Thus, providing the metal oxide layers 121 and 123 makes it possible to reduce variations in electrical characteristics of the transistor, such as threshold voltage.
In the case where the gate insulating layer 150 and the oxide semiconductor layer 122 are in contact with each other and a channel is formed at the interface therebetween, interface scattering occurs at the interface and the field-effect mobility of the transistor is decreased. However, since the metal oxide layers 121 and 123 containing one or more kinds of metal elements forming the oxide semiconductor layer 122 are provided in contact with the oxide semiconductor layer 122, scattering of carriers does not easily occur at the interfaces between the oxide semiconductor layer 122 and the metal oxide layer 121 and between the oxide semiconductor layer 122 and the metal oxide layer 123, and thus the field-effect mobility of the transistor can be increased.
In this embodiment, the amount of oxygen vacancies in the oxide semiconductor layer 122, and further the amount of oxygen vacancies in the metal oxide layers 121 and 123 in contact with the oxide semiconductor layer 122 can be reduced; thus, the density of localized states of the oxide semiconductor layer 122 can be reduced. As a result, the transistor 10 in this embodiment has small variations in threshold voltage and high reliability. Furthermore, the transistor 10 of this embodiment has excellent electrical characteristics.
An insulating film containing silicon is often used as a gate insulating layer of a transistor. For the above-described reason, it is preferable that a region of the oxide semiconductor layer, which serves as a channel, not be in contact with the gate insulating layer as in the transistor of one embodiment of the present invention. In the case where a channel is formed at the interface between the gate insulating layer and the oxide semiconductor layer, scattering of carriers occurs at the interface, whereby the field-effect mobility of the transistor is reduced in some cases. Also from the view of the above, it is preferable that the region of the oxide semiconductor layer, which serves as a channel, be separated from the gate insulating layer.
Accordingly, with the use of a stacked-layer structure including the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, a channel can be formed in the oxide semiconductor layer 122; thus, the transistor can have a high field-effect mobility and stable electrical characteristics.
Note that a three-layer structure is not necessarily used and a single layer, two layers, four layers, or five or more layers may be used. In the case of a single layer, a layer corresponding to the oxide semiconductor layer 122, which is described in this embodiment, can be used.
<Band Diagram>
Described here with reference to
As illustrated in
Oxide semiconductor films, which contain the same main components and are stacked, are not simply stacked but formed to have continuous junction (here, particularly a U-shaped (U shape) well structure where the conduction band minimum is continuously changed between the layers). In other words, a stacked-layer structure is formed such that there exist no impurities which form a defect state such as a trap center or a recombination center at each interface. If impurities are mixed between the stacked layers in the multilayer film, the continuity of the energy band is lost and carriers disappear by a trap or recombination at the interface.
Although Ec of the metal oxide layer 121 and that of the metal oxide layer 123 are equal to each other in
As illustrated in
Note that trap states due to impurities or defects can be formed in the vicinity of the interface between an insulating film such as a silicon oxide film and the metal oxide layers 121 and 123. The oxide semiconductor layer 122 can be distanced away from the trap states owing to existence of the metal oxide layer 123. However, when the energy difference between Ec of the metal oxide layer 121 or 123 and Ec of the oxide semiconductor layer 122 is small, an electron in the oxide semiconductor layer 122 might reach the trap state by passing over the energy difference. When electrons to be negative charge are captured by the trap states, a negative fixed charge is generated at the interface with the insulating film, whereby the threshold voltage of the transistor is shifted in the positive direction. In addition, a trap is not fixed and characteristics can be changed in a long-time preservation test of a transistor.
Thus, to reduce a change in the threshold voltage of the transistor, an energy difference between the Ec of the oxide semiconductor layer 122 and the Ec of each of the metal oxide layers 121 and 123 is necessary. The energy difference is preferably greater than or equal to 0.1 eV, and further preferably greater than or equal to 0.2 eV.
The metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123 preferably include a crystal part. In particular, when a crystal in which c-axes are aligned is used, the transistor can have stable electrical characteristics.
In the band diagram illustrated in
As the oxide semiconductor layer 122, an oxide having an electron affinity higher than those of the metal oxide layers 121 and 123 is used. The oxide which can be used for the oxide semiconductor layer 122 has, for example, an electron affinity higher than that of each of the metal oxide layers 121 and 123 by 0.07 eV or higher and 1.3 eV or lower, preferably 0.1 eV or higher and 0.7 eV or lower, and further preferably 0.2 eV or higher and 0.4 eV or lower.
Since the transistor described in this embodiment includes the metal oxide layer 121 and the metal oxide layer 123 that each include one or more kinds of metal elements included in the oxide semiconductor layer 122, an interface state is less likely to be formed at the interface between the metal oxide layer 121 and the oxide semiconductor layer 122 and the interface between the metal oxide layer 123 and the oxide semiconductor layer 122. Thus, providing the metal oxide layer 121 and the metal oxide layer 123 makes it possible to reduce variations or changes in electrical characteristics of the transistor, such as threshold voltage.
<<Gate Insulating Layer 150>>
The gate insulating layer 150 can contain oxygen (O), nitrogen (N), fluorine (F), aluminum (Al), magnesium (Mg), silicon (Si), gallium (Ga), germanium (Ge), yttrium (Y), zirconium (Zr), lanthanum (La), neodymium (Nd), hafnium (Hf), tantalum (Ta), titanium (Ti), or the like. For example, the gate insulating layer 150 can contain one or more of aluminum oxide (AlOx), magnesium oxide (MgOx), silicon oxide (SiOx), silicon oxynitride (SiOxNy), silicon nitride oxide (SiNxOy), silicon nitride (SiNx), gallium oxide (GaOx), germanium oxide (GeOx), yttrium oxide (YOx), zirconium oxide (ZrOx), lanthanum oxide (LaOx), neodymium oxide (NdOx), hafnium oxide (HfOx), and tantalum oxide (TaOx). The gate insulating layer 150 may be a stack of any of the above materials. The gate insulating layer 150 may contain lanthanum (La), nitrogen, zirconium (Zr), or the like as an impurity.
An example of a stacked-layer structure of the gate insulating layer 150 will be described. The gate insulating layer 150 contains, for example, oxygen, nitrogen, silicon, or hafnium. Specifically, the gate insulating layer 150 preferably contains hafnium oxide and silicon oxide or silicon oxynitride.
Hafnium oxide has higher dielectric constant than silicon oxide and silicon oxynitride. Therefore, the insulating layer 150 using hafnium oxide can have larger thickness than the insulating layer 150 using silicon oxide, so that leakage current due to tunnel current can be reduced. That is, it is possible to provide a transistor with low off-state current. Moreover, hafnium oxide with a crystalline structure has higher dielectric constant than hafnium oxide with an amorphous structure. Therefore, it is preferable to use hafnium oxide with a crystalline structure in order to provide a transistor with low off-state current. Examples of the crystalline structure include a monoclinic crystal structure and a cubic crystal structure. Note that one embodiment of the present invention is not limited to the above examples.
A surface over which the hafnium oxide with a crystalline structure is formed might have interface states due to defects. The interface state serves as a trap center in some cases. Therefore, when hafnium oxide is provided near a channel region of a transistor, the electrical characteristics of the transistor might deteriorate because of the interface state. In order to reduce the adverse effect of the interface state, in some cases, it is preferable to separate the channel region of the transistor and the hafnium oxide from each other by providing another film therebetween. The film has a buffer function. The film having a buffer function may be included in the gate insulating layer 150 or included in an oxide semiconductor film. That is, the film having a buffer function can be formed using silicon oxide, silicon oxynitride, an oxide semiconductor layer, or the like. Note that the film having a buffer function is formed using, for example, a semiconductor or an insulator having a larger energy gap than a semiconductor to be the channel region. Alternatively, the film having a buffer function is formed using, for example, a semiconductor or an insulator having lower electron affinity than a semiconductor to be the channel region. Further alternatively, the film having a buffer function is formed using, for example, a semiconductor or an insulator having higher ionization energy than a semiconductor to be the channel region.
In some cases, the threshold voltage of a transistor can be controlled by trapping an electric charge in an interface state (trap center) at the surface over which the hafnium oxide with a crystalline structure is formed. In order to make the electric charge exist stably, for example, an insulator having a larger energy gap than hafnium oxide may be provided between the channel region and the hafnium oxide. Alternatively, a semiconductor or an insulator having lower electron affinity than hafnium oxide may be provided. The film having a buffer function may be formed using a semiconductor or an insulator having higher ionization energy than hafnium oxide. With the use of such an insulator, an electric charge trapped in the interface state is less likely to be released; accordingly, the electric charge can be held for a long period of time.
Examples of such an insulator include silicon oxide and silicon oxynitride. In order to make the interface state in the gate insulating layer 150 trap an electric charge, an electron is transferred from an oxide semiconductor film toward the gate electrode layer 160. As a specific example, the potential of the gate electrode layer 160 is kept higher than the potential of the source electrode layer 130 or the drain electrode layer 140 at high temperatures (e.g., a temperature higher than or equal to 125° C. and lower than or equal to 450° C., typically higher than or equal to 150° C. and lower than or equal to 300° C.) for one second or longer, typically for one minute or longer.
The threshold voltage of a transistor in which a predetermined amount of electrons are trapped in interface states in the gate insulating layer 150 or the like shifts in the positive direction. The amount of electrons to be trapped (the amount of change in threshold voltage) can be controlled by adjusting a voltage of the gate electrode layer 160 or time in which the voltage is applied. Note that a location in which an electric charge is trapped is not necessarily limited to the inside of the gate insulating layer 150 as long as an electric charge can be trapped therein. A stacked film having a similar structure may be used as a different insulating layer.
In the case where a conductive layer is provided below the transistor 10, for example, the insulating layer 110 can have a structure and a function similar to those of the gate insulating layer 150.
<<Gate Electrode Layer 160>>
The gate electrode layer 160 can contain aluminum (Al), titanium (Ti), chromium (Cr), cobalt (Co), nickel (Ni), copper (Cu), yttrium (Y), zirconium (Zr), molybdenum (Mo), ruthenium (Ru), silver (Ag), tantalum (Ta), tungsten (W), or silicon (Si), for example. The gate electrode layer 160 may have a stacked-layer structure. When a stacked-layer structure is employed, the above materials may be combined with a material containing nitrogen, such as a nitride of any of the above materials. For example, the above materials may be used alone or in combination or may be combined with any of the above materials containing nitrogen, such as a nitride of any of the above materials.
<<Insulating Layer 180>>
The insulating layer 180 can be formed using an insulating film containing one or more of magnesium oxide (MgOx), silicon oxide (SiOx), silicon oxynitride (SiOxNy), silicon nitride oxide (SiNxOy), silicon nitride (SiNx), gallium oxide (GaOx), germanium oxide (GeOx), yttrium oxide (YOx), zirconium oxide (ZrOx), lanthanum oxide (LaOx), neodymium oxide (NdOx), hafnium oxide (HfOx), tantalum oxide (TaOx), and aluminum oxide (AlOx). The insulating layer 180 may be a stack of any of the above materials. The insulating layer preferably contains oxygen more than that in the stoichiometric composition. Oxygen released from the insulating layer 180 can be diffused into the channel formation region in the oxide semiconductor layer 122 through the gate insulating layer 150, so that oxygen vacancies formed in the channel formation region can be filled with the oxygen. In this manner, stable electrical characteristics of the transistor can be achieved.
<<Conductive Layer 190>>
The conductive layer 190 can be formed using a material similar to that of the gate electrode layer 160.
<<Conductive Layer 195>>
The conductive layer 195 can be formed using a material similar to that of the gate electrode layer 160.
<Manufacturing Method of Transistor>
Next, a manufacturing method of a semiconductor device of this embodiment will be described with reference to
In this embodiment, the layers included in the transistor (i.e., the insulating layer, the oxide semiconductor layer, the conductive layer, and the like) can be formed by any of a sputtering method, a chemical vapor deposition (CVD) method, a vacuum evaporation method, and a pulsed laser deposition (PLD) method. Alternatively, a coating method or a printing method can be used. Although the sputtering method and a plasma CVD method are typical examples of the film formation method, a thermal CVD method may be used. As the thermal CVD method, a metal organic chemical vapor deposition (MOCVD) method or an atomic layer deposition (ALD) method may be used, for example. As the sputtering method, a combination of a long throw sputtering method and a collimated sputtering method is employed, whereby the embeddability can be improved.
<Thermal CVD Method>
A thermal CVD method has an advantage that no defect due to plasma damage is generated since it does not utilize plasma for forming a film.
Deposition by a thermal CVD method may be performed in such a manner that a source gas and an oxidizer are supplied to a chamber at a time, the pressure in the chamber is set to an atmospheric pressure or a reduced pressure, and reaction is caused in the vicinity of the substrate or over the substrate.
The variety of films such as the metal film, the semiconductor film, and the inorganic insulating film which have been described above can be formed by a thermal CVD method, such as a MOCVD method or an ALD method. For example, in the case where an In—Ga—Zn—O film is formed, trimethylindium, trimethylgallium, and dimethylzinc can be used. Note that the chemical formula of trimethylindium is In(CH3)3. The chemical formula of trimethylgallium is Ga(CH3)3. The chemical formula of dimethylzinc is Zn(CH3)2. Without limitation to the above combination, triethylgallium (chemical formula: Ga(C2H5)3) can be used instead of trimethylgallium, and diethylzinc (chemical formula: Zn(C2H5)2) can be used instead of dimethylzinc.
<ALD Method>
In a conventional deposition apparatus utilizing a CVD method, one or more kinds of source gases (precursors) for reaction are supplied to a chamber at the same time at the time of deposition. In a deposition apparatus utilizing an ALD method, precursors for reaction are sequentially introduced into a chamber, and then the sequence of the gas introduction is repeated. For example, two or more kinds of precursors are sequentially supplied to the chamber by switching respective switching valves (also referred to as high-speed valves). For example, a first precursor is introduced, an inert gas (e.g., argon or nitrogen) or the like is introduced after the introduction of the first precursor so that the plural kinds of precursors are not mixed, and then a second precursor is introduced. Alternatively, the first precursor may be exhausted by vacuum evacuation instead of the introduction of the inert gas, and then the second precursor may be introduced.
An ALD method is a deposition method based on a surface chemical reaction, by which precursors are adsorbed onto a surface and adsorbing is stopped by a self-terminating mechanism, whereby a layer is formed. For example, precursors such as trimethylaluminum react with hydroxyl groups (OH groups) that exist at the surface. At this time, only a surface reaction due to heat occurs; therefore, the precursors come into contact with the surface and metal atoms or the like in the precursors can be adsorbed onto the surface through thermal energy. The precursors have characteristics of, for example, having a high vapor pressure, being thermally stable before being deposited and not dissolving, and being chemically adsorbed onto a substrate at a high speed. Since the precursors are introduced in a state of a gas, when the precursors, which are alternately introduced, have enough time to be diffused, a film can be formed with good coverage even onto a region having unevenness with a high aspect ratio.
In an ALD method, the sequence of the gas introduction is repeated a plurality of times until a desired thickness is obtained, whereby a thin film with excellent step coverage can be formed. The thickness of the thin film can be adjusted by the number of repetition times of the sequence of the gas introduction; therefore, an ALD method makes it possible to accurately adjust a thickness. The deposition rate can be increased and the impurity concentration in the film can be reduced by improving the evacuation capability.
ALD methods include an ALD method using heating (thermal ALD method) and an ALD method using plasma (plasma ALD method). In the thermal ALD method, precursors react using thermal energy, and in the plasma ALD method, precursors react in a state of a radical.
By an ALD method, an extremely thin film can be formed with high accuracy. In addition, the coverage of an uneven surface with the film and the film density of the film are high.
<Plasma ALD Method>
Alternatively, when a plasma ALD method is employed, the film can be formed at a lower temperature than when a thermal ALD method is employed. With a plasma ALD method, for example, the film can be formed without decreasing the deposition rate even at 100° C. or lower. Moreover, in a plasma ALD method, plasma can render nitrogen a radical; thus, a nitride film as well as an oxide film can be formed.
In addition, oxidizability of an oxidizer can be enhanced by a plasma ALD method. Thus, precursors remaining in a film formed by a plasma ALD method or organic components released from precursors can be reduced. In addition, carbon, chlorine, hydrogen, and the like in the film can be reduced. Therefore, a film with a low impurity concentration can be formed.
In the case of using a plasma ALD method, when radical species are generated, plasma can be generated from a place apart from the substrate like inductively coupled plasma (ICP) or the like, so that plasma damage to the substrate or a film on which the protective film is formed can be inhibited.
As described above, with a plasma ALD method, the film can be deposited in the state where the process temperature can be lowered and the coverage of the surface can be increased as compared with other deposition methods. Thus, entry of water and hydrogen from the outside can be inhibited, leading to an improvement of the reliability of characteristics of the transistor.
<ALD Apparatus>
A substrate holder 1716 with a heater is provided in the chamber, and a substrate 1700 over which a film is formed is provided over the substrate holder.
In the source material supply portions 1711a and 1711b, a source gas is formed from a solid source material or a liquid source material by using a vaporizer, a heating unit, or the like. Alternatively, the source material supply portions 1711a and 1711b may supply a source gas in a gas state.
Although two source material supply portions 1711a and 1711b are provided in this example, the number of source material supply portions is not limited thereto, and three or more source material supply portions may be provided. The high-speed valves 1712a and 1712b can be accurately controlled by time, and supply one of a source gas and an inert gas. The high-speed valves 1712a and 1712b are flow rate controllers for a source gas, and can also be referred to as flow rate controllers for an inert gas.
In the deposition apparatus illustrated in
In the deposition apparatus illustrated in
For example, in the case where a hafnium oxide layer is formed with a deposition apparatus using an ALD method, two kinds of gases, i.e., ozone (O3) as an oxidizer and a source gas which is obtained by vaporizing liquid containing a solvent and a hafnium precursor compound (hafnium alkoxide or hafnium amide such as tetrakis(dimethylamide)hafnium (TDMAH)), are used. In this case, the first source gas supplied from the source material supply portion 1711a is TDMAH, and the second source gas supplied from the source material supply portion 1711b is ozone. Note that the chemical formula of tetrakis(dimethylamide)hafnium is Hf[N(CH3)2]4. Examples of another material include tetrakis(ethylmethylamide)hafnium. Note that nitrogen has a function of eliminating charge trap states. Therefore, when the source gas contains nitrogen, a hafnium oxide film having low density of charge trap states can be formed.
For example, in the case where an aluminum oxide layer is formed with a deposition apparatus utilizing an ALD method, two kinds of gases, i.e., H2O as an oxidizer and a source gas which is obtained by vaporizing liquid containing a solvent and an aluminum precursor compound (e.g., trimethylaluminum (TMA)), are used. In this case, the first source gas supplied from the source material supply portion 1711a is TMA, and the second source gas supplied from the source material supply portion 1711b is H2O. Note that the chemical formula of trimethylaluminum is Al(CH3)3. Examples of another material liquid include tris(dimethylamide)aluminum, triisobutylaluminum, and aluminum tris(2,2,6,6-tetramethyl-3,5-heptanedionate).
For example, in the case where a silicon oxide film is formed with a deposition apparatus using an ALD method, hexachlorodisilane is adsorbed on a surface where a film is to be formed, chlorine contained in the adsorbate is removed, and radicals of an oxidizing gas (e.g., O2 or dinitrogen monoxide) are supplied to react with the adsorbate.
For example, in the case where a tungsten film is formed using a deposition apparatus employing an ALD method, a WF6 gas and a B2H6 gas are sequentially introduced plural times to form an initial tungsten film, and then a WF6 gas and an H2 gas are sequentially introduced plural times to form a tungsten film. Note that an SiH4 gas may be used instead of a B2H6 gas.
