Patent Grant
8758512
This application claims priority from and the benefit under 35 U.S.C. §119(e) of U.S. Patent Application No. 61/185,076, entitled “Reactor Apparatus For Atomic Layer Deposition And Method Of Forming Thin Film Using The Reactor Apparatus,” filed on Jun. 8, 2009, which is incorporated by reference herein in its entirety. This application is related to U.S. patent application Ser. No. 12/539,477, entitled “Vapor Deposition Reactor For Forming Thin Film,” filed on Aug. 11, 2009; U.S. patent application Ser. No. 12/539,490, entitled “Vapor Deposition Reactor,” filed on Aug. 11, 2009; and U.S. patent Ser. No. 12/560,690, entitled “Vapor Deposition Reactor Using Plasma And Method for Forming Thin Film Using the Same,” filed on Sep. 16, 2009, which are incorporated by reference herein in their entirety.
1. Field of the Invention
The disclosure relates to a vapor deposition reactor and a method for forming a thin film using the same.
2. Description of the Related Art
In general, a showerhead-type reactor is used in chemical vapor deposition (CVD) for injecting a precursor. In the showerhead-type reactor deposition is performed by mixing a source precursor and a reactant precursor within the interior of a showerhead and then spraying the mixed precursors onto a substrate. On the other hand, in a reactor for atomic layer deposition (ALD), a source precursor and a reactant precursor are alternately sprayed so that they are not mixed with each other. Based on the direction of the precursor spray, reactors are divided into (i) a cross-flow or traveling-wave type reactor and (ii) a type of reactor that injects the precursor vertically to the surface of the substrate. The cross-flow or traveling-wave type reactor injects a precursor in a direction parallel to a surface of a substrate surface for deposition of the precursor.
The ALD uses the bonding force of a chemisorbed layer that is different from the bonding force of a physisorbed layer. In the ALD, a precursor is absorbed into the surface of a substrate and then purged with an inert gas. As a result, physisorbed molecules of the precursor (bonded by the Van der Waals force) are desorbed from the substrate. However, chemisorbed molecules of the precursor are covalently bonded, and hence, these molecules are strongly adsorbed in the substrate. Hence, the chemisorbed molecules are not desorbed from the substrate. The ALD is performed using the properties that the chemisorbed molecules of the precursor (adsorbed in the substrate) react and/or replace a reactant precursor.
More specifically, a source precursor is injected into a chamber so that the source precursor is excessively adsorbed on a substrate. Then, the excessive precursor or physisorbed molecules are removed by injecting a purge gas and/or pumping the chamber, causing only chemisorbed molecules to remain on the substrate. The chemisorbed molecules results in a mono molecule layer. Subsequently, a reactant precursor (or replacement agent) is injected into the chamber. Then, the excessive precursor or physisorbed molecules are removed by injecting the purge gas and/or pumping the chamber, obtaining a final atomic layer.
In the ALD, a basic unit consisting of these four processes is usually referred to as a cycle. If a chemisorbed layer in a saturation state is obtained, a deposition velocity of about 1 Å per cycle is obtained. However, when a precursor is not adsorbed on the substrate in the saturation state, a deposition velocity is slower than about 1 Å per cycle. If the physisorbed molecule layer is not completely removed but a portion of the physisorbed molecule layer remains on the substrate, the deposition velocity is increased.
In the ALD, one atomic monolayer is usually formed per cycle. In the ALD, a source precursor, a reactant precursor and a purge gas are repeatedly injected into a chamber, and a valve and a pump are used for exhaustion. For example, the ALD technique has been disclosed in U.S. Pat. Nos. 7,422,636, 7,402,210, 6,511,539 and 6,820,570, which are incorporated by reference herein in their entirety.
If precursors injected into a chamber in each process remain in the chamber, a vapor phase reaction (referred to as a CVD reaction) occurs through the reaction of a source precursor and a reactant precursor. Therefore, only a valve for ALD operated at a high speed is necessary to perform the ALD, and purging and/or pumping must be performed so that no precursor remains in the chamber. At this time, the valve used for ALD requires an extended operation times. For example, operation times of more than 103 for each of the processes of injecting the source precursor, purging, injecting the reactant precursor, purging and the like are usually necessary to deposit an atomic layer with a thickness of 100 nm. As a result, the lifetime of the valve is shortened, and its reliability is decreased. As the number of operation times of the valve operated at a high speed is increased, problems related to the lifetime of the valve occur, such as erroneous operations or particles.