For example, in the case where an oxide semiconductor film, e.g., an In—Ga—Zn—O film is formed using a deposition apparatus employing an ALD method, an In(CH3)3 gas and an O3 gas are sequentially introduced plural times to form an In—O layer, a Ga(CH3)3 gas and an O3 gas are sequentially introduced plural times to form a GaO layer, and then a Zn(CH3)2 gas and an O3 gas are sequentially introduced plural times to form a ZnO layer. Note that the order of these layers is not limited to this example. A mixed compound layer such as an In—Ga—O layer, an In—Zn—O layer, or a Ga—Zn—O layer may be formed by mixing these gases. Note that although an H2O gas which is obtained by bubbling with an inert gas such as Ar may be used instead of an O3 gas, it is preferable to use an O3 gas, which does not contain H. Instead of an In(CH3)3 gas, an In(C2H5)3 gas may be used. Instead of a Ga(CH3)3 gas, a Ga(C2H5)3 gas may be used. A Zn(CH3)2 gas may be used.
<<Multi-Chamber Manufacturing Apparatus>>
In the manufacturing apparatus illustrated in
The manufacturing apparatus illustrated in
The chambers 1704 and 1705 may be deposition apparatuses utilizing an ALD method like the chamber 1701, deposition apparatuses utilizing a plasma CVD method, deposition apparatuses utilizing a sputtering method, or deposition apparatuses utilizing a metal organic chemical vapor deposition (MOCVD) method.
For example, an example in which a stack of films is formed under a condition that the chamber 1704 is a deposition apparatus utilizing a plasma CVD method and the chamber 1705 is a deposition apparatus utilizing an MOCVD method will be described below.
Although
<Formation of Insulating Layer 110>
First, the insulating layer 110 is formed over the substrate 100. The insulating layer 110 can be formed by a plasma CVD method, a thermal CVD method (an MOCVD method, an ALD method), a sputtering method, or the like with use of a metal oxide film of aluminum oxide, magnesium oxide, silicon oxide, silicon oxynitride, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, tantalum oxide, or the like; a nitride insulating film of silicon nitride, silicon nitride oxide, aluminum nitride, aluminum nitride oxide, or the like; or a mixed material of any of these. Alternatively, these materials may be stacked, in which case at least an upper layer of the stacked layer which is in contact with a first metal oxide film to be the metal oxide layer 121 later is preferably formed using a material containing excess oxygen that can serve as a supply source of oxygen to the oxide semiconductor layer 122.
The use of a material that contains no hydrogen or a material that contains hydrogen at 1% or lower for the insulating layer 110 can prevent oxygen vacancies from being generated in the oxide semiconductor layer, leading to stable operation of the transistor.
As the insulating layer 110, for example, a 100-nm-thick silicon oxynitride film can be formed by a plasma CVD method.
Next, first heat treatment may be performed to release water, hydrogen, or the like contained in the insulating layer 110. As a result, the concentration of water, hydrogen, or the like contained in the insulating layer 110 can be reduced. The heat treatment can reduce the amount of water, hydrogen, or the like diffused into the first metal oxide film that is to be formed later.
<Formation of First Metal Oxide Film and Oxide Semiconductor Film to be Oxide Semiconductor Layer 122>
Then, the first metal oxide film to be the metal oxide layer 121 later and the oxide semiconductor film to be the oxide semiconductor layer 122 later are formed over the insulating layer 110. The first metal oxide film and the oxide semiconductor film to be the oxide semiconductor layer 122 can be formed by a sputtering method, an MOCVD method, a PLD method, or the like, and especially, a sputtering method is preferable. As a sputtering method, an RF sputtering method, a DC sputtering method, an AC sputtering method, or the like can be used. In addition, a facing-target-type sputtering method (also referred to as a counter-electrode-type sputtering method, a gas phase sputtering method, and a vapor deposition sputtering (VDSP) method) is used, whereby plasma damage at the deposition can be reduced.
When the oxide semiconductor film to be the oxide semiconductor layer 122 is formed by a sputtering method, for example, it is preferable that each chamber of the sputtering apparatus be able to be evacuated to a high vacuum (approximately 5×10−7 Pa to 1×10−4 Pa) by an adsorption vacuum pump such as a cryopump, and that the chamber be able to heat a substrate over which a film is to be deposited to 100° C. or higher, preferably 400° C. or higher so that water and the like acting as impurities in the oxide semiconductor film can be removed as much as possible. Alternatively, a combination of a turbo molecular pump and a cold trap is preferably used to prevent back-flow of a gas containing a carbon component, moisture, or the like from an exhaust system into the chamber. Alternatively, a combination of a turbo molecular pump and a cryopump may be used as an exhaust system.
Not only high vacuum evacuation in a chamber but also high purity of a sputtering gas is desirable to obtain a highly purified intrinsic oxide semiconductor film. As an oxygen gas or an argon gas used as a sputtering gas, a highly purified gas having a dew point of −40° C. or lower, preferably −80° C. or lower, and further preferably −100° C. or lower is used, whereby moisture or the like can be prevented from entering an oxide semiconductor film as much as possible.
As a sputtering gas, a rare gas (typically argon), oxygen, or a mixed gas of a rare gas and oxygen is used as appropriate. In the case of using the mixed gas of a rare gas and oxygen, the proportion of oxygen to a rare gas is preferably increased.
Note that for example, in the case where the oxide semiconductor film to be the oxide semiconductor layer 122 is formed by a sputtering method at a substrate temperature higher than or equal to 150° C. and lower than or equal to 750° C., preferably higher than or equal to 150° C. and lower than or equal to 450° C., and further preferably higher than or equal to 200° C. and lower than or equal to 420° C., the oxide semiconductor film can be a CAAC-OS film.
The material for the first metal oxide film is selected so that the first metal oxide film can have a lower electron affinity than the oxide semiconductor film to be the oxide semiconductor layer 122.
When a sputtering method is used to form the first metal oxide film and the oxide semiconductor film to be the oxide semiconductor layer 122, the first metal oxide film and the oxide semiconductor film to be the oxide semiconductor layer 122 can be successively formed without being exposed to the air with use of a multi-chamber sputtering apparatus. In that case, entry of unnecessary impurities and the like into the interface between the first metal oxide film and the oxide semiconductor film to be the oxide semiconductor layer 122 can be prevented and the density of interface states can be reduced accordingly. Thus, the electrical characteristics of a transistor can be stabilized, particularly in a reliability test.
If the insulating layer 110 is damaged, the oxide semiconductor layer 122, which is a main conduction path, can keep a distance from the damaged part thanks to the existence of the metal oxide layer 121. Thus, the electrical characteristics of a transistor can be stabilized, particularly in a reliability test.
For example, as the first metal oxide film, a 20-nm-thick insulator film which is formed by a sputtering method using a target having an atomic ratio of In:Ga:Zn=1:3:4 can be used. In addition, as the oxide semiconductor film, a 15-nm-thick oxide semiconductor film which is formed by a sputtering method using a target having an atomic ratio of In:Ga:Zn=1:1:1 can be used.
The amount of oxygen vacancies in the first metal oxide film and the oxide semiconductor film to be the oxide semiconductor layer 122 can be reduced by performing second heat treatment after the first metal oxide film and the oxide semiconductor film to be the oxide semiconductor layer 122 are formed.
The temperature of the second heat treatment is higher than or equal to 250° C. and lower than the strain point of the substrate, preferably higher than or equal to 300° C. and lower than or equal to 650° C., and further preferably higher than or equal to 350° C. and lower than or equal to 550° C.
The second heat treatment is performed under an inert gas atmosphere containing nitrogen or a rare gas such as helium, neon, argon, xenon, or krypton. Further, after heat treatment performed in an inert gas atmosphere, heat treatment may be additionally performed in an oxygen atmosphere or a dry air atmosphere (air whose dew point is lower than or equal to −80° C., preferably lower than or equal to −100° C., and further preferably lower than or equal to −120° C.). The treatment may be performed under reduced pressure. Note that it is preferable that hydrogen, water, and the like not be contained in an inert gas and oxygen, like the dry air, and the dew point is preferably lower than or equal to −80° C., and further preferably lower than or equal to −100° C. The treatment time is 3 minutes to 24 hours.
In the heat treatment, instead of an electric furnace, any device for heating an object by heat conduction or heat radiation from a heating element, such as a resistance heating element, may be used. For example, an RTA (rapid thermal annealing) apparatus, such as a GRTA (gas rapid thermal annealing) apparatus or an LRTA (lamp rapid thermal annealing) apparatus, can be used. The LRTA apparatus is an apparatus for heating an object to be processed by radiation of light (an electromagnetic wave) emitted from a lamp, such as a halogen lamp, a metal halide lamp, a xenon arc lamp, a carbon arc lamp, a high pressure sodium lamp, or a high pressure mercury lamp. The GRTA apparatus is an apparatus for heat treatment using a high-temperature gas. As the high-temperature gas, an inert gas such as nitrogen or a rare gas such as argon is used.
Note that the second heat treatment may be performed after etching for forming the metal oxide layer 121 and the oxide semiconductor layer 122 described later.
For example, after heat treatment is performed at 450° C. in a nitrogen atmosphere for one hour, heat treatment is performed at 450° C. in an oxygen atmosphere for one hour.
Through the above-described steps, oxygen vacancies and impurities such as hydrogen and water in the first metal oxide film and the oxide semiconductor film to be the oxide semiconductor layer 122 can be reduced. The first metal oxide film and the oxide semiconductor film to be the oxide semiconductor layer 122 can have low density of localized states.
Note that high-density plasma irradiation using oxygen can produce an effect equivalent to that produced by heat treatment. Irradiation time is longer than or equal to 1 minute and shorter than or equal to 3 hours, preferably longer than or equal to 3 minutes and shorter than or equal to 2 hours, and further preferably longer than or equal to 5 minutes and shorter than or equal to 1 hour.
<Formation of First Conductive Film>
Next, a first conductive film used as a hard mask is formed over the oxide semiconductor layer 122. The first conductive film can be formed by a sputtering method, a chemical vapor deposition (CVD) method such as a metal organic chemical vapor deposition (MOCVD) method, a metal chemical vapor deposition method, an atomic layer deposition (ALD) method, or a plasma-enhanced chemical vapor deposition (PECVD) method, an evaporation method, a pulsed laser deposition (PLD) method, or the like.
The first conductive film is preferably, for example, a conductive film having a single-layer structure or a layered structure and containing a material selected from copper (Cu), tungsten (W), molybdenum (Mo), gold (Au), aluminum (Al), manganese (Mn), titanium (Ti), tantalum (Ta), nickel (Ni), chromium (Cr), lead (Pb), tin (Sn), iron (Fe), cobalt (Co), ruthenium (Ru), platinum (Pt), iridium (Ir), and strontium (Sr), an alloy of such a material, or a compound containing such a material as its main component.
As the first conductive film, for example, a tungsten film having a thickness of 20 nm to 100 nm can be formed by a sputtering method.
Although the first conductive film is formed as a hard mask in this embodiment, one embodiment of the present invention is not limited thereto; an insulating film may be formed instead.
<Formation of Metal Oxide Layer 121 and Oxide Semiconductor Layer 122>
Then, a resist mask is formed through a lithography process. The first conductive film is selectively etched using the resist mask, so that the conductive layer 130b is formed. After the resist over the hard mask is removed, the oxide semiconductor film to be the oxide semiconductor layer 122 and the first metal oxide film are selectively etched, whereby the island-shaped oxide semiconductor layer 122 and metal oxide layer 121 are formed (see
<Formation of Metal Oxide Film 123a>
Next, the metal oxide film 123a to be the metal oxide layer 123 is formed over the oxide semiconductor layer 122 and the insulating layer 110. The metal oxide film 123a can be formed in a manner similar to that of the oxide semiconductor film and the first metal oxide film. The materials can be selected such that the electron affinity of the metal oxide film 123a is smaller than that of the oxide semiconductor film.
Furthermore, if the metal oxide film 123a is formed by a long throw sputtering method, the embeddability of the metal oxide film 123a in the groove portion 174 can be improved.
For example, as the metal oxide film 123a, a 5-nm-thick oxide semiconductor film which is formed by a sputtering method using a target having an atomic ratio of In:Ga:Zn=1:3:2 can be used.
<Formation of First Insulating Film>
Next, a first insulating film to be an insulating layer 175 later is formed over the metal oxide film 123a. The first insulating film can be formed in a manner similar to that of the insulating layer 110.
The first insulating film can be formed by a plasma CVD method, a thermal CVD method (an MOCVD method, an ALD method), a sputtering method, or the like with use of a metal oxide film of aluminum oxide, magnesium oxide, silicon oxide, silicon oxynitride, silicon oxyfluoride, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, tantalum oxide, or the like; a nitride insulating film of silicon nitride, silicon nitride oxide, aluminum nitride, aluminum nitride oxide, or the like; or a mixed material of any of these. Alternatively, a stack of any of the above materials may be used.
<Planarization of First Insulating Film>
Then, planarization treatment is performed on the first insulating film, so that an insulating layer 175b is formed (see
<Formation of Groove Portion>
Next, a resist mask is formed over the planarized insulating layer 175b by a lithography process. Note that the lithography process may be performed after an organic film is applied to the insulating layer or after an organic film is applied to the resist mask. The organic film can contain propylene glycolmonomethyl ether, ethyl lactate, or the like. The use of the organic film leads to, in addition to an anti-reflection effect during light exposure, an improvement in adhesion between the resist mask and a film, an improvement in resolution, and the like. The organic film can also be used in another process.
Note that in the case where a transistor having an extremely short channel length is formed, etching is performed using a resist mask that is processed by a method suitable for micropatterning, such as electron beam exposure, liquid immersion exposure, or extreme ultraviolet (EUV) exposure. Note that in the case of forming the resist mask by electron beam exposure, a positive resist mask is used, so that an exposed region can be minimized and throughput can be improved. In the above manner, a transistor having a channel length of 100 nm or less, 30 nm or less, or 20 nm or less can be formed. Alternatively, minute processing may be performed by an exposure technology which uses X-rays or the like.
With the use of the resist mask, groove processing is performed on the insulating layer 175b by a dry etching method until the metal oxide film 123a is exposed. As a result of the processing, the insulating layer 175 and the groove portion 174 are formed.
Note that the groove portion 174 is preferably perpendicular to a substrate surface.
Note that the processing method of the groove portion 174 is not limited to the above method. For example, not only the resist mask but also a hard mask may be used, or a half-tone mask may be used in a lithography process to control the shape of the resist mask. Alternatively, the shape of the mask may be controlled by nanoimprint lithography or the like. The nanoimprint lithography can be used in another process.
<Formation of Second Insulating Film 150a>
Next, a second insulating film 150a to be the gate insulating layer 150 is formed over the metal oxide film 123a and the insulating layer 175. The second insulating film 150a can be formed using aluminum oxide (AlOx), magnesium oxide (MgOx), silicon oxide (SiOx), silicon oxynitride (SiOxNy), silicon nitride oxide (SiNxOy), silicon nitride (SiNx), gallium oxide (GaOx), germanium oxide (GeOx), yttrium oxide (YOx), zirconium oxide (ZrOx), lanthanum oxide (LaOx), neodymium oxide (NdOx), hafnium oxide (HfOx), tantalum oxide (TaOx), or the like. The second insulating film 150a may be a stack containing any of these materials. The second insulating film 150a can be formed by a sputtering method, a CVD method (e.g., a plasma CVD method, an MOCVD method, or an ALD method), an MBE method, or the like. The second insulating film 150a can be formed by a method similar to that of the insulating layer 110 as appropriate.
For example, as the second insulating film 150a, silicon oxynitride can be deposited to a thickness of 10 nm by a plasma CVD method.
<Formation of Conductive Film 160a>
Next, a conductive film 160a to be the gate electrode layer 160 is formed over the second insulating film 150a (see
For example, a stack of 10-nm-thick titanium nitride deposited by an ALD method and 150-nm-thick tungsten deposited by a metal CVD method can be used for the conductive film 160a.
<Planarization Treatment>
Then, planarization treatment is performed. The planarization treatment can be performed by a CMP method, a dry etching method, or the like. The planarization treatment may be terminated at the time when the second insulating film 150a is exposed, or may be terminated at the time when the insulating layer 175 is exposed. Accordingly, the gate electrode layer 160 and the gate insulating layer 150 can be formed (see
<Etch-Back Treatment of Insulating Layer 175>
Next, the insulating layer 175 is subjected to etch-back treatment by a dry etching method so that the metal oxide film 123a is exposed. Furthermore, the metal oxide film 123a is etched to remove a portion not overlapping with the gate electrode layer 160, so that the metal oxide layer 123 is formed (see
Note that a method for forming a structure illustrated in
A structure in which a metal oxide layer 123b, a gate insulating layer 150b, and the gate electrode layer 160 are provided in the groove portion 174 may be employed as illustrated in
<Ion Addition Treatment>
Next, an ion 167 is added to the oxide semiconductor layer 122 (see
In the ion addition treatment, the acceleration voltage is desirably adjusted in accordance with the ion species and the implantation depth, and can be higher than or equal to 1 kV and lower than or equal to 100 kV, or higher than or equal to 3 kV and lower than or equal to 60 kV, for example. It is desirable that the dose of the ion be greater than or equal to 1×1012 ions/cm2 and less than or equal to 1×1017 ions/cm2, and preferably greater than or equal to 1×1014 ions/cm2 and less than or equal to 5×1016 ions/cm2.
By the ion addition treatment, oxygen vacancies are formed in the oxide semiconductor layer 122, so that the low-resistance region 125 is provided (see
By performing heat treatment after the ion addition treatment, damage caused to a film during the ion addition treatment can be repaired.
Then, a third insulating film to be the insulating layer 180 later is formed. The third insulating film can be formed in a manner similar to that of the insulating layer 110. It is desirable to perform planarization after the formation of the third insulating film.
After that, the third insulating film is etched by a dry etching method to form an opening.
Subsequently, a third conductive film to be the conductive layer 190 is formed in the opening, and then planarization treatment is performed, whereby the conductive layer 190 is formed.
Next, a fourth conductive film to be the conductive layer 195 is formed over the conductive layer 190. To form the conductive layer 195, the fourth conductive film is processed by a photolithography method, a nanoimprinting method, or the like.
The transistor 10 can be manufactured by the above manufacturing method. With the above manufacturing method, an extremely miniaturized transistor whose channel length is less than or equal to 100 nm, less than or equal to 30 nm, or less than or equal to 20 nm can be manufactured stably.
Note that the transistor 10 may have a region where the gate insulating layer 150 is in contact with a side surface of the gate electrode layer (see
<Modification Example 1 of Transistor 10: Transistor 11>
A transistor 11 with a shape different from that of the transistor 10 illustrated in
The transistor 11 is different from the transistor 10 in that an insulating layer 170 and an insulating layer 172 are included.
<<Insulating Layer 170>>
The insulating layer 170 can contain oxygen, nitrogen, fluorine, aluminum (Al), magnesium (Mg), silicon (Si), gallium (Ga), germanium (Ge), yttrium (Y), zirconium (Zr), lanthanum (La), neodymium (Nd), hafnium (Hf), tantalum (Ta), titanium (Ti), or the like. The insulating layer 170 can contain one or more of aluminum oxide (AlOx), magnesium oxide (MgOx), silicon oxide (SiOx), silicon oxynitride (SiOxNy), silicon nitride oxide (SiNxOy), silicon nitride (SiNx), gallium oxide (GaOx), germanium oxide (GeOx), yttrium oxide (YOx), zirconium oxide (ZrOx), lanthanum oxide (LaOx), neodymium oxide (NdOx), hafnium oxide (HfOx), and tantalum oxide (TaOx).
An aluminum oxide (AlOx) film is preferably included in the insulating layer 170. The aluminum oxide film can prevent the passage of both oxygen and impurities such as hydrogen and moisture. Thus, during and after the manufacturing process of the transistor, the aluminum oxide film can suitably function as a protective film that has effects of preventing entry of impurities such as hydrogen and moisture, which cause variations in the electrical characteristics of the transistor, into the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, preventing release of oxygen, which is a main component, from the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, and preventing unnecessary release of oxygen from the insulating layer 110.
The insulating layer 170 is preferably a film having oxygen supply capability. In the formation of the insulating layer 170, a mixed layer is formed at an interface with a different oxide layer and oxygen is supplied to the mixed layer or the different oxide layer. The oxygen is diffused into the oxide semiconductor layer by heat treatment performed after that, and the oxygen can fill oxygen vacancies in the oxide semiconductor layer; therefore, the transistor characteristics (e.g., threshold voltage and reliability) can be improved.
Furthermore, the insulating layer 170 may be a single layer or a stacked layer. Alternatively, another insulating layer may be provided over or under the insulating layer. For example, an insulating film containing one or more of magnesium oxide, silicon oxide, silicon oxynitride, silicon nitride oxide, silicon nitride, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, and tantalum oxide can be used. The insulating layer preferably contains oxygen more than that in the stoichiometric composition. Oxygen released from the insulating layer can be diffused into the channel formation region in the oxide semiconductor layer 122 through the gate insulating layer 150 or the insulating layer 110, so that oxygen vacancies formed in the channel formation region can be filled with the oxygen. In this manner, stable electrical characteristics of the transistor can be achieved.
<<Insulating Layer 172>>
The insulating layer 172 can contain oxygen (O), nitrogen (N), fluorine (F), aluminum (Al), magnesium (Mg), silicon (Si), gallium (Ga), germanium (Ge), yttrium (Y), zirconium (Zr), lanthanum (La), neodymium (Nd), hafnium (Hf), tantalum (Ta), titanium (Ti), or the like. For example, an insulating film containing one or more of aluminum oxide (AlOx), magnesium oxide (MgOx), silicon oxide (SiOx), silicon oxynitride (SiOxNy), silicon nitride oxide (SiNxOy), silicon nitride (SiNx), gallium oxide (GaOx), germanium oxide (GeOx), yttrium oxide (YOx), zirconium oxide (ZrOx), lanthanum oxide (LaOx), neodymium oxide (NdOx), hafnium oxide (HfOx), and tantalum oxide (TaOx) can be used. The insulating layer 172 may be a stack of any of the above materials.
An aluminum oxide film is preferably included in the insulating layer 172. The aluminum oxide film can prevent the passage of both oxygen and impurities such as hydrogen and moisture. Thus, during and after the manufacturing process of the transistor, the aluminum oxide film can suitably function as a protective film that has effects of preventing entry of impurities such as hydrogen and moisture, which cause variations in the electrical characteristics of the transistor, into the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, preventing release of oxygen, which is a main component, from the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123, and preventing release of oxygen from the insulating layer 110.
The insulating layer 172 can function as a protective film. The insulating layer 172 can protect the gate insulating layer 150 against plasma damage. As a result, an electron trap can be prevented from being formed in the vicinity of a channel.
<Manufacturing Method of Transistor 11>
A manufacturing method of the transistor 11 will be described with reference to
<Formation of Insulating Layer 172>
The insulating layer 172 is formed over the insulating layer 110, the oxide semiconductor layer 122, and the gate electrode layer 160 (see
The thickness of the insulating layer 172 is preferably greater than or equal to 1 nm and less than or equal to 30 nm, and further preferably greater than or equal to 3 nm and less than or equal to 10 nm.
An ion may be added to the oxide semiconductor layer 122 after the insulating layer 172 is formed (see
The insulating layer 172 may be used as deposited or may be processed by a lithography method, a nanoimprinting method, a dry etching method, or the like.
<Formation of Insulating Layer 170>
Next, the insulating layer 170 is formed over the insulating layer 172. The insulating layer 170 may have a single-layer structure or a stacked-layer structure. The insulating layer 170 can be formed using a material, a method, and the like similar to those of the insulating layer 110.
The insulating layer 170 is preferably an aluminum oxide film formed by a sputtering method. A sputtering gas used for forming the aluminum oxide film preferably contains an oxygen gas. The oxygen gas is contained at 1 vol % or more and 100 vol % or less, preferably 4 vol % or more and 100 vol % or less, and further preferably 10 vol % or more and 100 vol % or less. When oxygen is contained at 1 vol % or more, excess oxygen can be supplied to the insulating layer or insulating layers in contact with the insulating layer. Furthermore, oxygen can be added to the layers in contact with the layer.
For example, the insulating layer 170 having a thickness from 20 nm to 40 nm can be formed using aluminum oxide as a sputtering target and a sputtering gas that contains an oxygen gas at 50 vol %.
Next, heat treatment is preferably performed. The temperature of the heat treatment is typically higher than or equal to 150° C. and lower than the strain point of the substrate, preferably higher than or equal to 250° C. and lower than or equal to 500° C., and further preferably higher than or equal to 300° C. and lower than or equal to 450° C. By the heat treatment, oxygen 173 added to an insulating layer (e.g., the insulating layer 110) is diffused and moved to the oxide semiconductor layer 122, and oxygen vacancies in the oxide semiconductor layer 122 can be filled with the oxygen (see
In this embodiment, the heat treatment can performed at 400° C. in an oxygen atmosphere for one hour.
Note that heat treatment may be performed in other processes. Through heat treatment, defects in a film can be repaired, and the density of interface states can be reduced.
<Oxygen Addition>
Oxygen is not necessarily added through the insulating layer 170. Oxygen may be added to the insulating layer 110 and the insulating layer 175, the first metal oxide film and the metal oxide film 123a, or another insulating layer. As the oxygen that is added, at least one selected from oxygen radicals, oxygen atoms, oxygen atomic ions, oxygen molecular ions, and the like is used. As a method for adding the oxygen, an ion doping method, an ion implantation method, a plasma immersion ion implantation method, or the like can be used.
In the case of using an ion implantation method as the method for adding oxygen, oxygen atomic ions or oxygen molecular ions can be used. The use of oxygen molecular ions can reduce damage to a film to which oxygen is added. Oxygen molecular ions are broken down into oxygen atomic ions at the surface of the film to which oxygen is added, and the oxygen atomic ions are added. Since energy for breaking oxygen molecules down into oxygen atoms is used, the energy per oxygen atomic ion in the case of adding oxygen molecular ions to the film to which oxygen is added is lower than that in the case of adding oxygen atomic ions to the film to which oxygen is added. Therefore, damage to the film to which oxygen is added can be reduced.
By using oxygen molecular ions, the energy of each oxygen atomic ion injected to the film to which oxygen is added is lowered, which makes the injected oxygen atomic ion be positioned in a shallow region. Accordingly, oxygen atoms easily move by later heat treatment, so that more oxygen can be supplied to the metal oxide layer 121, the oxide semiconductor layer 122, and the metal oxide layer 123.
In the case of injecting oxygen molecular ions, the energy per oxygen atomic ion is low as compared with the case of injecting oxygen atomic ions. Thus, by using oxygen molecular ions for injection, the acceleration voltage can be increased and throughput can be increased. Moreover, by using oxygen molecular ions for injection, the dose can be half of the amount that is necessary in the case of using oxygen atomic ions. As a result, throughput can be increased.
In the case of adding oxygen to the film to which oxygen is added, it is preferable that oxygen be added to the film to which oxygen is added so that a peak of the concentration profile of oxygen atomic ions is located in the film to which oxygen is added. In that case, the acceleration voltage for injection can be lowered as compared to the case where oxygen atomic ions are injected, and damage to the film to which oxygen is added can be reduced. In other words, defects in the film to which oxygen is added can be reduced, suppressing variations in electrical characteristics of the transistor. Furthermore, in the case where oxygen is added to the film to which oxygen is added so that the amount of added oxygen atoms at the interface between the insulating layer 110 and the metal oxide layer 121 is less than 1×1021 atoms/cm3, less than 1×1020 atoms/cm3, or less than 1×1019 atoms/cm3, the amount of oxygen added to the insulating layer 110 can be reduced. As a result, damage to the film to which oxygen is added can be reduced, suppressing variations in electrical characteristics of the transistor.
Plasma treatment (plasma immersion ion implantation method) in which the film to which oxygen is added is exposed to plasma generated in an atmosphere containing oxygen may be performed to add oxygen to the film to which oxygen is added. As an example of the atmosphere containing oxygen, an atmosphere containing an oxidation gas such as oxygen, ozone, dinitrogen monoxide, or nitrogen dioxide can be given. Note that it is preferable that the film to which oxygen is added be exposed to plasma generated in a state where bias is applied to the substrate 100 side because the amount of oxygen added to the film to which oxygen is added can be increased. As an example of an apparatus with which such plasma treatment is performed, an ashing apparatus is given.
For example, oxygen molecular ions can be added to the insulating layer 110 by an ion implantation method with a dose of 2×1016/cm2 at an acceleration voltage of 60 kV.
The above process is applicable to the transistor 10 and other transistors.
In this manner, the density of localized states of the oxide semiconductor film is lowered, and thus a transistor with excellent electrical characteristics can be manufactured. In addition, a highly reliable transistor in which variations in electrical characteristics with time or variations in electrical characteristics due to a stress test are reduced can be manufactured.
<Modification Example 2 of Transistor 10: Transistor 12>
A transistor 12 with a shape different from that of the transistor 10 illustrated in
The transistor 12 is different from the transistor 10 in that the metal oxide layer 123 includes a region in contact with side end portions of the oxide semiconductor layer 122 and the metal oxide layer 121 and that a conductive layer 165 is included. Note that in the transistor 12, the metal oxide film 123a can be used as the metal oxide layer 123 without etching.
<<Conductive Layer 165>>
The conductive layer 165 can contain a material such as aluminum (Al), titanium (Ti), chromium (Cr), cobalt (Co), nickel (Ni), copper (Cu), yttrium (Y), zirconium (Zr), molybdenum (Mo), ruthenium (Ru), silver (Ag), tantalum (Ta), tungsten (W), or silicon (Si). The conductive layer 165 may have a stacked-layer structure. When a stacked-layer structure is employed, the above materials may be combined with a material containing nitrogen, such as a nitride of any of the above materials.
The conductive layer 165 can have a function similar to that of the gate electrode layer 160. The conductive layer 165 and the gate electrode layer 160 may be configured to be applied with the same potential or different potentials.
In the transistor 12 including the conductive layer 165, the insulating layer 110 can have a structure and a function similar to those of the gate insulating layer 150.
The above structure can prevent damage to the oxide semiconductor layer caused by the ion addition treatment (see
<Modification Example 3 of Transistor 10: Transistor 13>
A transistor 13 with a shape different from that of the transistor 10 illustrated in
The transistor 13 is different from the transistor 10 in that, as in the transistor 12, the metal oxide layer 123 includes a region in contact with side end portions of the oxide semiconductor layer 122 and the metal oxide layer 121 in the channel length direction and the channel width direction and that a gate insulating layer 151 and a gate insulating layer 152 are included.
<<Gate Insulating Layer 151 and Gate Insulating Layer 152>>
For the gate insulating layer 151 and the gate insulating layer 152, a material similar to that of the gate insulating layer 150 can be used.
Note that the gate insulating layer 151 and the gate insulating layer 152 are preferably formed using different materials.
<Manufacturing Method of Transistor 13>
A manufacturing method of the transistor 13 will be described with reference to
<Formation of Gate Insulating Layer 151>
After the metal oxide layer 123 is formed, the gate insulating layer 151 is formed. The gate insulating layer 151 can be formed by a sputtering method, a CVD method (e.g., a plasma CVD method, an MOCVD method, or an ALD method), an MBE method, or the like.
For example, a 5-nm-thick aluminum oxide can be formed as the gate insulating layer 151 by an ALD method.
<Formation of Insulating Film 152a>
Next, an insulating film 152a and the conductive film 160a are formed over the gate insulating layer 151 and the insulating layer 175 after the formation of the groove portion 174 (see
The insulating film 152a can be formed using a material and a method similar to those of the second insulating film 150a of the transistor 10. For example, a 5-nm-thick silicon oxide can be formed as the insulating film 152a by a plasma CVD method.
Then, the insulating film 152a and the conductive film 160a are subjected to planarization treatment, so that the gate electrode layer 160 and an insulating layer 152b are formed (see
Subsequently, the insulating layer 175 is etched until the gate insulating layer 151 is exposed. The insulating layer 152b is etched off except for a portion overlapping with the gate electrode layer 160, whereby the gate insulating layer 152 can be formed.
Next, the ion 167 is added to the oxide semiconductor layer 122 through the gate insulating layer 151 and the metal oxide layer 123 (see
In the above manner, a reduction in the thickness of the metal oxide layer 123 or the like in manufacture of a miniaturized transistor can be reduced, for example. Furthermore, damage during processing can be reduced. Accordingly, the miniaturized transistor can have a stable shape. In addition, the electrical characteristics and reliability of the transistor can be improved.
<Modification Example 4 of Transistor 10: Transistor 14>
A transistor 14 with a shape different from that of the transistor 10 illustrated in
The shape of the metal oxide layer 123 in the transistor 14 is similar to that in the transistor 12. The transistor 14 is different from the transistor 10 in that the gate insulating layer 150 includes a region in contact with a side surface of the gate electrode layer 160 and that an insulating layer 176 including a region in contact with a side surface of the gate insulating layer 150 is provided.
Note that an angle between the bottom surface of the substrate and a tangent of the side surface of the gate electrode layer (i.e., gradient) is desirably greater than or equal to 30° and less than 90°, preferably greater than or equal to 60° and less than or equal to 85°.
Owing to such a structure, the size of the low-resistance region 125 can be controlled. Accordingly, the on-state current can be improved. In addition, the transistor can have stable electrical characteristics.
<<Insulating Layer 176>>
The insulating layer 176 can be formed using a material similar to that of the insulating layer 175.
<Manufacturing Method of Transistor 14>
A manufacturing method of the transistor 14 will be described with reference to
The second insulating film 150a and the conductive film 160a are formed in the groove portion 174 provided over the metal oxide film 123a (see
The manufacturing process illustrated in
The same can be applied to the gradient of the conductive film 160a that faces the insulating layer 175.
Then, the second insulating film 150a and the conductive film 160a are subjected to planarization treatment, so that the gate electrode layer 160 and the gate insulating layer 150 are formed (see
After that, the insulating layer 175 and the gate insulating layer 150 are etched by a dry etching method using the gate electrode layer 160 as a mask until the metal oxide film 123a is exposed, whereby the metal oxide layer 123 and the insulating layer 176 are formed (see
Then, the ion 167 is added (see
With the insulating layer 176, the size of the low-resistance region can be controlled even when the ion is diffused in the lateral direction by heat treatment and a region to which the ion is not added contains the ion, for example. Accordingly, even with a channel length of less than or equal to 100 nm, less than or equal to 60 nm, less than or equal to 30 nm, or less than or equal to 20 nm, the transistor can operate stably.
Note that the transistor 14 may have any of the following structures: a structure in which the insulating layer 170 is provided (see
In the case where an angle between the bottom surface of the substrate and a tangent of a side surface of the gate electrode layer 160 (i.e., gradient) is large, there might be a region where the insulating layer 176 is not provided (see
This embodiment can be combined as appropriate with any of the other embodiments and an example in this specification.
<Structure of Oxide Semiconductor>
The structure of an oxide semiconductor will be described below.
An oxide semiconductor is classified into a single crystal oxide semiconductor and a non-single-crystal oxide semiconductor. Examples of a non-single-crystal oxide semiconductor include a c-axis aligned crystalline oxide semiconductor (CAAC-OS), a polycrystalline oxide semiconductor, a nanocrystalline oxide semiconductor (nc-OS), an amorphous-like oxide semiconductor (a-like OS), and an amorphous oxide semiconductor.
From another perspective, an oxide semiconductor is classified into an amorphous oxide semiconductor and a crystalline oxide semiconductor. Examples of a crystalline oxide semiconductor include a single crystal oxide semiconductor, a CAAC-OS, a polycrystalline oxide semiconductor, and an nc-OS.
An amorphous structure is generally thought to be isotropic and have no non-uniform structure, to be metastable and have no fixed positions of atoms, to have a flexible bond angle, and to have a short-range order but have no long-range order, for example.
In other words, a stable oxide semiconductor cannot be regarded as a completely amorphous oxide semiconductor. Moreover, an oxide semiconductor that is not isotropic (e.g., an oxide semiconductor that has a periodic structure in a microscopic region) cannot be regarded as a completely amorphous oxide semiconductor. In contrast, an a-like OS, which is not isotropic, has an unstable structure that contains a void. Because of its instability, an a-like OS is close to an amorphous oxide semiconductor in terms of physical properties.
<CAAC-OS>
First, a CAAC-OS is described.
A CAAC-OS is one of oxide semiconductors having a plurality of c-axis aligned crystal parts (also referred to as pellets).
Analysis of a CAAC-OS by X-ray diffraction (XRD) is described. For example, when the structure of a CAAC-OS including an InGaZnO4 crystal that is classified into the space group R-3m is analyzed by an out-of-plane method, a peak appears at a diffraction angle (2θ) of around 31° as shown in
On the other hand, in structural analysis of the CAAC-OS by an in-plane method in which an X-ray is incident on the CAAC-OS in a direction parallel to the formation surface, a peak appears at a 2θ of around 56°. This peak is attributed to the (110) plane of the InGaZnO4 crystal. When analysis (φ scan) is performed with 2θ fixed at around 56° and with the sample rotated using a normal vector to the sample surface as an axis (φ axis), as shown in
Next, a CAAC-OS analyzed by electron diffraction is described. For example, when an electron beam with a probe diameter of 300 nm is incident on a CAAC-OS including an InGaZnO4 crystal in a direction parallel to the formation surface of the CAAC-OS, a diffraction pattern (also referred to as a selected-area electron diffraction pattern) shown in
In a combined analysis image (also referred to as a high-resolution TEM image) of a bright-field image and a diffraction pattern of a CAAC-OS, which is obtained with a transmission electron microscope (TEM), a plurality of pellets can be observed. However, even in the high-resolution TEM image, a boundary between pellets, that is, a grain boundary is not clearly observed in some cases. Thus, in the CAAC-OS, a reduction in electron mobility due to the grain boundary is less likely to occur.
In
In
As described above, the CAAC-OS has c-axis alignment, its pellets (nanocrystals) are connected in an a-b plane direction, and the crystal structure has distortion. For this reason, the CAAC-OS can also be referred to as an oxide semiconductor including a c-axis-aligned a-b-plane-anchored (CAA) crystal.
The CAAC-OS is an oxide semiconductor with high crystallinity. Entry of impurities, formation of defects, or the like might decrease the crystallinity of an oxide semiconductor. This means that the CAAC-OS has small amounts of impurities and defects (e.g., oxygen vacancies).
Note that the impurity means an element other than the main components of the oxide semiconductor, such as hydrogen, carbon, silicon, or a transition metal element. For example, an element (specifically, silicon or the like) having higher strength of bonding to oxygen than a metal element included in an oxide semiconductor extracts oxygen from the oxide semiconductor, which results in disorder of the atomic arrangement and reduced crystallinity of the oxide semiconductor. A heavy metal such as iron or nickel, argon, carbon dioxide, or the like has a large atomic radius (or molecular radius), and thus disturbs the atomic arrangement of the oxide semiconductor and decreases crystallinity.
The characteristics of an oxide semiconductor having impurities or defects might be changed by light, heat, or the like. Impurities included in the oxide semiconductor might serve as carrier traps or carrier generation sources, for example. For example, oxygen vacancy in the oxide semiconductor serves as a carrier trap or serves as a carrier generation source when hydrogen is captured therein.
The CAAC-OS having small amounts of impurities and oxygen vacancies is an oxide semiconductor with low carrier density. Specifically, an oxide semiconductor with a carrier density of lower than 8×1011/cm3, preferably lower than 1×1011/cm3, further preferably lower than 1×1010/cm3, and higher than or equal to 1×10−9/cm3 can be used. Such an oxide semiconductor is referred to as a highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor. A CAAC-OS has a low impurity concentration and a low density of defect states. Thus, the CAAC-OS can be referred to as an oxide semiconductor having stable characteristics.
<nc-OS>
Next, an nc-OS is described.
Analysis of an nc-OS by XRD is described. When the structure of an nc-OS is analyzed by an out-of-plane method, a peak indicating orientation does not appear. That is, a crystal of an nc-OS does not have orientation.
For example, when an electron beam with a probe diameter of 50 nm is incident on a 34-nm-thick region of thinned nc-OS including an InGaZnO4 crystal in a direction parallel to the formation surface, a ring-shaped diffraction pattern (a nanobeam electron diffraction pattern) shown in
Furthermore, an electron diffraction pattern in which spots are arranged in an approximately hexagonal shape is observed in some cases as shown in
As described above, in the nc-OS, a microscopic region (for example, a region with a size greater than or equal to 1 nm and less than or equal to 10 nm, in particular, a region with a size greater than or equal to 1 nm and less than or equal to 3 nm) has a periodic atomic arrangement. There is no regularity of crystal orientation between different pellets in the nc-OS. Thus, the orientation of the whole film is not ordered. Accordingly, the nc-OS cannot be distinguished from an a-like OS or an amorphous oxide semiconductor, depending on an analysis method.