However, when a thin film is formed using the ALD, it is important to form the thin film having uniform characteristics (i.e., physical, chemical and electrical characteristics) required to satisfy requirements of a device. To this end, it is necessary that times at which the respective source and reactant precursors reach a substrate be identical in the injection of the source and the reactant precursor. In the cross-flow or traveling-wave type reactor in which precursors used for the ALD are injected parallel to a substrate, an adsorption phenomenon is gradually performed while the substrate is passes from the side adjacent to an injection portion of the precursors and to the side of an exhaust portion. Therefore, the adsorption phenomenon is represented by a function of time. Particularly, for a large-area substrate, such a phenomenon becomes more pronounced, and therefore, the composition, thickness or property of the thin film varies depending on each portion of the substrate. Particularly, the compositions, thicknesses or properties of the thin films respectively positioned at the injection and exhaust portions are different from each other.
In the reactor for receiving the precursors, the precursors are injected in a direction vertical to the substrate to avoid such a problem. However, when the distance between the injection portion (typically, showerhead) of the precursors and the substrate is short, the thickness of the thin film is increased or decreased by the proximity phenomenon in the vicinity of a hole of the showerhead through which the precursors are injected, and therefore, an irregular thin film having a hole pattern of the showerhead is obtained. Accordingly, the distance between the injection portion and the substrate need to be sufficiently large. As a result, the space portion of the chamber is increased. Also, a large amount of precursor is required because a sufficient amount of precursor is necessarily filled in the interior of the chamber for the purpose of saturation adsorption of precursors on a surface of the substrate. Also, the source precursors and the reactant precursors do not come in contact with each other so as to avoid a CVD reaction. Therefore, much time is taken to perform sufficient purging and/or pumping to prevent the source precursors or reactant precursors from remaining in the chamber. In addition, since the source precursors and the reactant precursors are exhausted through the same exhaust line, a reactant byproduct (e.g., powder, gum or the like) is produced by the reaction of these precursors. Therefore, the reliability, durability and economy of the device are decreased as well as yielding thinner film.
In U.S. Pat. No. 6,821,563, for example, gas steam flowed through a plurality of gas ports is supplied to a substrate, and purge and pump ports are installed adjacent to each other so that the ALD is performed by purging and pumping while consecutively injecting precursors. However, partitions for isolating or separating the ports from each other are installed, and pumping ports are positioned at both sides of each of the partitions, respectively. Hence, its structure is complicated. In addition, since the partitions serve as only physical barriers for isolating the ports from each other, there is a structural limitation in that pumping ports are necessarily positioned at both sides (or left and right sides) of each of the ports through which the precursors are injected or purged.
Embodiments provide a vapor deposition reactor of a closed-loop type, which performs within its interior, a series of processes of adsorbing a source precursor or a reactant precursor on a substrate, desorbing physisorbed molecule layer of the source precursor or the reactant precursor and externally exhausting the desorbed molecule layer.
In one embodiment, the vapor deposition reactor includes at least one first injection portion. The at least one first injection portion injects a first material. A first portion of the vapor deposition reactor has a first recess formed therein. The first recess is connected to the at least one first injection portion to receive the first material. A second portion is adjacent to the first portion and has a second recess formed therein. The second recess is connected to the first recess so that the first material via the first recess. A third portion has a third recess formed therein that is connected to the second recess, and receives the first material via the second recess. The pressure of the third recess is maintained lower than the first recess by an exhaust portion. A substrate moves across the first recess, the second recess and the third recess to absorb the first material in its surface.
In one embodiment, the first portion includes a plurality of first recesses, and the second portion includes a plurality of second recesses. The vapor deposition reactor may be configured by sequentially connecting the recesses in one of the first recesses, one of the second recesses, the third recess of the third portion, another of the first recesses and another of the second recesses.
In one embodiment, the vapor deposition reactor further includes an additional first portion and an additional second portion. The additional first portion and the additional second portion have an additional first recess and an additional second recess formed therein, respectively. The pressure in the additional second recess is lower than the pressure in the additional first recess. The additional first and second recesses are filled with a second material. The substrate moves across the first and second recesses to absorb the second material on the substrate.
The above and other aspects, features and advantages of the present invention will become apparent from the following description of preferred embodiments given in conjunction with the accompanying drawings, in which:
Exemplary embodiments now will be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments are shown. This disclosure may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth therein. Rather, these example embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of this disclosure to those skilled in the art. In the description, details of well-known features and techniques may be omitted to avoid unnecessarily obscuring the presented embodiments.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of this disclosure. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. Furthermore, the use of the terms a, an, etc. does not denote a limitation of quantity, but rather denotes the presence of at least one of the referenced item. The use of the terms “first”, “second”, and the like does not imply any particular order, but they are included to identify individual elements. Moreover, the use of the terms first, second, etc. does not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another. It will be further understood that the terms “comprises” and/or “comprising”, or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In the drawings, like reference numerals in the drawings denote like elements. The shape, size and regions, and the like, of the drawing may be exaggerated for clarity.
For example, when the vapor deposition reactor is used in atomic layer deposition (ALD), the reacting material may be a source precursor or reactant precursor. The source precursor may be determined depending on the type of thin film to be ultimately formed in the vapor deposition reactor. For example, the source precursor may be a compound containing atoms for forming a metal, insulator or semiconductor thin film, and an organic or inorganic compound may all be use as the source precursor. The reactant precursor is a material that forms a metal, oxide, nitride, carbide, material for semiconductor, or the like through reaction and/or replacement of the reactant precursor with the source precursor, thereby obtaining a thin film. For example, the reactant precursor may include one or more of H2O, H2O2, O2, N2O, NO, O3, O* radical, NH3, NH2—NH2, N* radical, CO, CO2, CH4, C2H6, H2 and H* radical.
In one embodiment, a substrate (not shown) may pass by the first to third portions 10 to 30 by moving across the vapor deposition reactor so that an atomic-layer or molecular-layer thin film is formed on the substrate. For example, the substrate may be moved in a linear or rotating manner adjacent to a lower portion of the vapor deposition reactor so that a thin film is formed on the substrate. In another embodiment, the vapor deposition reactor may be moved with respect to the substrate with the substrate fixed.
The first and second portions 10 and 20 include square-column-shaped recesses formed on a bottom portion of the body 9 of the vapor deposition reactor and have predetermined widths WE and WC, heights H and z and lengths L. The third portions 30 may have predetermined width WX and length L, and an upper portion of the third portion 30 may be connected to an exhaust portion 32 in which an exhaust portion 31 is formed. The structure of the vapor deposition reactor is merely illustrative. That is, the shapes of the first to third portions 10 to 30 may be configured differently from those described above depending on the object of the vapor deposition reactor.
The width of each of the first to third portions 10 to 30 herein refers to the dimension of recess formed in the first to third portions 10 to 30 parallel to the moving direction of the substrate. Also, the length of each of the first to third portions 10 to 30 refers to the dimension of each of the first to third portions 10 to 30 in the direction perpendicular to the movement direction of the substrate. Also, the height of each of the first and second portions 10 and 20 refers to the distance between a lower surface of the body 9 and an inner upper surface of the corresponding recesses in the first and second portions 10 and 20.
Properties of the thin film formed on the substrate may be determined at least partially based on the width WE and height H of the first portion 10, the width WC and height z of the second portion 20, the width WX of the third portion 30, and the movement velocity v of the substrate. For example, assuming that the movement velocity of the substrate is v and the width of a corresponding portion through which the substrate passes among the first to third portions 10 to 30 is x, the exposure time of the substrate for the corresponding portion is determined by the following equation:
t=x/v (1)
The recess of the first portion 10 may be filled with the reacting material injected through the injection portion 11. If the substrate moving at the movement velocity v passes by the lower portion of the first portion 10, the substrate is exposed to the reacting material for time WE/v. As a result, physisorbed and chemisorbed layers of the reacting material may be formed on the substrate. As the width WE of the first portion 10 is increased, an increasing amount of the reacting material is supplied to the first portion 10. As the width WE of the first portion 10 is decreased, the possibility that the reacting material is adsorbed on the substrate is decreased. Therefore, in designing the vapor deposition reaction, the width WE of the first portion 10 may be determined based on the property of the reacting material. As the steam pressure of the reacting material is increased, the width WE of the first portion 10 may be decreased, and/or the movement velocity v of the substrate may be increased. As a result, the amount of reacting material adsorbed on the substrate can be adjusted since the period during which the substrate resides at the first portion 10 is decreased.