Since there is no regularity of crystal orientation between the pellets (nanocrystals) as mentioned above, the nc-OS can also be referred to as an oxide semiconductor including random aligned nanocrystals (RANC) or an oxide semiconductor including non-aligned nanocrystals (NANC).
The nc-OS is an oxide semiconductor that has high regularity as compared to an amorphous oxide semiconductor. Therefore, the nc-OS is likely to have a lower density of defect states than an a-like OS and an amorphous oxide semiconductor. Note that there is no regularity of crystal orientation between different pellets in the nc-OS. Therefore, the nc-OS has a higher density of defect states than the CAAC-OS.
<a-Like OS>
An a-like OS is an oxide semiconductor having a structure between the nc-OS and the amorphous oxide semiconductor.
The a-like OS has an unstable structure because it contains a void. To verify that an a-like OS has an unstable structure as compared with a CAAC-OS and an nc-OS, a change in structure caused by electron irradiation is described below.
An a-like OS, an nc-OS, and a CAAC-OS are prepared as samples. Each of the samples is an In—Ga—Zn oxide.
First, a high-resolution cross-sectional TEM image of each sample is obtained. The high-resolution cross-sectional TEM images show that all the samples have crystal parts.
It is known that a unit cell of an InGaZnO4 crystal has a structure in which nine layers including three In—O layers and six Ga—Zn—O layers are stacked in the c-axis direction. The distance between the adjacent layers is equivalent to the lattice spacing on the (009) plane (also referred to as d value). The value is calculated to be 0.29 nm from crystal structural analysis. Accordingly, a portion where the spacing between lattice fringes is greater than or equal to 0.28 nm and less than or equal to 0.30 nm is regarded as a crystal part of InGaZnO4 in the following description. Each of lattice fringes corresponds to the a-b plane of the InGaZnO4 crystal.
In this manner, growth of the crystal part in the a-like OS is sometimes induced by electron irradiation. In contrast, in the nc-OS and the CAAC-OS, growth of the crystal part is hardly induced by electron irradiation. Therefore, the a-like OS has an unstable structure as compared with the nc-OS and the CAAC-OS.
The a-like OS has a lower density than the nc-OS and the CAAC-OS because it contains a void. Specifically, the density of the a-like OS is higher than or equal to 78.6% and lower than 92.3% of the density of the single crystal oxide semiconductor having the same composition. The density of each of the nc-OS and the CAAC-OS is higher than or equal to 92.3% and lower than 100% of the density of the single crystal oxide semiconductor having the same composition. Note that it is difficult to deposit an oxide semiconductor having a density of lower than 78% of the density of the single crystal oxide semiconductor.
For example, in the case of an oxide semiconductor having an atomic ratio of In:Ga:Zn=1:1:1, the density of single crystal InGaZnO4 with a rhombohedral crystal structure is 6.357 g/cm3. Accordingly, in the case of the oxide semiconductor having an atomic ratio of In:Ga:Zn=1:1:1, the density of the a-like OS is higher than or equal to 5.0 g/cm3 and lower than 5.9 g/cm3. For example, in the case of the oxide semiconductor having an atomic ratio of In:Ga:Zn=1:1:1, the density of each of the nc-OS and the CAAC-OS is higher than or equal to 5.9 g/cm3 and lower than 6.3 g/cm3.
Note that in the case where an oxide semiconductor having a certain composition does not exist in a single crystal structure, single crystal oxide semiconductors with different compositions are combined at an adequate ratio, which makes it possible to calculate density equivalent to that of a single crystal oxide semiconductor with the desired composition. The density of a single crystal oxide semiconductor having the desired composition can be calculated using a weighted average according to the combination ratio of the single crystal oxide semiconductors with different compositions. Note that it is preferable to use as few kinds of single crystal oxide semiconductors as possible to calculate the density.
As described above, oxide semiconductors have various structures and various properties. Note that an oxide semiconductor may be a stacked layer including two or more films of an amorphous oxide semiconductor, an a-like OS, an nc-OS, and a CAAC-OS, for example.
<CAC Composition>
Described below is the composition of a cloud aligned complementary oxide semiconductor (CAC-OS) applicable to one embodiment of the present invention.
The CAC refers to, for example, a composition of a material in which elements included in an oxide semiconductor are unevenly distributed. The material including unevenly distributed elements has a size of greater than or equal to 0.5 nm and less than or equal to 10 nm, preferably greater than or equal to 1 nm and less than or equal to 2 nm, or a similar size. Note that in the following description of an oxide semiconductor, a state in which one or more metal elements are unevenly distributed and regions including the metal element(s) are mixed is referred to as a mosaic pattern or a patch-like pattern. The region has a size of greater than or equal to 0.5 nm and less than or equal to 10 nm, preferably greater than or equal to 1 nm and less than or equal to 2 nm, or a similar size.
For example, of an In—Ga—Zn oxide (hereinafter also referred to as IGZO), CAC-IGZO has a composition in which materials are separated into indium oxide (InOX1, where X1 is a real number greater than 0) or indium zinc oxide (InX2ZnY2OZ2, where X2, Y2, and Z2 are real numbers greater than 0), and gallium oxide (GaOX3, where X3 is a real number greater than 0), gallium zinc oxide (GaX4ZnY4OZ4, where X4, Y4, and Z4 are real numbers greater than 0), or the like, and a mosaic pattern is formed. Then, InOX1 and InX2ZnY2OZ2 forming the mosaic pattern are evenly distributed in the film. This composition is also referred to as a cloud-like composition.
That is, the CAC-IGZO is a composite oxide semiconductor with a composition in which a region including GaOX3 as a main component and a region including InX2ZnY2OZ2 or InOX1 as a main component are mixed. Note that in this specification, for example, when the atomic ratio of In to an element M in a first region is greater than the atomic ratio of In to an element M in a second region, the first region has higher In concentration than the second region.
Note that a compound including In, Ga, Zn, and O is also known as IGZO. Typical examples of IGZO include a crystalline compound represented by InGaO3(ZnO)m1 (m1 is a natural number) and a crystalline compound represented by In(1+x0)Ga(1−x0)O3(ZnO)m0 (−1≦x0≦1; m0 is a given number).
The above crystalline compounds have a single crystal structure, a polycrystalline structure, or a CAAC structure. Note that the CAAC structure is a crystal structure in which a plurality of IGZO nanocrystals have c-axis alignment and are connected in the a-b plane direction without alignment.
On the other hand, the CAC relates to the material composition. In a CAC material including In, Ga, Zn, and O, regions where nanoparticles including Ga as a main component are partly observed and regions where nanoparticles including In as a main component are partly observed are randomly dispersed to form a mosaic pattern. Therefore, the crystal structure is a secondary element for the CAC composition.
Note that in the CAC composition, a stacked-layer structure including two or more films with different atomic ratios is not included. For example, a two-layer structure of a film including In as a main component and a film including Ga as a main component is not included.
A boundary between the region including GaOX3 as a main component and the region including InX2ZnY2OZ2 or InOX1 as a main component is not clearly observed in some cases.
<Analysis of CAC-IGZO>
Next, measurement results of an oxide semiconductor over a substrate by a variety of methods are described.
<<Structure of Samples and Formation Method Thereof>>
Nine samples of one embodiment of the present invention are described below. The samples are formed at different substrate temperatures and with different ratios of an oxygen gas flow rate in formation of the oxide semiconductor. Note that each sample includes a substrate and an oxide semiconductor over the substrate.
A method for forming the samples is described.
A glass substrate is used as the substrate. Over the glass substrate, a 100-nm-thick In—Ga—Zn oxide is formed as an oxide semiconductor with a sputtering apparatus. The formation conditions are as follows: the pressure in a chamber is 0.6 Pa, and an oxide target (with an atomic ratio of In:Ga:Zn=4:2:4.1) is used as a target. The oxide target provided in the sputtering apparatus is supplied with an AC power of 2500 W.
As for the conditions in the formation of the oxide of the nine samples, the substrate temperature is set to a temperature that is not increased by intentional heating (hereinafter such a temperature is also referred to as R.T.), to 130° C., and to 170° C. The ratio of a flow rate of an oxygen gas to a flow rate of a mixed gas of Ar and oxygen (also referred to as an oxygen gas flow rate ratio) is set to 10%, 30%, and 100%.
<<Analysis by X-Ray Diffraction>>
In this section, results of X-ray diffraction (XRD) measurement performed on the nine samples are described. As an XRD apparatus, D8 ADVANCE manufactured by Bruker AXS is used. The conditions are as follows: scanning is performed by an out-of-plane method at θ/2θ, the scanning range is 15 deg. to 50 deg., the step width is 0.02 deg., and the scanning speed is 3.0 deg./min.
In the XRD spectra shown in
As shown in the XRD spectra in
<<Analysis with Electron Microscope>>
This section describes the observation and analysis results of the samples formed at a substrate temperature of R.T. and with an oxygen gas flow rate ratio of 10% with a high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM). An image obtained with an HAADF-STEM is also referred to as a TEM image.
Described are the results of image analysis of plan-view images and cross-sectional images obtained with an HAADF-STEM (also referred to as plan-view TEM images and cross-sectional TEM images, respectively). The TEM images are observed with a spherical aberration corrector function. The HAADF-STEM images are obtained using an atomic resolution analytical electron microscope JEM-ARM200F manufactured by JEOL Ltd. under the following conditions: the acceleration voltage is 200 kV, and irradiation with an electron beam with a diameter of approximately 0.1 nm is performed.
<<Analysis of Electron Diffraction Patterns>>
This section describes electron diffraction patterns obtained by irradiation of the sample formed at a substrate temperature of R.T. and an oxygen gas flow rate ratio of 10% with an electron beam with a probe diameter of 1 nm (also referred to as a nanobeam).
Electron diffraction patterns of points indicated by black dots a1, a2, a3, a4, and a5 in the plan-view TEM image in
In
Electron diffraction patterns of points indicated by black dots b1, b2, b3, b4, and b5 in the cross-sectional TEM image in
In
For example, when an electron beam with a probe diameter of 300 nm is incident on a CAAC-OS including an InGaZnO4 crystal in a direction parallel to the sample surface, a diffraction pattern including a spot derived from the (009) plane of the InGaZnO4 crystal is obtained. That is, the CAAC-OS has c-axis alignment and the c-axes are aligned in the direction substantially perpendicular to the formation surface or the top surface of the CAAC-OS. Meanwhile, a ring-like diffraction pattern is shown when an electron beam with a probe diameter of 300 nm is incident on the same sample in a direction perpendicular to the sample surface. That is, it is found that the CAAC-OS has neither a-axis alignment nor b-axis alignment.
Furthermore, a diffraction pattern like a halo pattern is observed when an oxide semiconductor including a nanocrystal (a nanocrystalline oxide semiconductor (nc-OS)) is subjected to electron diffraction using an electron beam with a large probe diameter (e.g., 50 nm or larger). Meanwhile, bright spots are shown in a nanobeam electron diffraction pattern of the nc-OS obtained using an electron beam with a small probe diameter (e.g., smaller than 50 nm). Furthermore, in a nanobeam electron diffraction pattern of the nc-OS, regions with high luminance in a circular (ring) pattern are shown in some cases. Also in a nanobeam electron diffraction pattern of the nc-OS, a plurality of bright spots are shown in a ring-like shape in some cases.
The electron diffraction pattern of the sample formed at a substrate temperature of R.T. and with an oxygen gas flow rate ratio of 10% has regions with high luminance in a ring pattern and a plurality of bright spots appear in the ring-like pattern. Accordingly, the sample formed at a substrate temperature of R.T. and with an oxygen gas flow rate ratio of 10% exhibits an electron diffraction pattern similar to that of the nc-OS and does not show alignment in the plane direction and the cross-sectional direction.
According to what is described above, an oxide semiconductor formed at a low substrate temperature or with a low oxygen gas flow rate ratio is likely to have characteristics distinctly different from those of an oxide semiconductor film having an amorphous structure and an oxide semiconductor film having a single crystal structure.
<<Elementary Analysis>>
This section describes the analysis results of elements included in the sample formed at a substrate temperature of R.T. and with an oxygen gas flow rate ratio of 10%. For the analysis, by energy dispersive X-ray spectroscopy (EDX), EDX mapping images are obtained. An energy dispersive X-ray spectrometer AnalysisStation JED-2300T manufactured by JEOL Ltd. is used as an elementary analysis apparatus in the EDX measurement. A Si drift detector is used to detect an X-ray emitted from the sample.
In the EDX measurement, an EDX spectrum of a point is obtained in such a manner that electron beam irradiation is performed on the point in a detection target region of a sample, and the energy of characteristic X-ray of the sample generated by the irradiation and its frequency are measured. In this embodiment, peaks of an EDX spectrum of the point are attributed to electron transition to the L shell in an In atom, electron transition to the K shell in a Ga atom, and electron transition to the K shell in a Zn atom and the K shell in an O atom, and the proportions of the atoms in the point are calculated. An EDX mapping image indicating distributions of proportions of atoms can be obtained through the process in an analysis target region of a sample.
The EDX mapping images in
In
That is, the areas surrounded by the solid lines are regions including a relatively large number of In atoms and the areas surrounded by the dashed lines are regions including a relatively small number of In atoms. In
The area surrounded by the solid line is a region including a relatively small number of Ga atoms and the area surrounded by the dashed line is a region including a relatively large number of Ga atoms. In
Furthermore, as shown in
An In—Ga—Zn oxide having a composition in which the regions including GaOX3 as a main component and the regions including InX2ZnY2OZ2 or InOX1 as main components are unevenly distributed and mixed can be referred to as CAC-IGZO.
The crystal structure of CAC-IGZO includes an nc structure. In an electron diffraction pattern of the CAC-IGZO with the nc structure, several or more bright spots appear in addition to bright sports derived from IGZO including a single crystal, a polycrystal, or a CAAC. Alternatively, in addition to the several or more bright spots, the crystal structure is defined as having high luminance regions appearing in a ring pattern.
As shown in
As described above, CAC-IGZO has a structure different from that of an IGZO compound in which metal elements are evenly distributed, and has characteristics different from those of the IGZO compound. That is, in CAC-IGZO, regions including GaOX3 or the like as a main component and regions including InX2ZnY2OZ2 or InOX1 as a main component are separated to form a mosaic pattern. Accordingly, when CAC-IGZO is used for a semiconductor element, the property derived from GaOX3 or the like and the property derived from InX2ZnY2OZ2 or InOX1 complement each other, whereby high on-state current (Ion) and high field-effect mobility (μ) can be achieved.
A semiconductor element including CAC-IGZO has high reliability. Thus, CAC-IGZO is suitably used in a variety of semiconductor devices typified by a display.
This embodiment can be combined as appropriate with any of the other embodiments and an example in this specification.
In this embodiment, an example of a circuit including the transistor of one embodiment of the present invention will be described with reference to drawings.
<Cross-Sectional Structure>
Here, the first semiconductor material and the second semiconductor material are preferably materials having different band gaps. For example, the first semiconductor material can be a semiconductor material other than an oxide semiconductor (examples of such a semiconductor material include silicon (including strained silicon), germanium, silicon germanium, silicon carbide, gallium arsenide, aluminum gallium arsenide, indium phosphide, gallium nitride, and an organic semiconductor), and the second semiconductor material can be an oxide semiconductor. A transistor using a material other than an oxide semiconductor, such as single crystal silicon, can operate at high speed easily. In contrast, a transistor using an oxide semiconductor and described in the above embodiment as an example can have a small subthreshold value (S value) and a minute structure. Furthermore, the transistor can operate at a high speed because of its high switching speed and has low leakage current because of its low off-state current.
The transistor 2200 may be either an n-channel transistor or a p-channel transistor, and an appropriate transistor may be used in accordance with a circuit. Furthermore, the specific structure of the semiconductor device, such as the material or the structure used for the semiconductor device, is not necessarily limited to those described here except for the use of the transistor of one embodiment of the present invention which uses an oxide semiconductor.
The stack of the two kinds of transistors reduces the area occupied by the circuit, allowing a plurality of circuits to be highly integrated.
Here, in the case where a silicon-based semiconductor material is used for the transistor 2200 provided in a lower portion, hydrogen in an insulator provided in the vicinity of the semiconductor film of the transistor 2200 terminates dangling bonds of silicon; accordingly, the reliability of the transistor 2200 can be improved. Meanwhile, in the case where an oxide semiconductor is used for the transistor 2100 provided in an upper portion, hydrogen in an insulator provided in the vicinity of the semiconductor film of the transistor 2100 becomes a factor of generating carriers in the oxide semiconductor; thus, the reliability of the transistor 2100 might be decreased. Therefore, in the case where the transistor 2100 using an oxide semiconductor is provided over the transistor 2200 using a silicon-based semiconductor material, providing the insulator 2207 having a function of preventing diffusion of hydrogen between the transistors 2100 and 2200 is particularly effective. The insulator 2207 makes hydrogen remain in the lower portion, thereby improving the reliability of the transistor 2200. In addition, since the insulator 2207 suppresses diffusion of hydrogen from the lower portion to the upper portion, the reliability of the transistor 2100 can also be improved.
The insulator 2207 can be, for example, formed using aluminum oxide, aluminum oxynitride, gallium oxide, gallium oxynitride, yttrium oxide, yttrium oxynitride, hafnium oxide, hafnium oxynitride, or yttria-stabilized zirconia (YSZ).
Furthermore, a blocking film having a function of preventing diffusion of hydrogen is preferably formed over the transistor 2100 to cover the transistor 2100 including an oxide semiconductor film. For the blocking film, a material that is similar to that of the insulator 2207 can be used, and in particular, an aluminum oxide film is preferably used. The aluminum oxide film has a high shielding (blocking) effect of preventing penetration of both oxygen and impurities such as hydrogen and moisture. Thus, by using the aluminum oxide film as the blocking film covering the transistor 2100, release of oxygen from the oxide semiconductor film included in the transistor 2100 can be prevented and entry of water and hydrogen into the oxide semiconductor film can be prevented. Note that as the block film, the insulator 2204 having a stacked-layer structure may be used, or the block film may be provided under the insulator 2204.
Note that the transistor 2200 can be a transistor of various types without being limited to a planar type transistor. For example, the transistor 2200 can be a fin-type transistor, a tri-gate transistor, or the like. An example of a cross-sectional view in this case is illustrated in
<Circuit Configuration Example>
In the above structure, electrodes of the transistor 2100 and the transistor 2200 can be connected as appropriate; thus, a variety of circuits can be formed. Examples of circuit configurations which can be achieved by using a semiconductor device of one embodiment of the present invention are described below.
<CMOS Inverter Circuit>
A circuit diagram in
<CMOS Analog Switch>
A circuit diagram in
<Memory Device Example>
An example of a semiconductor device (memory device) which includes the transistor of one embodiment of the present invention, which can retain stored data even when not powered, and which has an unlimited number of write cycles is illustrated in
The semiconductor device illustrated in
The transistor 3300 is a transistor in which a channel is formed in a semiconductor including an oxide semiconductor. Since the off-state current of the transistor 3300 is low, stored data can be retained for a long period. In other words, power consumption can be sufficiently reduced because a semiconductor memory device in which refresh operation is unnecessary or the frequency of refresh operation is extremely low can be provided.
In
The semiconductor device in
Writing and retaining of data are described. First, the potential of the fourth wiring 3004 is set to a potential at which the transistor 3300 is turned on, so that the transistor 3300 is turned on. Accordingly, the potential of the third wiring 3003 is supplied to the gate electrode of the transistor 3200 and the capacitor 3400. That is, a predetermined charge is supplied to the gate electrode of the transistor 3200 (writing). Here, one of two kinds of charges providing different potential levels (hereinafter referred to as a low-level charge and a high-level charge) is supplied. After that, the potential of the fourth wiring 3004 is set to a potential at which the transistor 3300 is turned off, so that the transistor 3300 is turned off. Thus, the charge supplied to the gate electrode of the transistor 3200 is held (retaining).
Since the off-state current of the transistor 3300 is extremely low, the charge of the gate electrode of the transistor 3200 is retained for a long time.
Next, reading of data is described. An appropriate potential (a reading potential) is supplied to the fifth wiring 3005 while a predetermined potential (a constant potential) is supplied to the first wiring 3001, whereby the potential of the second wiring 3002 varies depending on the amount of charge retained in the gate electrode of the transistor 3200. This is because in the case of using an n-channel transistor as the transistor 3200, an apparent threshold voltage Vth_H at the time when the high-level charge is given to the gate electrode of the transistor 3200 is lower than an apparent threshold voltage Vth_L at the time when the low-level charge is given to the gate electrode of the transistor 3200. Here, an apparent threshold voltage refers to the potential of the fifth wiring 3005 which is needed to turn on the transistor 3200. Thus, the potential of the fifth wiring 3005 is set to a potential V0 which is between Vth_H and Vth_L, whereby charge supplied to the gate electrode of the transistor 3200 can be determined. For example, in the case where the high-level charge is supplied to the gate electrode of the transistor 3200 in writing and the potential of the fifth wiring 3005 is V0 (>Vth_H), the transistor 3200 is turned on. In the case where the low-level charge is supplied to the gate electrode of the transistor 3200 in writing, even when the potential of the fifth wiring 3005 is V0 (<Vth_L), the transistor 3200 remains off. Thus, the data retained in the gate electrode of the transistor 3200 can be read by determining the potential of the second wiring 3002.
Note that in the case where memory cells are arrayed to be used, it is necessary that only data of a desired memory cell be able to be read. For example, the fifth wiring 3005 of memory cells from which data is not read may be supplied with a potential at which the transistor 3200 is turned off regardless of the state of the gate electrode, that is, a potential lower than Vth_H, whereby only data of a desired memory cell can be read. Alternatively, the fifth wiring 3005 of the memory cells from which data is not read may be supplied with a potential at which the transistor 3200 is turned on regardless of the state of the gate electrode, that is, a potential higher than Vth_L, whereby only data of a desired memory cell can be read.
The semiconductor device illustrated in
Next, reading of data is described. When the transistor 3300 is turned on, the third wiring 3003 which is in a floating state and the capacitor 3400 are electrically connected to each other, and the charge is redistributed between the third wiring 3003 and the capacitor 3400. As a result, the potential of the third wiring 3003 is changed. The amount of change in the potential of the third wiring 3003 varies depending on the potential of a first terminal of the capacitor 3400 (or the charge accumulated in the capacitor 3400).
For example, the potential of the third wiring 3003 after the charge redistribution is (CB×VB0+C×V)/(CB+C), where V is the potential of the first terminal of the capacitor 3400, C is the capacitance of the capacitor 3400, CB is the capacitance component of the third wiring 3003, and VB0 is the potential of the third wiring 3003 before the charge redistribution. Thus, it can be found that, assuming that the memory cell is in either of two states in which the potential of the first terminal of the capacitor 3400 is V1 and V0 (V1>V0), the potential of the third wiring 3003 in the case of retaining the potential V1 (=(CB×VB0+C×V1)/(CB+C)) is higher than the potential of the third wiring 3003 in the case of retaining the potential V0 (=(CB×VB0+C×V0)/(CB+C)).
Then, by comparing the potential of the third wiring 3003 with a predetermined potential, data can be read.
In this case, a transistor including the first semiconductor material may be used for a driver circuit for driving a memory cell, and a transistor including the second semiconductor material may be stacked over the driver circuit as the transistor 3300.
When including a transistor in which a channel formation region is formed using an oxide semiconductor and which has extremely low off-state current, the semiconductor device described in this embodiment can retain stored data for an extremely long time. In other words, refresh operation becomes unnecessary or the frequency of the refresh operation can be extremely low, which leads to a sufficient reduction in power consumption. Moreover, stored data can be retained for a long time even when power is not supplied (note that a potential is preferably fixed).
Furthermore, in the semiconductor device described in this embodiment, high voltage is not needed for writing data and there is no problem of deterioration of elements. Unlike in a conventional nonvolatile memory, for example, it is not necessary to inject and extract electrons into and from a floating gate; thus, a problem such as deterioration of a gate insulating layer is not caused. That is, the semiconductor device of the disclosed invention does not have a limit on the number of times data can be rewritten, which is a problem of a conventional nonvolatile memory, and the reliability thereof is drastically improved. Furthermore, data is written depending on the state of the transistor (on or off), whereby high-speed operation can be easily achieved.
With the use of the semiconductor device described in this embodiment, a memory device with low power consumption and high capacity (e.g., 1 terabit or more) can be fabricated.
Note that in this specification and the like, it might be possible for those skilled in the art to constitute one embodiment of the invention even when portions to which all the terminals of an active element (e.g., a transistor or a diode), a passive element (e.g., a capacitor or a resistor), or the like are connected are not specified. In other words, one embodiment of the invention can be clear even when connection portions are not specified. Further, in the case where a connection portion is disclosed in this specification and the like, it can be determined that one embodiment of the invention in which a connection portion is not specified is disclosed in this specification and the like, in some cases. In particular, in the case where the number of portions to which the terminal is connected might be plural, it is not necessary to specify the portions to which the terminal is connected. Therefore, it might be possible to constitute one embodiment of the invention by specifying only portions to which some of terminals of an active element (e.g., a transistor or a diode), a passive element (e.g., a capacitor or a resistor), or the like are connected.
Note that in this specification and the like, it might be possible for those skilled in the art to specify the invention when at least the connection portion of a circuit is specified. Alternatively, it might be possible for those skilled in the art to specify the invention when at least a function of a circuit is specified. In other words, when a function of a circuit is specified, one embodiment of the invention can be clear. Furthermore, it can be determined that one embodiment of the invention whose function is specified is disclosed in this specification and the like. Therefore, when a connection portion of a circuit is specified, the circuit is disclosed as one embodiment of the invention even when a function is not specified, and one embodiment of the invention can be constituted. Alternatively, when a function of a circuit is specified, the circuit is disclosed as one embodiment of the invention even when a connection portion is not specified, and one embodiment of the invention can be constituted.
Note that in this specification and the like, in a diagram or a text described in one embodiment, it is possible to take out part of the diagram or the text and constitute an embodiment of the invention. Thus, in the case where a diagram or a text related to a certain portion is described, the context taken out from part of the diagram or the text is also disclosed as one embodiment of the invention, and one embodiment of the invention can be constituted. Therefore, for example, in a diagram or text in which one or more active elements (e.g., transistors or diodes), wirings, passive elements (e.g., capacitors or resistors), conductive layers, insulating layers, semiconductors, organic materials, inorganic materials, components, devices, operating methods, manufacturing methods, or the like are described, part of the diagram or the text is taken out, and one embodiment of the invention can be constituted. For example, from a circuit diagram in which N circuit elements (e.g., transistors or capacitors; N is an integer) are provided, it is possible to constitute one embodiment of the invention by taking out M circuit elements (e.g., transistors or capacitors; M is an integer, where M<N). As another example, it is possible to constitute one embodiment of the invention by taking out M layers (M is an integer, where M<N) from a cross-sectional view in which N layers (N is an integer) are provided. As another example, it is possible to constitute one embodiment of the invention by taking out M elements (M is an integer, where M<N) from a flow chart in which N elements (N is an integer) are provided.
<Imaging Device>
An imaging device of one embodiment of the present invention will be described below.
The peripheral circuit includes at least one of a logic circuit, a switch, a buffer, an amplifier circuit, and a converter circuit. The peripheral circuit may be provided over a substrate where the pixel portion 210 is formed. A semiconductor device such as an IC chip may be used as part or the whole of the peripheral circuit. Note that as the peripheral circuit, one or more of the peripheral circuits 260, 270, 280, and 290 may be omitted.
As illustrated in
<Configuration Example 1 of Pixel>
The pixel 211 included in the imaging device 200 is formed with a plurality of subpixels 212, and each subpixel 212 is combined with a filter which transmits light in a specific wavelength range (color filter), whereby data for achieving color image display can be obtained.
The subpixel 212 (the subpixel 212R, the subpixel 212G, and the subpixel 212B) is electrically connected to a wiring 231, a wiring 247, a wiring 248, a wiring 249, and a wiring 250. In addition, the subpixel 212R, the subpixel 212G, and the subpixel 212B are connected to respective wirings 253 which are independent of one another. In this specification and the like, for example, the wiring 248 and the wiring 249 that are connected to the pixel 211 in the n-th row (n is an integer greater than or equal to 1 and less than or equal to p) are referred to as a wiring 248[n] and a wiring 249[n]. For example, the wiring 253 connected to the pixel 211 in the m-th column (m is an integer greater than or equal to 1 and less than or equal to q) is referred to as a wiring 253[m]. Note that in
The imaging device 200 has a structure in which the subpixel 212 is electrically connected to the subpixel 212 in an adjacent pixel 211 which is provided with a color filter transmitting light in the same wavelength range as the subpixel 212, via a switch.
The color filter used in the subpixel 212 is not limited to red (R), green (G), and blue (B) color filters, and color filters that transmit light of cyan (C), yellow (Y), and magenta (M) may be used. By provision of the subpixels 212 that sense light in three different wavelength ranges in one pixel 211, a full-color image can be obtained.
The pixel 211 including the subpixel 212 provided with a color filter transmitting yellow (Y) light may be provided, in addition to the subpixels 212 provided with the color filters transmitting red (R), green (G), and blue (B) light. The pixel 211 including the subpixel 212 provided with a color filter transmitting blue (B) light may be provided, in addition to the subpixels 212 provided with the color filters transmitting cyan (C), yellow (Y), and magenta (M) light. When the subpixels 212 sensing light in four different wavelength ranges are provided in one pixel 211, the reproducibility of colors of an obtained image can be increased.
For example, in
Although the number of subpixels 212 provided in the pixel 211 may be one, two or more subpixels are preferably provided. For example, when two or more subpixels 212 sensing light in the same wavelength range are provided, the redundancy is increased, and the reliability of the imaging device 200 can be increased.
When an infrared (IR) filter that transmits infrared light and absorbs or reflects visible light is used as the filter, the imaging device 200 that senses infrared light can be provided.
Furthermore, when a neutral density (ND) filter (dark filter) is used, output saturation which occurs when a large amount of light enters a photoelectric conversion element (light-receiving element) can be prevented. With a combination of ND filters with different dimming capabilities, the dynamic range of the imaging device can be increased.
Besides the above-described filter, the pixel 211 may be provided with a lens. An arrangement example of the pixel 211, a filter 254, and a lens 255 is described with cross-sectional views in
However, as indicated by a region surrounded with dashed-dotted lines, part of the light 256 indicated by arrows might be blocked by some wirings 257. Thus, a preferable structure is that the lens 255 and the filter 254 are provided on the photoelectric conversion element 220 side, so that the photoelectric conversion element 220 can efficiently receive the light 256 as illustrated in
As the photoelectric conversion element 220 illustrated in
The photoelectric conversion element 220 may be formed using a substance that has a function of absorbing a radiation and generating electric charges. Examples of the substance that has a function of absorbing a radiation and generating electric charges include selenium, lead iodide, mercury iodide, gallium arsenide, cadmium telluride, and cadmium zinc alloy.
For example, when selenium is used for the photoelectric conversion element 220, the photoelectric conversion element 220 can have a light absorption coefficient in a wide wavelength range, such as visible light, ultraviolet light, infrared light, X-rays, and gamma rays.
One pixel 211 included in the imaging device 200 may include the subpixel 212 with a first filter in addition to the subpixel 212 illustrated in
<Configuration Example 2 of Pixel>
An example of a pixel including a transistor using silicon and a transistor using an oxide semiconductor will be described below.
The imaging device illustrated in
The imaging device includes a layer 310 including the transistor 351 provided on the silicon substrate 300 and the photodiode 360 provided in the silicon substrate 300, a layer 320 which is in contact with the layer 310 and includes the wirings 371, a layer 330 which is in contact with the layer 320 and includes the transistor 353, and a layer 340 which is in contact with the layer 330 and includes the wiring 372 and the wiring 373.
Note that in the example of the cross-sectional view in
In the case where a pixel is formed with use of transistors using an oxide semiconductor, the layer 310 may include the transistor using an oxide semiconductor. Alternatively, the layer 310 may be omitted, and the pixel may include only transistors using an oxide semiconductor.
In addition, in the cross-sectional view in
An imaging device illustrated in
The element structure illustrated in
Alternatively, a PIN diode element formed using an amorphous silicon film, a microcrystalline silicon film, or the like may be used as the photodiode 365. In the photodiode 365, an n-type semiconductor 368, an i-type semiconductor 367, and a p-type semiconductor 366 are stacked in this order. The i-type semiconductor 367 is preferably formed using amorphous silicon. The p-type semiconductor 366 and the n-type semiconductor 368 can each be formed using amorphous silicon, microcrystalline silicon, or the like which includes a dopant imparting the corresponding conductivity type. The photodiode 365 in which a photoelectric conversion layer is formed using amorphous silicon has high sensitivity in a visible light wavelength region, and therefore can easily sense weak visible light.
This embodiment can be combined as appropriate with any of the other embodiments and an example in this specification.
In this embodiment, circuit configuration examples to which the transistors including oxide semiconductor layers (OS transistors) described in the above embodiment can be applied will be described with reference to
Note that the inverter 2800 including the OS transistors can be provided over a CMOS circuit including Si transistors. Since the inverter 2800 can be provided so as to overlap with the CMOS circuit, no additional area is required for the inverter 2800, and thus, an increase in the circuit area can be suppressed.
Each of the OS transistors 2810 and 2820 includes a first gate functioning as a front gate, a second gate functioning as a back gate, a first terminal functioning as one of a source and a drain, and a second terminal functioning as the other of the source and the drain.
The first gate of the OS transistor 2810 is connected to its second terminal. The second gate of the OS transistor 2810 is connected to a wiring that transmits the signal SBG. The first terminal of the OS transistor 2810 is connected to a wiring that supplies a voltage VDD. The second terminal of the OS transistor 2810 is connected to the output terminal OUT.
The first gate of the OS transistor 2820 is connected to the input terminal IN. The second gate of the OS transistor 2820 is connected to the input terminal IN. The first terminal of the OS transistor 2820 is connected to the output terminal OUT. The second terminal of the OS transistor 2820 is connected to a wiring that supplies a voltage VSS.
The signal SBG supplied to the second gate of the OS transistor 2810 can control the threshold voltage of the OS transistor 2810.
The signal SBG includes a voltage VBG_A for shifting the threshold voltage in the negative direction and a voltage VBG_B for shifting the threshold voltage in the positive direction. The threshold voltage of the OS transistor 2810 can be shifted in the negative direction to be a threshold voltage VTH_A when the voltage VBG_A is applied to the second gate. The threshold voltage of the OS transistor 2810 can be shifted in the positive direction to be a threshold voltage VTH_B when the voltage VBG_B is applied to the second gate.
To visualize the above description,
When a high voltage such as the voltage VBG_A is applied to the second gate, the electrical characteristics of the OS transistor 2810 can be shifted to match a curve shown by a dashed line 2840 in
The shift of the threshold voltage in the positive direction toward the threshold voltage VTH_B can make current less likely to flow in the OS transistor 2810.
Since a state in which current is less likely to flow in the OS transistor 2810 as illustrated in
The shift of the threshold voltage in the negative direction toward the threshold voltage VTH_A can make current flow easily in the OS transistor 2810.
Since a state in which current is likely to flow in the OS transistor 2810 as illustrated in
Note that the threshold voltage of the OS transistor 2810 is preferably controlled by the signal SBG before the state of the OS transistor 2820 is switched, i.e., before Time T1 or T2. For example, as in
Although the timing chart in
The circuit configuration in
The operation with the circuit configuration in
The voltage for controlling the threshold voltage of the OS transistor 2810 is supplied to the second gate of the OS transistor 2810 before Time T3 at which the level of the signal supplied to the input terminal IN is switched to a high level. The signal SF is set to a high level and the OS transistor 2850 is turned on, so that the voltage VBG_B for controlling the threshold voltage is supplied to a node NBG.
The OS transistor 2850 is turned off after the voltage of the node NBG becomes VBG_B. Since the off-state current of the OS transistor 2850 is extremely low, the voltage VBG_B held by the node NBG can be retained while the OS transistor 2850 remains off. Therefore, the number of times the voltage VBG_B is supplied to the second gate of the OS transistor 2850 can be reduced and accordingly, the power consumption for rewriting the voltage VBG_B can be reduced.
Although
The circuit configuration in
The operation with the circuit configuration in
The output waveform IN_B which corresponds to a signal whose logic is inverted from the logic of the signal supplied to the input terminal IN can be used as a signal that controls the threshold voltage of the OS transistor 2810. Therefore, the threshold voltage of the OS transistor 2810 can be controlled as described with reference to
Moreover, the signal supplied to the input terminal IN is at a low level and the OS transistor 2820 is turned off at Time T5 in
As described above, in the configuration of the inverter including the OS transistor in this embodiment, the voltage of the back gate is switched in accordance with the logic of the signal supplied to the input terminal IN. In such a configuration, the threshold voltage of the OS transistor can be controlled. The control of the threshold voltage of the OS transistor by the signal supplied to the input terminal IN can make a change in the voltage of the output terminal OUT steep. Moreover, shoot-through current between the wirings that supply power supply voltages can be reduced. Thus, power consumption can be reduced.
<RF Tag>
In this embodiment, an RF tag that includes the transistor described in the above embodiment or the memory device described in the above embodiment will be described with reference to
The RF tag of this embodiment includes a memory circuit, stores necessary data in the memory circuit, and transmits and receives data to/from the outside by using a contactless means, for example, wireless communication. With these features, the RF tag can be used for an individual authentication system in which an object or the like is recognized by reading the individual information, for example. Note that the RF tag is required to have extremely high reliability in order to be used for this purpose.
A configuration of the RF tag will be described with reference to
As shown in
Next, the structure of each circuit will be described. The antenna 804 exchanges the radio signal 803 with the antenna 802 which is connected to the communication device 801. The rectifier circuit 805 generates an input potential by rectification, for example, half-wave voltage doubler rectification of an input alternating signal generated by reception of a radio signal at the antenna 804 and smoothing of the rectified signal with a capacitor provided in a later stage. Note that a limiter circuit may be provided on an input side or an output side of the rectifier circuit 805. The limiter circuit controls electric power so that electric power which is higher than or equal to certain electric power is not input to a circuit in a later stage if the amplitude of the input alternating signal is high and an internal generation voltage is high.
The constant voltage circuit 806 generates a stable power supply voltage from an input potential and supplies it to each circuit. Note that the constant voltage circuit 806 may include a reset signal generation circuit. The reset signal generation circuit is a circuit which generates a reset signal of the logic circuit 809 by utilizing rise of the stable power supply voltage.
The demodulation circuit 807 demodulates the input alternating signal by envelope detection and generates the demodulated signal. Furthermore, the modulation circuit 808 performs modulation in accordance with data to be output from the antenna 804.
The logic circuit 809 analyzes and processes the demodulated signal. The memory circuit 810 holds the input data and includes a row decoder, a column decoder, a memory region, and the like. Further, the ROM 811 stores an identification number (ID) or the like and outputs it in accordance with processing.
Note that the decision whether each circuit described above is provided or not can be made as appropriate as needed.
Here, the semiconductor device described in the above embodiment can be used for the memory circuit 810. Since the memory circuit of one embodiment of the present invention can retain data even when not powered, the memory circuit can be favorably used for an RF tag. Furthermore, the memory circuit of one embodiment of the present invention needs power (voltage) needed for data writing significantly lower than that needed in a conventional nonvolatile memory; thus, it is possible to prevent a difference between the maximum communication range in data reading and that in data writing. In addition, it is possible to suppress malfunction or incorrect writing which is caused by power shortage in data writing.
Since the memory circuit of one embodiment of the present invention can be used as a nonvolatile memory, it can also be used as the ROM 811. In this case, it is preferable that a manufacturer separately prepare a command for writing data to the ROM 811 so that a user cannot rewrite data freely. Since the manufacturer gives identification numbers before shipment and then starts shipment of products, instead of putting identification numbers to all the manufactured RF tags, it is possible to put identification numbers to only good products to be shipped. Thus, the identification numbers of the shipped products are in series and customer management corresponding to the shipped products is easily performed.
This embodiment can be combined as appropriate with any of the other embodiments and an example in this specification.
In this embodiment, a CPU that includes the memory device described in the above embodiment will be described.
<Circuit Diagram of CPU>
The CPU illustrated in
An instruction that is input to the CPU through the bus interface 1198 is input to the instruction decoder 1193 and decoded therein, and then, input to the ALU controller 1192, the interrupt controller 1194, the register controller 1197, and the timing controller 1195.
The ALU controller 1192, the interrupt controller 1194, the register controller 1197, and the timing controller 1195 conduct various controls in accordance with the decoded instruction. Specifically, the ALU controller 1192 generates signals for controlling the operation of the ALU 1191. While the CPU is executing a program, the interrupt controller 1194 judges an interrupt request from an external input/output device or a peripheral circuit on the basis of its priority or a mask state, and processes the request. The register controller 1197 generates an address of the register 1196, and reads/writes data from/to the register 1196 in accordance with the state of the CPU.
The timing controller 1195 generates signals for controlling operation timings of the ALU 1191, the ALU controller 1192, the instruction decoder 1193, the interrupt controller 1194, and the register controller 1197. For example, the timing controller 1195 includes an internal clock generator for generating an internal clock signal based on a reference clock signal, and supplies the internal clock signal to the above circuits.
In the CPU illustrated in
In the CPU illustrated in
<Memory Circuit>
Here, the memory device described in the above embodiment can be used as the circuit 1202. When supply of a power supply voltage to the memory element 1200 is stopped, a ground potential (0 V) or a potential at which the transistor 1209 in the circuit 1202 is turned off continues to be input to a gate of the transistor 1209. For example, a first gate of the transistor 1209 is grounded through a load such as a resistor.
Shown here is an example in which the switch 1203 is a transistor 1213 having one conductivity type (e.g., an n-channel transistor) and the switch 1204 is a transistor 1214 having a conductivity type opposite to the one conductivity type (e.g., a p-channel transistor). A first terminal of the switch 1203 corresponds to one of a source and a drain of the transistor 1213, a second terminal of the switch 1203 corresponds to the other of the source and the drain of the transistor 1213, and conduction or non-conduction between the first terminal and the second terminal of the switch 1203 (i.e., the on/off state of the transistor 1213) is selected by a control signal RD input to a gate of the transistor 1213. A first terminal of the switch 1204 corresponds to one of a source and a drain of the transistor 1214, a second terminal of the switch 1204 corresponds to the other of the source and the drain of the transistor 1214, and conduction or non-conduction between the first terminal and the second terminal of the switch 1204 (i.e., the on/off state of the transistor 1214) is selected by the control signal RD input to a gate of the transistor 1214.
One of a source and a drain of the transistor 1209 is electrically connected to a first terminal of the capacitor 1208 and a gate of the transistor 1210. Here, the connection portion is referred to as a node M2. One of a source and a drain of the transistor 1210 is electrically connected to a line which can supply a low power supply potential (e.g., a GND line), and the other thereof is electrically connected to the first terminal of the switch 1203 (the one of the source and the drain of the transistor 1213). The second terminal of the switch 1203 (the other of the source and the drain of the transistor 1213) is electrically connected to the first terminal of the switch 1204 (the one of the source and the drain of the transistor 1214). The second terminal of the switch 1204 (the other of the source and the drain of the transistor 1214) is electrically connected to a line which can supply a power supply potential VDD. The second terminal of the switch 1203 (the other of the source and the drain of the transistor 1213), the first terminal of the switch 1204 (the one of the source and the drain of the transistor 1214), an input terminal of the logic element 1206, and a first terminal of the capacitor 1207 are electrically connected to each other. Here, the connection portion is referred to as a node M1. A second terminal of the capacitor 1207 can be supplied with a constant potential. For example, the second terminal of the capacitor 1207 can be supplied with a low power supply potential (e.g., GND) or a high power supply potential (e.g., VDD). The second terminal of the capacitor 1207 is electrically connected to the line which can supply a low power supply potential (e.g., a GND line). A second terminal of the capacitor 1208 can be supplied with a constant potential. For example, the second terminal of the capacitor 1208 can be supplied with a low power supply potential (e.g., GND) or a high power supply potential (e.g., VDD). The second terminal of the capacitor 1208 is electrically connected to the line which can supply a low power supply potential (e.g., a GND line).
The capacitor 1207 and the capacitor 1208 are not necessarily provided as long as the parasitic capacitance of the transistor, the wiring, or the like is actively utilized.
A control signal WE is input to the first gate (first gate electrode) of the transistor 1209. As for each of the switch 1203 and the switch 1204, a conduction state or a non-conduction state between the first terminal and the second terminal is selected by the control signal RD which is different from the control signal WE. When the first terminal and the second terminal of one of the switches are in the conduction state, the first terminal and the second terminal of the other of the switches are in the non-conduction state.
Note that the transistor 1209 in
A signal corresponding to data retained in the circuit 1201 is input to the other of the source and the drain of the transistor 1209.
In the example of
In
As the circuit 1201 in
In a period during which the memory element 1200 is not supplied with the power supply voltage, the semiconductor device of one embodiment of the present invention can retain data stored in the circuit 1201 by the capacitor 1208 which is provided in the circuit 1202.
The off-state current of a transistor in which a channel is formed in an oxide semiconductor is extremely low. For example, the off-state current of a transistor in which a channel is formed in an oxide semiconductor is significantly lower than that of a transistor in which a channel is formed in silicon having crystallinity. Thus, when the transistor is used as the transistor 1209, a signal held in the capacitor 1208 is retained for a long time also in a period during which the power supply voltage is not supplied to the memory element 1200. The memory element 1200 can accordingly retain the stored content (data) also in a period during which the supply of the power supply voltage is stopped.
Since the above-described memory element performs pre-charge operation with the switch 1203 and the switch 1204, the time required for the circuit 1201 to retain original data again after the supply of the power supply voltage is restarted can be shortened.
In the circuit 1202, a signal retained by the capacitor 1208 is input to the gate of the transistor 1210. Therefore, after supply of the power supply voltage to the memory element 1200 is restarted, the signal retained by the capacitor 1208 can be converted into the one corresponding to the state (the on state or the off state) of the transistor 1210 to be read from the circuit 1202. Consequently, an original signal can be accurately read even when a potential corresponding to the signal retained by the capacitor 1208 varies to some degree.
By applying the above-described memory element 1200 to a memory device such as a register or a cache memory included in a processor, data in the memory device can be prevented from being lost owing to the stop of the supply of the power supply voltage. Furthermore, shortly after the supply of the power supply voltage is restarted, the memory device can be returned to the same state as that before the power supply is stopped. Therefore, the power supply can be stopped even for a short time in the processor or one or a plurality of logic circuits included in the processor, resulting in lower power consumption.
Although the memory element 1200 is used in a CPU in this embodiment, the memory element 1200 can also be used in an LSI such as a digital signal processor (DSP), a custom LSI, or a programmable logic device (PLD), and a radio frequency (RF) tag.
This embodiment can be combined as appropriate with any of the other embodiments and an example in this specification.
In this embodiment, configuration examples of a display device using a transistor of one embodiment of the present invention will be described.
<Circuit Configuration Example of Display Device>
The transistor in the pixel portion can be formed in accordance with Embodiment 1. The transistor can be easily formed as an n-channel transistor, and thus part of a driver circuit that can be formed using an n-channel transistor can be formed over the same substrate as the transistor of the pixel portion. With the use of the transistor described in the above embodiment for the pixel portion or the driver circuit in this manner, a highly reliable display device can be provided.
In
<Liquid Crystal Display Device>
This pixel circuit can be applied to a structure in which one pixel includes a plurality of pixel electrode layers. The pixel electrode layers are connected to different transistors, and the transistors can be driven with different gate signals. Accordingly, signals applied to individual pixel electrode layers in a multi-domain pixel can be controlled independently.
A scan line 712 of a transistor 716 and a scan line 713 of a transistor 717 are separated so that different gate signals can be supplied thereto. In contrast, a data line 714 is shared by the transistors 716 and 717. The transistor described in Embodiment 1 can be used as appropriate as each of the transistors 716 and 717. Thus, a highly reliable liquid crystal display device can be provided.
A first pixel electrode layer is electrically connected to the transistor 716 and a second pixel electrode layer is electrically connected to the transistor 717. The first pixel electrode layer and the second pixel electrode layer are separated. There is no particular limitation on the shapes of the first pixel electrode layer and the second pixel electrode layer. For example, the first pixel electrode layer may have a V-like shape.
A gate electrode of the transistor 716 is connected to the scan line 712, and a gate electrode of the transistor 717 is connected to the scan line 713. When different gate signals are supplied to the scan line 712 and the scan line 713, operation timings of the transistor 716 and the transistor 717 can be varied. As a result, alignment of liquid crystals can be controlled.
Furthermore, a storage capacitor may be formed using a capacitor wiring 710, a gate insulating layer functioning as a dielectric, and a capacitor electrode electrically connected to the first pixel electrode layer or the second pixel electrode layer.
The multi-domain pixel includes a first liquid crystal element 718 and a second liquid crystal element 719. The first liquid crystal element 718 includes the first pixel electrode layer, a counter electrode layer, and a liquid crystal layer therebetween. The second liquid crystal element 719 includes the second pixel electrode layer, a counter electrode layer, and a liquid crystal layer therebetween.
Note that a pixel circuit of the present invention is not limited to that illustrated in
The display device 20 using the liquid crystal element includes the following in addition to transistors 50 and 52 (the transistor 10 described in Embodiment 1): the conductive layer 165, a conductive layer 197, an insulating layer 420, a liquid crystal layer 490, a liquid crystal element 80, a capacitor 60, a capacitor 62, an insulating layer 430, a spacer 440, a coloring layer 460, a bonding layer 470, a conductive layer 480, a light-shielding layer 418, a substrate 400, a bonding layer 473, a bonding layer 474, a bonding layer 475, a bonding layer 476, a polarizing plate 103, a polarizing plate 403, a protective substrate 105, a protective substrate 402, and an anisotropic conductive layer 510.
<Organic EL Display Device>
In an organic EL element, by application of voltage to a light-emitting element, electrons are injected from one of a pair of electrodes and holes are injected from the other of the pair of electrodes, into a layer containing a light-emitting organic compound; thus, current flows. The electrons and holes are recombined, and thus, the light-emitting organic compound is excited. The light-emitting organic compound returns to a ground state from the excited state, thereby emitting light. Owing to such a mechanism, this light-emitting element is referred to as a current-excitation light-emitting element.
The configuration of the applicable pixel circuit and operation of a pixel employing digital time grayscale driving will be described.
A pixel 720 includes a switching transistor 721, a driver transistor 722, a light-emitting element 724, and a capacitor 723. A gate electrode layer of the switching transistor 721 is connected to a scan line 726, a first electrode (one of a source electrode layer and a drain electrode layer) of the switching transistor 721 is connected to a signal line 725, and a second electrode (the other of the source electrode layer and the drain electrode layer) of the switching transistor 721 is connected to a gate electrode layer of the driver transistor 722. The gate electrode layer of the driver transistor 722 is connected to a power supply line 727 through the capacitor 723, a first electrode of the driver transistor 722 is connected to the power supply line 727, and a second electrode of the driver transistor 722 is connected to a first electrode (a pixel electrode) of the light-emitting element 724. A second electrode of the light-emitting element 724 corresponds to a common electrode 728. The common electrode 728 is electrically connected to a common potential line formed over the same substrate as the common electrode 728.
As the switching transistor 721 and the driver transistor 722, any of the transistors described in Embodiments 1 to 3 can be used as appropriate. In this manner, a highly reliable organic EL display device can be provided.
The potential of the second electrode (the common electrode 728) of the light-emitting element 724 is set to be a low power supply potential. Note that the low power supply potential is lower than a high power supply potential supplied to the power supply line 727. For example, the low power supply potential can be GND, 0 V, or the like. The high power supply potential and the low power supply potential are set to be higher than or equal to the forward threshold voltage of the light-emitting element 724, and the difference between the potentials is applied to the light-emitting element 724, whereby current is supplied to the light-emitting element 724, leading to light emission. The forward voltage of the light-emitting element 724 refers to a voltage at which a desired luminance is obtained, and includes at least a forward threshold voltage.
Note that gate capacitance of the driver transistor 722 may be used as a substitute for the capacitor 723, so that the capacitor 723 can be omitted.
Next, a signal input to the driver transistor 722 is described. In the case of a voltage-input voltage driving method, a video signal for sufficiently turning on or off the driver transistor 722 is input to the driver transistor 722. In order for the driver transistor 722 to operate in a linear region, voltage higher than the voltage of the power supply line 727 is applied to the gate electrode layer of the driver transistor 722. Note that voltage higher than or equal to voltage which is the sum of power supply line voltage and the threshold voltage Vth of the driver transistor 722 is applied to the signal line 725.
In the case of performing analog grayscale driving, a voltage higher than or equal to a voltage which is the sum of the forward voltage of the light-emitting element 724 and the threshold voltage Vth of the driver transistor 722 is applied to the gate electrode layer of the driver transistor 722. A video signal by which the driver transistor 722 is operated in a saturation region is input, so that current is supplied to the light-emitting element 724. In order for the driver transistor 722 to operate in a saturation region, the potential of the power supply line 727 is set higher than the gate potential of the driver transistor 722. When an analog video signal is used, it is possible to supply current to the light-emitting element 724 in accordance with the video signal and perform analog grayscale driving.
Note that the configuration of the pixel circuit of the present invention is not limited to that illustrated in
In the case where the transistor described in the above embodiment is used for the circuit illustrated in
The display device 24 using the light-emitting element includes the following in addition to the transistors 50 and 52 (the transistor 10 described in Embodiment 1): the conductive layer 197, a conductive layer 410, an optical adjustment layer 530, an EL layer 450, a conductive layer 415, a light-emitting element 70, the capacitor 60, the capacitor 62, the insulating layer 430, the spacer 440, the coloring layer 460, the bonding layer 470, a partition 445, the light-shielding layer 418, the substrate 400, and the anisotropic conductive layer 510.
In this specification and the like, a display element, a display device which is a device including a display element, a light-emitting element, and a light-emitting device which is a device including a light-emitting element can employ a variety of modes or can include a variety of elements, for example. A display element, a display device, a light-emitting element, or a light-emitting device include at least one of the following, for example: an EL (electroluminescent) element (e.g., an EL element including organic and inorganic materials, an organic EL element, or an inorganic EL element), an LED (e.g., a white LED, a red LED, a green LED, or a blue LED), a transistor (a transistor which emits light depending on current), an electron emitter, a liquid crystal element, electronic ink, an electrophoretic element, a grating light valve (GLV), a plasma display panel (PDP), micro electro mechanical systems (MEMS), a digital micromirror device (DMD), a digital micro shutter (DMS), MIRASOL (registered trademark), an interferometric modulator display (IMOD) element, an electrowetting element, a piezoelectric ceramic display, and a display element using a carbon nanotube. Other than the above, display media whose contrast, luminance, reflectivity, transmittance, or the like is changed by electric or electromagnetic action may be included. Note that examples of display devices having EL elements include an EL display. Examples of display devices including electron emitters include a field emission display (FED) and an SED-type flat panel display (SED: surface-conduction electron-emitter display). Examples of display devices including liquid crystal elements include a liquid crystal display (e.g., a transmissive liquid crystal display, a transflective liquid crystal display, a reflective liquid crystal display, a direct-view liquid crystal display, or a projection liquid crystal display). Examples of display devices including electronic ink or electrophoretic elements include electronic paper.
This embodiment can be combined as appropriate with any of the other embodiments and an example in this specification.
In this embodiment, a display module using a semiconductor device of one embodiment of the present invention will be described with reference to
<Display Module>
In a display module 6000 in
The semiconductor device of one embodiment of the present invention can be used for, for example, the display panel 6006 and an integrated circuit mounted on a printed circuit board.
The shapes and sizes of the upper cover 6001 and the lower cover 6002 can be changed as appropriate in accordance with the sizes of the touch panel 6004 and the display panel 6006.
The touch panel 6004 can be a resistive touch panel or a capacitive touch panel and may be formed to overlap with the display panel 6006. A counter substrate (sealing substrate) of the display panel 6006 can have a touch panel function. A photosensor may be provided in each pixel of the display panel 6006 so that an optical touch panel function is added. An electrode for a touch sensor may be provided in each pixel of the display panel 6006 so that a capacitive touch panel function is added.
The backlight unit 6007 includes a light source 6008. The light source 6008 may be provided at an end portion of the backlight unit 6007 and a light diffusing plate may be used.
The frame 6009 protects the display panel 6006 and also functions as an electromagnetic shield for blocking electromagnetic waves generated from the printed circuit board 6010. The frame 6009 may function as a radiator plate.
The printed circuit board 6010 has a power supply circuit and a signal processing circuit for outputting a video signal and a clock signal. As a power source for supplying power to the power supply circuit, an external commercial power source or the battery 6011 provided separately may be used. Note that the battery 6011 is not necessary in the case where a commercial power source is used.
The display module 6000 can be additionally provided with a member such as a polarizing plate, a retardation plate, or a prism sheet.
This embodiment can be combined as appropriate with any of the other embodiments and an example in this specification.
In this embodiment, application examples of the semiconductor device of one embodiment of the present invention will be described.
<Package Using Lead Frame Interposer>
This embodiment can be combined as appropriate with any of the other embodiments and an example in this specification.
In this embodiment, electronic devices and lighting devices of embodiments of the present invention will be described with reference to drawings.
<Electronic Device>
Electronic devices and lighting devices can be fabricated using the semiconductor device of one embodiment of the present invention. In addition, highly reliable electronic devices and lighting devices can be fabricated using the semiconductor device of one embodiment of the present invention. Furthermore, electronic devices and lighting devices including touch sensors with improved detection sensitivity can be fabricated using the semiconductor device of one embodiment of the present invention.
Examples of electronic devices are television devices (also referred to as TVs or television receivers), monitors for computers and the like, cameras such as digital cameras and digital video cameras, digital photo frames, cellular phones (also referred to as mobile phones or portable telephone devices), portable game machines, portable information terminals, audio playback devices, large game machines such as pin-ball machines, and the like.
In the case of having flexibility, the electronic device or lighting device of one embodiment of the present invention can be incorporated along a curved inside/outside wall surface of a house or a building or a curved interior/exterior surface of a car.
Furthermore, the electronic device of one embodiment of the present invention may include a secondary battery. It is preferable that the secondary battery be capable of being charged by non-contact power transmission.
Examples of the secondary battery include a lithium ion secondary battery such as a lithium polymer battery using a gel electrolyte (lithium ion polymer battery), a lithium-ion battery, a nickel-hydride battery, a nickel-cadmium battery, an organic radical battery, a lead-acid battery, an air secondary battery, a nickel-zinc battery, and a silver-zinc battery.
The electronic device of one embodiment of the present invention may include an antenna. When a signal is received by the antenna, the electronic device can display an image, data, or the like on a display portion. When the electronic device includes a secondary battery, the antenna may be used for non-contact power transmission.
The display portion 9710 and the display portion 9711 are display devices or input/output devices provided in an automobile windshield. The display device or input/output device of one embodiment of the present invention can be a see-through display device or input/output device, through which the opposite side can be seen, by using a light-transmitting conductive material for its electrodes. Such a see-through display device or input/output device does not hinder driver's vision during the driving of the automobile 9700. Therefore, the display device or input/output device of one embodiment of the present invention can be provided in the windshield of the automobile 9700. Note that in the case where a transistor or the like for driving the display device or input/output device is provided in the display device or input/output device, a transistor having light-transmitting properties, such as an organic transistor using an organic semiconductor material or a transistor using an oxide semiconductor, is preferably used.
The display portion 9712 is a display device provided on a pillar portion. For example, the display portion 9712 can compensate for the view hindered by the pillar portion by showing an image taken by an imaging unit provided on the car body. The display portion 9713 is a display device provided on a dashboard portion. For example, the display portion 9713 can compensate for the view hindered by the dashboard portion by showing an image taken by an imaging unit provided on the car body. That is, showing an image taken by an imaging unit provided on the outside of the car body leads to elimination of blind areas and enhancement of safety. In addition, showing an image so as to compensate for the area which a driver cannot see makes it possible for the driver to confirm safety easily and comfortably.
The display portion 9714, the display portion 9715, and the display portion 9722 can display a variety of kinds of information such as navigation data, a speedometer, a tachometer, a mileage, a fuel meter, a gearshift indicator, and air-condition setting. The content, layout, or the like of the display on the display portions can be changed freely by a user as appropriate. The information listed above can also be displayed on the display portions 9710 to 9713, 9721, and 9723. The display portions 9710 to 9715 and 9721 to 9723 can also be used as lighting devices. The display portions 9710 to 9715 and 9721 to 9723 can also be used as heating devices.
The connection portion 8005 includes an electrode to connect a finder 8100, which will be described below, a stroboscope, or the like.
Although the lens 8006 of the camera 8000 here is detachable from the housing 8001 for replacement, the lens 8006 may be included in the housing 8001.
Images can be taken at the press of the shutter button 8004. In addition, images can be taken at the touch of the display portion 8002 which serves as a touch panel.
The display device or input/output device of one embodiment of the present invention can be used in the display portion 8002.
The finder 8100 includes a housing 8101, a display portion 8102, a button 8103, and the like.
The housing 8101 includes a connection portion for engagement with the connection portion 8005 of the camera 8000 so that the finder 8100 can be connected to the camera 8000. The connection portion includes an electrode, and an image or the like received from the camera 8000 through the electrode can be displayed on the display portion 8102.
The button 8103 has a function of a power button, and the display portion 8102 can be turned on and off with the button 8103.
The semiconductor device of one embodiment of the present invention can be used for an integrated circuit and an image sensor included in the housing 8101.
Although the camera 8000 and the finder 8100 are separate and detachable electronic devices in
The head-mounted display 8200 includes a mounting portion 8201, a lens 8202, a main body 8203, a display portion 8204, a cable 8205, and the like. The mounting portion 8201 includes a battery 8206.
Power is supplied from the battery 8206 to the main body 8203 through the cable 8205. The main body 8203 includes a wireless receiver or the like to receive video data, such as image data, and display it on the display portion 8204. The movement of the eyeball and the eyelid of a user is captured by a camera in the main body 8203 and then coordinates of the points the user looks at are calculated using the captured data to utilize the eye point of the user as an input means.
The mounting portion 8201 may include a plurality of electrodes so as to be in contact with the user. The main body 8203 may be configured to sense current flowing through the electrodes with the movement of the user's eyeball to recognize the direction of his or her eyes. The main body 8203 may be configured to sense current flowing through the electrodes to monitor the user's pulse. The mounting portion 8201 may include sensors, such as a temperature sensor, a pressure sensor, or an acceleration sensor so that the user's biological information can be displayed on the display portion 8204. The main body 8203 may be configured to sense the movement of the user's head or the like to move an image displayed on the display portion 8204 in synchronization with the movement of the user's head or the like.
The semiconductor device of one embodiment of the present invention can be used for an integrated circuit included in the main body 8203.
At least part of this embodiment can be implemented in combination with any of the embodiments described in this specification as appropriate.
In this embodiment, application examples of an RF tag using the semiconductor device of one embodiment of the present invention will be described with reference to
<Application Examples of RF Tag>
The RF tag is widely used and can be provided for, for example, products such as bills, coins, securities, bearer bonds, documents (e.g., driver's licenses or resident's cards, see
An RF tag 4000 of one embodiment of the present invention is fixed to a product by being attached to a surface thereof or embedded therein. For example, the RF tag 4000 is fixed to each product by being embedded in paper of a book, or embedded in an organic resin of a package. Since the RF tag 4000 of one embodiment of the present invention can be reduced in size, thickness, and weight, it can be fixed to a product without spoiling the design of the product. Furthermore, bills, coins, securities, bearer bonds, documents, or the like can have an identification function by being provided with the RF tag 4000 of one embodiment of the present invention, and the identification function can be utilized to prevent counterfeiting. Moreover, the efficiency of a system such as an inspection system can be improved by providing the RF tag of one embodiment of the present invention for packaging containers, recording media, personal belongings, foods, clothing, household goods, electronic devices, or the like. Vehicles can also have higher security against theft or the like by being provided with the RF tag of one embodiment of the present invention.
As described above, by using the RF tag including the semiconductor device of one embodiment of the present invention for each application described in this embodiment, power for operation such as writing or reading of data can be reduced, which results in an increase in the maximum communication distance. Moreover, data can be held for an extremely long period even in the state where power is not supplied; thus, the RF tag can be favorably used for application in which data is not frequently written or read.
This embodiment can be combined as appropriate with any of the other embodiments and an example in this specification.
In this example, measurement results of the resistance of the oxide semiconductor layer 122 after ion addition treatment will be described.
A measurement sample with a structure illustrated in
As the substrate 100, a Si wafer with a thickness of approximately 700 μm was used.
As the insulating layer 110, a stack including a silicon oxide film and a silicon oxynitride film was formed.
A 100-nm-thick thermal oxide film was formed as the silicon oxide film by hydrochloric acid oxidation of the Si wafer at 950° C.
The silicon oxynitride film was formed to have a thickness of 300 nm by a plasma CVD method. The deposition conditions were as follows: the gas flow rates of silane and dinitrogen monoxide were 2.3 sccm and 800 sccm, respectively; the pressure in a chamber was controlled to be 40 Pa using a diaphragm-type baratron sensor and an APC valve; the RF power frequency was 27 MHz; the power was 50 W; the distance between electrodes was 15 mm; and the substrate heating temperature was 400° C.
As the oxide semiconductor layer 122, an oxide semiconductor film formed by a sputtering method to have a thickness of 50 nm using an oxide having an atomic ratio of In:Ga:Zn=1:1:1 as a target was used. The deposition conditions were as follows: the pressure in a chamber was 0.7 Pa; a DC power source was used and the power was 0.5 kW; the sputtering gas flow rates of an Ar gas and an oxygen gas were 30 sccm and 15 sccm, respectively; the distance between the sample and the target was 60 mm; and the substrate heating temperature was 300° C.
After the oxide semiconductor layer 122 was formed, heat treatment was performed at 450° C. in a nitrogen atmosphere for an hour, and then heat treatment was performed at 450° C. in an oxygen atmosphere for an hour.
The ion addition treatment was performed by an ion implantation method. Table 1 lists the ion implantation conditions that vary from one sample to another.
The resistance measurement was performed on the samples with a sheet resistance measurement equipment “VR-200” manufactured by Hitachi Kokusai Electric Inc.
The results in
10: transistor, 11: transistor, 12: transistor, 13: transistor, 14: transistor, 20: display device, 21: display region, 22: peripheral circuit, 24: display device, 50: transistor, 52: transistor, 60: capacitor, 62: capacitor, 70: light-emitting element, 80: liquid crystal element, 100: substrate, 103: polarizing plate, 105: protective substrate, 110: insulating layer, 121: metal oxide layer, 122: oxide semiconductor layer, 123: metal oxide layer, 123a: metal oxide film, 123b: metal oxide layer, 125: low-resistance region, 130: source electrode layer, 130b: conductive layer, 140: drain electrode layer, 150: gate insulating layer, 150a: insulating film, 150b: gate insulating layer, 151: gate insulating layer, 152: gate insulating layer, 152a: insulating film, 152b: insulating layer, 160: gate electrode layer, 160a: conductive film, 165: conductive layer, 167: ion, 170: insulating layer, 172: insulating layer, 173: oxygen, 174: groove portion, 175: insulating layer, 175b: insulating layer, 176: insulating layer, 180: insulating layer, 190: conductive layer, 195: conductive layer, 197: conductive layer, 200: imaging device, 201: switch, 202: switch, 203: switch, 210: pixel portion, 211: pixel, 212: sub-pixel, 212B: sub-pixel, 212G: sub-pixel, 212R: sub-pixel, 220: photoelectric conversion element, 230: pixel circuit, 231: wiring, 247: wiring, 248: wiring, 249: wiring, 250: wiring, 253: wiring, 254: filter, 254B: filter, 254G: filter, 254R: filter, 255: lens, 256: light, 257: wiring, 260: peripheral circuit, 270: peripheral circuit, 280: peripheral circuit, 290: peripheral circuit, 300: silicon substrate, 310: layer, 320: layer, 330: layer, 340: layer, 351: transistor, 353: transistor, 360: photodiode, 361: anode, 362: cathode, 363: low-resistance region, 365: photodiode, 366: semiconductor, 367: semiconductor, 368: semiconductor, 370: plug, 371: wiring, 372: wiring, 373: wiring, 374: wiring, 380: insulating layer, 400: substrate, 402: protective substrate, 403: polarizing plate, 410: conductive layer, 415: conductive layer, 418: light-blocking layer, 420: insulating layer, 430: insulating layer, 440: spacer, 445: partition, 450: EL layer, 460: coloring layer, 470: adhesive layer, 473: adhesive layer, 474: adhesive layer, 475: adhesive layer, 476: adhesive layer, 480: conductive layer, 490: liquid crystal layer, 510: anisotropic conductive layer, 530: optical adjustment layer, 601: precursor, 602: precursor, 700: substrate, 701: pixel portion, 702: scan line driver circuit, 703: scan line driver circuit, 704: signal line driver circuit, 710: capacitor wiring, 712: scan line, 713: scan line, 714: signal line, 716: transistor, 717: transistor, 718: liquid crystal element, 719: liquid crystal element, 720: pixel, 721: switching transistor, 722: driver transistor, 723: capacitor, 724: light-emitting element, 725: signal line, 726: scan line, 727: power line, 728: common electrode, 800: RF tag, 801: communication device, 802: antenna, 803: radio signal, 804: antenna, 805: rectifier circuit, 806: constant voltage circuit, 807: demodulation circuit, 808: modulation circuit, 809: logic circuit, 810: memory circuit, 811: ROM, 1189: ROM interface, 1190: substrate, 1191: ALU, 1192: ALU controller, 1193: instruction decoder, 1194: interrupt controller, 1195: timing controller, 1196: register, 1197: register controller, 1198: bus interface, 1199: ROM, 1200: memory element, 1201: circuit, 1202: circuit, 1203: switch, 1204: switch, 1206: logic element, 1207: capacitor, 1208: capacitor, 1209: transistor, 1210: transistor, 1213: transistor, 1214: transistor, 1220: circuit, 1700: substrate, 1701: chamber, 1702: load chamber, 1703: pretreatment chamber, 1704: chamber, 1705: chamber, 1706: unload chamber, 1711a: source material supply portion, 1711b: source material supply portion, 1712a: high-speed valve, 1712b: high-speed valve, 1713a: source material introduction port, 1713b: source material introduction port, 1714: source material exhaust port, 1715: evacuation unit, 1716: substrate holder, 1720: transfer chamber, 1750: interposer, 1751: chip, 1752: terminal, 1753: mold resin, 1800: panel, 1801: printed wiring board, 1802: package, 1803: FPC, 1804: battery, 2100: transistor, 2200: transistor, 2201: insulator, 2202: wiring, 2203: plug, 2204: insulator, 2205: wiring, 2207: insulator, 2211: semiconductor substrate, 2212: insulator, 2213: gate electrode, 2214: gate insulator, 2215: source and drain regions, 2800: inverter, 2810: OS transistor, 2820: OS transistor, 2831: signal waveform, 2832: signal waveform, 2840: dashed line, 2841: solid line, 2850: OS transistor, 2860: CMOS inverter, 3001: wiring, 3002: wiring, 3003: wiring, 3004: wiring, 3005: wiring, 3200: transistor, 3300: transistor, 3400: capacitor, 4000: RF tag, 6000: display module, 6001: upper cover, 6002: lower cover, 6003: FPC, 6004: touch panel, 6005: FPC, 6006: display panel, 6007: backlight unit, 6008: light source, 6009: frame, 6010: print substrate, 6011: battery, 7101: housing, 7102: housing, 7103: display portion, 7104: display portion, 7105: microphone, 7106: speaker, 7107: operation key, 7108: stylus, 7302: housing, 7304: display portion, 7311: operation button, 7312: operation button, 7313: connection terminal, 7321: band, 7322: clasp, 7501: housing, 7502: display portion, 7503: operation button, 7504: external connection port, 7505: speaker, 7506: microphone, 7701: housing, 7702: housing, 7703: display portion, 7704: operation key, 7705: lens, 7706: connection portion, 7901: utility pole, 7902: display portion, 8000: camera, 8001: housing, 8002: display portion, 8003: operation button, 8004: shutter button, 8005: connection portion, 8006: lens, 8100: finder, 8101: housing, 8102: display portion, 8103: button, 8121: housing, 8122: display portion, 8123: keyboard, 8124: pointing device, 8200: head-mounted display, 8201: mounting portion, 8202: lens, 8203: main body, 8204: display portion, 8205: cable, 8206: battery, 9700: automobile, 9701: car body, 9702: wheel, 9703: dashboard, 9704: light, 9710: display portion, 9711: display portion, 9712: display portion, 9713: display portion, 9714: display portion, 9715: display portion, 9721: display portion, 9722: display portion, and 9723: display portion.
This application is based on Japanese Patent Application serial no. 2015-123865 filed with Japan Patent Office on Jun. 19, 2015, Japanese Patent Application serial no. 2015-124067 filed with Japan Patent Office on Jun. 19, 2015, and Japanese Patent Application serial no. 2016-101672 filed with Japan Patent Office on May 20, 2016, the entire contents of which are hereby incorporated by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2015-123865 | Jun 2015 | JP | national |
| 2015-124067 | Jun 2015 | JP | national |
| 2016-101672 | May 2016 | JP | national |
This application is a divisional of U.S. application Ser. No. 15/182,812, filed Jun. 15, 2016, now allowed, which claims the benefit of foreign priority applications filed in Japan as Serial No. 2015-123865 on Jun. 19, 2015, Serial No. 2015-124067 on Jun. 19, 2015, and Serial No. 2016-101672 on May 20, 2016, all of which are incorporated by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 5731856 | Kim et al. | Mar 1998 | A |
| 5744864 | Cillessen et al. | Apr 1998 | A |
| 6294274 | Kawazoe et al. | Sep 2001 | B1 |
| 6563174 | Kawasaki et al. | May 2003 | B2 |
| 6673683 | Sheu et al. | Jan 2004 | B1 |
| 6727522 | Kawasaki et al. | Apr 2004 | B1 |
| 6841831 | Hanafi et al. | Jan 2005 | B2 |
| 7049190 | Takeda et al. | May 2006 | B2 |
| 7061014 | Hosono et al. | Jun 2006 | B2 |
| 7064346 | Kawasaki et al. | Jun 2006 | B2 |
| 7105868 | Nause et al. | Sep 2006 | B2 |
| 7211825 | Shih et al. | May 2007 | B2 |
| 7282782 | Hoffman et al. | Oct 2007 | B2 |
| 7297977 | Hoffman et al. | Nov 2007 | B2 |
| 7323356 | Hosono et al. | Jan 2008 | B2 |
| 7385224 | Ishii et al. | Jun 2008 | B2 |
| 7402506 | Levy et al. | Jul 2008 | B2 |
| 7411209 | Endo et al. | Aug 2008 | B2 |
| 7453065 | Saito et al. | Nov 2008 | B2 |
| 7453087 | Iwasaki | Nov 2008 | B2 |
| 7462862 | Hoffman et al. | Dec 2008 | B2 |
| 7468304 | Kaji et al. | Dec 2008 | B2 |
| 7501293 | Ito et al. | Mar 2009 | B2 |
| 7674650 | Akimoto et al. | Mar 2010 | B2 |
| 7732819 | Akimoto et al. | Jun 2010 | B2 |
| 7791072 | Kumomi et al. | Sep 2010 | B2 |
| 8779418 | Miyanaga | Jul 2014 | B2 |
| 8822991 | Sakata | Sep 2014 | B2 |
| 9142593 | Okano | Sep 2015 | B2 |
| 20010046027 | Tai et al. | Nov 2001 | A1 |
| 20020056838 | Ogawa | May 2002 | A1 |
| 20020132454 | Ohtsu et al. | Sep 2002 | A1 |
| 20030189401 | Kido et al. | Oct 2003 | A1 |
| 20030218222 | Wager, III et al. | Nov 2003 | A1 |
| 20040038446 | Takeda et al. | Feb 2004 | A1 |
| 20040127038 | Carcia et al. | Jul 2004 | A1 |
| 20050017302 | Hoffman | Jan 2005 | A1 |
| 20050199959 | Chiang et al. | Sep 2005 | A1 |
| 20060035452 | Carcia et al. | Feb 2006 | A1 |
| 20060043377 | Hoffman et al. | Mar 2006 | A1 |
| 20060091793 | Baude et al. | May 2006 | A1 |
| 20060108529 | Saito et al. | May 2006 | A1 |
| 20060108636 | Sano et al. | May 2006 | A1 |
| 20060110867 | Yabuta et al. | May 2006 | A1 |
| 20060113536 | Kumomi et al. | Jun 2006 | A1 |
| 20060113539 | Sano et al. | Jun 2006 | A1 |
| 20060113549 | Den et al. | Jun 2006 | A1 |
| 20060113565 | Abe et al. | Jun 2006 | A1 |
| 20060169973 | Isa et al. | Aug 2006 | A1 |
| 20060170111 | Isa et al. | Aug 2006 | A1 |
| 20060197092 | Hoffman et al. | Sep 2006 | A1 |
| 20060208977 | Kimura | Sep 2006 | A1 |
| 20060228974 | Thelss et al. | Oct 2006 | A1 |
| 20060231882 | Kim et al. | Oct 2006 | A1 |
| 20060238135 | Kimura | Oct 2006 | A1 |
| 20060244107 | Sugihara et al. | Nov 2006 | A1 |
| 20060284171 | Levy et al. | Dec 2006 | A1 |
| 20060284172 | Ishii | Dec 2006 | A1 |
| 20060292777 | Dunbar | Dec 2006 | A1 |
| 20070024187 | Shin et al. | Feb 2007 | A1 |
| 20070046191 | Saito | Mar 2007 | A1 |
| 20070052025 | Yabuta | Mar 2007 | A1 |
| 20070054507 | Kaji et al. | Mar 2007 | A1 |
| 20070090365 | Hayashi et al. | Apr 2007 | A1 |
| 20070108446 | Akimoto | May 2007 | A1 |
| 20070152217 | Lai et al. | Jul 2007 | A1 |
| 20070172591 | Seo et al. | Jul 2007 | A1 |
| 20070187678 | Hirao et al. | Aug 2007 | A1 |
| 20070187760 | Furuta et al. | Aug 2007 | A1 |
| 20070194379 | Hosono et al. | Aug 2007 | A1 |
| 20070252928 | Ito et al. | Nov 2007 | A1 |
| 20070272922 | Kim et al. | Nov 2007 | A1 |
| 20070287296 | Chang | Dec 2007 | A1 |
| 20080006877 | Mardilovich et al. | Jan 2008 | A1 |
| 20080038882 | Takechi et al. | Feb 2008 | A1 |
| 20080038929 | Chang | Feb 2008 | A1 |
| 20080050595 | Nakagawara et al. | Feb 2008 | A1 |
| 20080073653 | Iwasaki | Mar 2008 | A1 |
| 20080083950 | Pan et al. | Apr 2008 | A1 |
| 20080106191 | Kawase | May 2008 | A1 |
| 20080128689 | Lee et al. | Jun 2008 | A1 |
| 20080129195 | Ishizaki et al. | Jun 2008 | A1 |
| 20080166834 | Kim et al. | Jul 2008 | A1 |
| 20080182358 | Cowdery-Corvan et al. | Jul 2008 | A1 |
| 20080224133 | Park et al. | Sep 2008 | A1 |
| 20080254569 | Hoffman et al. | Oct 2008 | A1 |
| 20080258139 | Ito et al. | Oct 2008 | A1 |
| 20080258140 | Lee et al. | Oct 2008 | A1 |
| 20080258141 | Park et al. | Oct 2008 | A1 |
| 20080258143 | Kim et al. | Oct 2008 | A1 |
| 20080296568 | Ryu et al. | Dec 2008 | A1 |
| 20090068773 | Lai et al. | Mar 2009 | A1 |
| 20090073325 | Kuwabara et al. | Mar 2009 | A1 |
| 20090114910 | Chang | May 2009 | A1 |
| 20090134399 | Sakakura et al. | May 2009 | A1 |
| 20090152506 | Umeda et al. | Jun 2009 | A1 |
| 20090152541 | Maekawa et al. | Jun 2009 | A1 |
| 20090278122 | Hosono et al. | Nov 2009 | A1 |
| 20090280600 | Hosono et al. | Nov 2009 | A1 |
| 20100065844 | Tokunaga | Mar 2010 | A1 |
| 20100092800 | Itagaki et al. | Apr 2010 | A1 |
| 20100109002 | Itagaki et al. | May 2010 | A1 |
| 20110084272 | Miyanaga | Apr 2011 | A1 |
| 20140361289 | Suzawa | Dec 2014 | A1 |
| 20150060896 | Okano | Mar 2015 | A1 |
| 20150187775 | Yamamoto et al. | Jul 2015 | A1 |
| 20150187898 | Miyairi | Jul 2015 | A1 |
| 20150270402 | Endo et al. | Sep 2015 | A1 |
| 20150280013 | Yamazaki et al. | Oct 2015 | A1 |
| 20160284859 | Asami | Sep 2016 | A1 |
| Number | Date | Country |
|---|---|---|
| 1737044 | Dec 2006 | EP |
| 2226847 | Sep 2010 | EP |
| 60-198861 | Oct 1985 | JP |
| 63-210022 | Aug 1988 | JP |
| 63-210023 | Aug 1988 | JP |
| 63-210024 | Aug 1988 | JP |
| 63-215519 | Sep 1988 | JP |
| 63-239117 | Oct 1988 | JP |
| 63-265818 | Nov 1988 | JP |
| 05-251705 | Sep 1993 | JP |
| 08-264794 | Oct 1996 | JP |
| 11-505377 | May 1999 | JP |
| 2000-044236 | Feb 2000 | JP |
| 2000-150900 | May 2000 | JP |
| 2002-076356 | Mar 2002 | JP |
| 2002-289859 | Oct 2002 | JP |
| 2003-086000 | Mar 2003 | JP |
| 2003-086808 | Mar 2003 | JP |
| 2004-103957 | Apr 2004 | JP |
| 2004-273614 | Sep 2004 | JP |
| 2004-273732 | Sep 2004 | JP |
| 2006-165528 | Jun 2006 | JP |
| 2015-015458 | Jan 2015 | JP |
| 2015-144251 | Aug 2015 | JP |
| 2015-187902 | Oct 2015 | JP |
| 201533903 | Sep 2015 | TW |
| WO-2004114391 | Dec 2004 | WO |
| WO-2015097633 | Jul 2015 | WO |
| Entry |
|---|
| Asakuma.N et al., “Crystallization and Reduction of Sol-Gel-Derived Zinc Oxide Films by Irradiation With Ultraviolet Lamp”, Journal of Sol-Gel Science and Technology, 2003, vol. 26, pp. 181-184. |
| Asaoka.Y et al., “29.1:Polarizer-Free Reflective LCD Combined With Ultra Low-Power Driving Technology”, SID Digest '09 : SID International Symposium Digest of Technical Papers, May 31, 2009, pp. 395-398. |
| Chern.H et al., “An Analytical Model for the Above-Threshold Characteristics of Polysilicon Thin-Film Transistors”, IEEE Transactions on Electron Devices, Jul. 1, 1995, vol. 42, No. 7, pp. 1240-1246. |
| Cho.D et al., “21.2:Al and Sn-Doped Zinc Indium Oxide Thin Film Transistors for AMOLED Back-Plane”, SID Digest '09 : SID International Symposium Digest of Technical Papers, May 31, 2009, pp. 280-283. |
| Clark.S et al., “First Principles Methods Using CASTEP”, Zeitschrift fur Kristallographie, 2005, vol. 220, pp. 567-570. |
| Coates.D et al., “Optical Studies of the Amorphous Liquid-Cholesteric Liquid Crystal Transition:The “Blue Phase””, Physics Letters, Sep. 10, 1973, vol. 45A, No. 2, pp. 115-116. |
| Costello.M et al., “Electron Microscopy of a Cholesteric Liquid Crystal and its Blue Phase”, Phys. Rev. A (Physical Review, A) May 1, 1984, vol. 29, No. 5, pp. 2957-2959. |
| Dembo.H et al., “RFCPUS on Glass and Plastic Substrates Fabricated by TFT Transfer Technology”, IEDM 05: Technical Digest of International Electron Devices Meeting, Dec. 5, 2005, pp. 1067-1069 |
| Fortunato.E et al., “Wide-Bandgap High-Mobility ZnO Thin-Film Transistors Produced at Room Temperature”, Appl. Phys. Lett. (Applied Physics Letters) , Sep. 27, 2004, vol. 85, No. 13, pp. 2541-2543. |
| Fung.T et al., “2-D Numerical Simulation of High Performance Amorphous In—Ga—Zn—O TFTs for Flat Panel Displays”, AM-FPD '08 Digest of Technical Papers, Jul. 2, 2008, pp. 251-252, The Japan Society of Applied Physics. |
| Godo.H et al., “P-9:Numerical Analysis on Temperature Dependence of Characteristics of Amorphous In—Ga—Zn-Oxide TFT”, SID Digest '09 : SID International Symposium Digest of Technical Papers, May 31, 2009, pp. 1110-1112. |
| Godo.H et al., “Temperature Dependence of Characteristics and Electronic Structure for Amorphous In—Ga—Zn-Oxide TFT”, AM-FPD '09 Digest of Technical Papers, Jul. 1, 2009, pp. 41-44. |
| Hayashi.R et al., “42.1: Invited Paper: Improved Amorphous In—Ga—Zn—O TFTs”, SID Digest '08 : SID International Symposium Digest of Technical Papers, May 20, 2008, vol. 39, pp. 621-624. |
| Hirao.T et al., “Novel Top-Gate Zinc Oxide Thin-Film Transistors (ZnO TFTs) for AMLCDs”, J. Soc. Inf. Display (Journal of the Society for Information Display), 2007, vol. 15, No. 1, pp. 17-22. |
| Hosono.H et al., “Working hypothesis to explore novel wide band gap electrically conducting amorphous oxides and examples”, J. Non-Cryst. Solids (Journal of Non-Crystalline Solids), 1996, vol. 198-200, pp. 165-169. |
| Hosono.H, “68.3:Invited Paper:Transparent Amorphous Oxide Semiconductors for High Performance TFT”, SID Digest '07 : SID International Symposium Digest of Technical Papers, 2007, vol. 38, pp. 1830-1833. |
| Hsieh.H et al., “P-29:Modeling of Amorphous Oxide Semiconductor Thin Film Transistors and Subgap Density of States”, SID Digest '08 : SID International Symposium Digest of Technical Papers, May 20, 2008, vol. 39, pp. 1277-1280. |
| Ikeda.T et al., “Full-Functional System Liquid Crystal Display Using CG-Silicon Technology”, SID Digest '04 : SID International Symposium Digest of Technical Papers, 2004, vol. 35, pp. 860-863. |
| Janotti.A et al., “Native Point Defects in ZnO”, Phys. Rev. B (Physical Review. B), Oct. 4, 2007, vol. 76, No. 16, pp. 165202-1-165202-22. |
| Janotti.A et al., “Oxygen Vacancies in ZnO”, Appl. Phys. Lett. (Applied Physics Letters) , 2005, vol. 87, pp. 122102-1-122102-3. |
| Jeong.J et al., “3.1: Distinguished Paper: 12.1-Inch WXGA AMOLED Display Driven by Indium-Gallium-Zinc Oxide TFTs Array”, SID Digest '08 : SID International Symposium of Technical Papers, May 20, 2008, vol. 39, No. 1, pp. 1-4. |
| Jin.D et al., “65.2:Distinguished Paper:World-Largest (6.5″) Flexible Full Color Top Emission AMOLED Display on Plastic Film and Its Bending Properties”, SID Digest '09 : SID International Symposium Digest of Technical Papers, May 31, 2009, pp. 983-985. |
| Kanno.H et al., “White Stacked Electrophosphorecent Organic Light-Emitting Devices Emplying MOO3 as a Charge-Generation Layer”, Adv. Mater. (Advanced Materials) , 2006, vol. 18, No. 3, pp. 339-342. |
| Kikuchi.H et al., “39.1:Invited Paper:Optically Isotropic Nano-Structured Liquid Crystal Composites for Display Applications”, SID Digest '09 : SID International Symposium Digest of Technical Papers, May 31, 2009, pp. 578-581. |
| Kikuchi.H et al., “62.2:Invited Paper:Fast Electro-Optical Switching in Polymer-Stabilized Liquid Crystalline Blue Phases for Display Application”, SID Digest '07 : SID International Symposium Digest of Technical Papers, 2007, vol. 38, pp. 1737-1740. |
| Kikuchi.H et al., “Polymer-Stabilized Liquid Crystal Blue Phases”, Nature Materials, Sep. 2, 2002, vol. 1, pp. 64-68. |
| Kim.S et al., “High-Performance oxide thin film transistors passivated by various gas plasmas”, 214th ECS Meeting, 2008, No. 2317, ECS. |
| Kimizuka.N et al., “Spinel,YbFe2O4, and Yb2Fe3O7 Types of Structures for Compounds in the In2O3 and Sc2O3—A2O3—Bo Systems [A; Fe, or Al; B: Mn, Fe, Ni, Cu,or Zn]at Temperatures over 1000° C.”, Journal of Solid State Chemistry, 1985, vol. 60, pp. 382-384. |
| Kimizuka.N et al., “Syntheses and Single-Crystal Data of Homologous Compounds, In2O3(ZnO)m (m=3, 4, and 5), InGaO3(ZnO)3, and Ga2O3(ZnO)m (m=7, 8, 9, and 16) in the In2O3—ZnGa2O4—ZnO System”, Journal of Solid State Chemistry, Apr. 1, 1995, vol. 116, No. 1, pp. 170-178. |
| Kitzerow.H et al., “Observation of Blue Phases in Chiral Networks”, Liquid Crystals, 1993, vol. 14, No. 3, pp. 911-916. |
| Kurokawa.Y et al., “UHF RFCPUS on Flexible and Glass Substrates for Secure RFID Systems”, Journal of Solid-State Circuits , 2008, vol. 43, No. 1. 292-299. |
| Lany.S et al., “Dopability, Intrinsic Conductivity, and Nonstoichiometry of Transparent Conducting Oxides”, Phys. Rev. Lett. (Physical Review Letters), Jan. 26, 2007, vol. 98, pp. 045501-1-045501-4. |
| Lee.H et al., “Current Status of, Challenges to, and Perspective View of AM-OLED”, IDW '06 : Proceedings of the 13th International Display Workshops, Dec. 7, 2006, pp. 663-666. |
| Lee.J et al., “World's Largest (15-Inch) XGA AMLCD Panel Using IGZO Oxide TFT”, SID Digest '08 : SID International Symposium Digest of Technical Papers, May 20, 2008, vol. 39, pp. 625-628. |
| Lee.M et al., “15.4:Excellent Performance of Indium-Oxide-Based Thin-Film Transistors by DC Sputtering”, SID Digest '09 : SID International Symposium of Technical Papers, May 31, 2009, pp. 191-193. |
| Li.C et al., “Modulated Structures of Homologous Compounds InMO3(ZnO)m (M=In,Ga; m=Integer) Described by Four-Dimensional Superspace Group”, Journal of Solid State Chemistry, 1998, vol. 139, pp. 347-355. |
| Masuda.S et al., “Transparent thin film transistors using ZnO as an active channel layer and their electrical properties”, J. Appl. Phys. (Journal of Applied Physics) , Feb. 1, 2003, vol. 93, No. 3, pp. 1624-1630. |
| Meiboom.S et al., “Theory of the Blue Phase of Cholesteric Liquid Crystals”, Phys. Rev. Lett. (Physical Review Letters), May 4, 1981, vol. 46, No. 18, pp. 1216-1219. |
| Miyasaka.M, “SUFTLA Flexible Microelectronics on Their Way to Business”, SID Digest '07 : SID International Symposium Digest of Technical Papers, 2007, vol. 38, pp. 1673-1676. |
| Mo.Y et al., “Amorphous Oxide TFT Backplanes for Large Size AMOLED Displays”, IDW '08 : Proceedings of The 6th International Display Workshops, Dec. 3, 2008, pp. 581-584. |
| Nakamura.M et al., “The phase relations in the In2O3—Ga2ZnO4—ZnO system at 1350° C.”, Journal of Solid State Chemistry, Aug. 1, 1991, vol. 93, No. 2, pp. 298-315. |
| Nakamura.M, “Synthesis of Homologous Compound with New Long-Period Structure”, Nirim Newsletter, Mar. 1, 1995, vol. 150, pp. 1-4. |
| Nomura.K et al., “Amorphous Oxide Semiconductors for High-Performance Flexible Thin-Film Transistors”, Jpn. J. Appl. Phys. (Japanese Journal of Applied Physics) , 2006, vol. 45, No. 5B, pp. 4303-4308. |
| Nomura.K et al., “Carrier transport in transparent oxide semiconductor with intrinsic structural randomness probed using single-crystalline InGaO3(ZnO)5 films”, Appl. Phys. Lett. (Applied Physics Letters) , Sep. 13, 2004, vol. 85, No. 11, pp. 1993-1995. |
| Nomura.K et al., “Room-Temperature Fabrication of Transparent Flexible Thin-Film Transistors Using Amorphous Oxide Semiconductors”, Nature, Nov. 25, 2004, vol. 432, pp. 488-492. |
| Nomura.K et al., “Thin-Film Transistor Fabricated in Single-Crystalline Transparent Oxide Semiconductor”, Science, May 23, 2003, vol. 300, No. 5623, pp. 1269-1272. |
| Nowatari.H et al., “60.2: Intermediate Connector With Suppressed Voltage Loss for White Tandem OLEDs”, SID Digest '09 : SID International Symposium Digest of Technical Papers, May 31, 2009, vol. 40, pp. 899-902. |
| Oba.F et al., “Defect energetics in ZnO: A hybrid Hartree-Fock density functional study”, Phys. Rev. B (Physical Review. B), 2008, vol. 77, pp. 245202-1-245202-6. |
| Oh.M et al., “Improving the Gate Stability of ZnO Thin-Film Transistors With Aluminum Oxide Dielectric Layers”, J. Electrochem. Soc. (Journal of the Electrochemical Society), 2008, vol. 155, No. 12, pp. H1009-H1014. |
| Ohara.H et al., “21.3:4.0 In. QVGA AMOLED Display Using In—Ga—Zn-Oxide TFTs With a Novel Passivation Layer”, SID Digest '09 : SID International Symposium Digest of Technical Papers, May 31, 2009, pp. 284-287. |
| Ohara.H et al., “Amorphous In—Ga—Zn-Oxide TFTs with Suppressed Variation for 4.0 inch QVGA AMOLED Display”, AM-FPD '09 Digest of Technical Papers, Jul. 1, 2009, pp. 227-230, The Japan Society of Applied Physics. |
| Orita.M et al., “Amorphous transparent conductive oxide InGaO3(ZnO)m (m<4):a Zn4s conductor”, Philosophical Magazine, 2001, vol. 5, No. 5, pp. 501-515. |
| Orita.M et al., “Mechanism of Electrical Conductivity of Transparent InGaZnO4”, Phys. Rev. B (Physical Review. B), Jan. 15, 2000, vol. 61, No. 3, pp. 1811-1816. |
| Osada.T et al., “15.2: Development of Driver-Integrated Panel using Amorphous In—Ga—Zn-Oxide TFT”, SID Digest '09 : SID International Symposium Digest of Technical Papers, May 31, 2009, vol. 40, pp. 184-187. |
| Osada.T et al., “Development of Driver-Integrated Panel Using Amorphous In—Ga—Zn-Oxide TFT”, AM-FPD '09 Digest of Technical Papers, Jul. 1, 2009, pp. 33-36. |
| Park.J et al., “Amorphous Indium-Gallium-Zinc Oxide TFTs and Their Application for Large Size AMOLED”, AM-FPD '08 Digest of Technical Papers, Jul. 2, 2008, pp. 275-278. |
| Park.J et al., “Dry etching of ZnO films and plasma-induced damage to optical properties”, J. Vac. Sci. Technol. B (Journal of Vacuum Science & Technology B), Mar. 1, 2003, vol. 21, No. 2, pp. 800-803. |
| Park.J et al., “Electronic Transport Properties of Amorphous Indium-Gallium-Zinc Oxide Semiconductor Upon Exposure to Water”, Appl. Phys. Lett. (Applied Physics Letters) , 2008, vol. 92, pp. 072104-1-072104-3. |
| Park.J et al., “High performance amorphous oxide thin film transistors with self-aligned top-gate structure”, IEDM 09: Technical Digest of International Electron Devices Meeting, Dec. 7, 2009, pp. 191-194. |
| Park.J et al., “Improvements in The Device Characteristics of Amorphous Indium Gallium Zinc Oxide Thin-Film Transistors by Ar Plasma Treatment”, Appl. Phys. Lett. (Applied Physics Letters), Jun. 26, 2007, vol. 90, No. 26, pp. 262106-1-262106-3. |
| Park.S et al., “Challenge to Future Displays: Transparent AM-OLED Driven by Peald Grown ZnO TFT”, IMID '07 Digest, 2007, pp. 1249-1252. |
| Park.Sang-Hee et al., “42.3: Transparent ZnO Thin Film Transistor for the Application of High Aperture Ratio Bottom Emission AM-OLED Display”, SID Digest '08 : SID International Symposium Digest of Technical Papers, May 20, 2008, vol. 39, pp. 629-632. |
| Prins.M et al., “A Ferroelectric Transparent Thin-Film Transistor”, Appl. Phys. Lett. (Applied Physics Letters) , Jun. 17, 1996, vol. 68, No. 25, pp. 3650-3652. |
| Sakata.J et al., “Development of 4.0-In. AMOLED Display With Driver Circuit Using Amorphous In—Ga—Zn-Oxide TFTs”, IDW '09 : Proceedings of The 16th International Display Workshops, 2009, pp. 689-692 |
| Son.K et al., “42.4L: Late-News Paper: 4 Inch QVGA AMOLED Driven by The Threshold Voltage Controlled Amorphous GIZO (Ga2O3—In2O3—ZnO) TFT”, SID Digest '08 : SID International Symposium Digest of Technical Papers, May 20, 2008, vol. 39, pp. 633-636. |
| Takahashi.M et al., “Theoretical Analysis of IGZO Transparent Amorphous Oxide Semiconductor”, IDW '08 : Proceedings of The 15th International Display Workshops, Dec. 3, 2008, pp. 1637-1640. |
| Tsuda.K et al., “Ultra Low Power Consumption Technologies for Mobile TFT-LCDs”, IDW '02 : Proceedings of The 9th International Display Workshops, Dec. 4, 2002, pp. 295-298. |
| Ueno.K et al., “Field-Effect transistor on SrTiO3 With Sputtered Al2O3 Gate Insulator”, Appl. Phys. Lett. (Applied Physics Letters), Sep. 1, 2003, vol. 83, No. 9, pp. 1755-1757. |
| Van de Walle.C, “Hydrogen as a Cause of Doping in Zinc Oxide”, Phys. Rev. Lett. (Physical Review Letters), Jul. 31, 2000, vol. 85, No. 5, pp. 1012-1015. |
| International Search Report (Application No. PCT/IB2016/053461) dated Sep. 20, 2016. |
| Written Opinion (Application No. PCT/IB2016/053461) dated Sep. 20, 2016. |
| Number | Date | Country | |
|---|---|---|---|
| 20170288064 A1 | Oct 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15182812 | Jun 2016 | US |
| Child | 15628699 | US |