The substrate passing by the lower portion of the first portion 10 subsequently passes by a lower portion of the second portion 20. The pressure PC in the recess of the second portion 20 may be relatively lower than the pressure PE in the recess of the first portion 10 (PC<PE). As a result, a portion of the reactant precursor adsorbed on the substrate may be desorbed for time WC/v during which the substrate passes by the lower portion of the second portion 20. For example, the physisorbed layer of the reacting material may be desorbed from a surface of the substrate while the substrate passes by the lower portion of the second portion 20.
The substrate passing by the lower portion of the second portion 20 subsequently passes by a lower portion of the third portion 30. The reacting material desorbed from the substrate while the substrate posses by the second portion 20 may be discharged to the exterior of the vapor deposition reactor through the exhaust portion 31 for time WX/v at which the substrate passes by the lower portion of the third portion 30. As a result, the physisorbed layer of the reacting material is at least partially removed from the substrate but the chemisorbed layer of the reacting material remains on the substrate. In an embodiment, the pressure PX in the third portion 30 may be relatively lower than the pressure PE in the first portion 10 (PX<PE).
As described above, while a substrate passes by the first to third portions 10 to 30 of the vapor deposition reactor, a series of processes is performed. During the series of processes, the substrate is exposed to a reacting material such as a source precursor and/or reactant precursor, and the reacting material is adsorbed in the surface of the substrate. Then, a physisorbed layer of the reacting material is desorbed from the substrate for at least partially removal from the substrate, and a chemisorbed layer of the reacting material is formed on the substrate.
The aforementioned processes may be performed using a source precursor as the reacting material in one vapor deposition reactor, and the aforementioned processes may be performing using a reactant precursor as the reacting material in a subsequent vapor deposition reactor. As a result, the substrate passes by four processes of adsorbing a source precursor, removing a physisorbed layer, adsorbing a reactant precursor and removing the physisorbed layer to form a thin film on the substrate. The produced thin film may be an atomic layer or mono molecule layer or may include a plurality of molecule layers. The moving velocity of the substrate that passes by the vapor deposition reactor filled with the source precursor may be controlled to be identical to or different from the moving velocity of the substrate that passes by the vapor deposition reactor filled with the reactant precursor.
The aforementioned processes may also be performed using a single vapor deposition reactor by injecting a source precursor and a reactant precursor alternately into the recess of the first portion 10 of the vapor deposition reactor. For example, a valve for ALD (not shown) and its driving unit may be connected to the channel 12. The source precursor and the reactant precursor may be injected in an alternating manner according to the opening or closing of the valve. Further, an inert gas may be injected as a purge gas after the injection of each of the source precursor and the reactant precursor. In this case, the substrate that passes by the first portion 10 undergoes the following four steps: adsorbing the source precursor, injecting the inert gas, adsorbing the reactant precursor and injecting the inert gas. As a result, an atomic layer thin film may be formed on the substrate. A portion of the precursor adsorbed on the substrate and/or the inert gas may be desorbed from the substrate and discharged while the substrate passes by the second portion 20 and the third portion 30.
When a source precursor, an inert gas and a reactant precursor are injected into a single vapor deposition reactor in an alternating manner, the moving velocity of the substrate that passes by the single vapor deposition reactor may be relatively smaller than the moving velocity of a substrate that passes by another vapor deposition reactor into which only one of the source precursor and the reactant precursor is injected. For example, the moving velocity of the substrate may be controlled such that the substrate is sequentially exposed to a source precursor, an inert gas, a reactant precursor and an inert gas while the substrate passes by one first portion 10. When the ALD is performed according to the aforementioned processes, an atomic layer thin film may be formed using the single vapor deposition reactor. Thus, the number of atomic layer thin films which are formed using the same number of vapor deposition reactors may be increased.
Meanwhile, the lower portion of the vapor deposition reactor may be spaced apart from the substrate. For example, the lower portion of the vapor deposition reactor may be spaced apart from the substrate at about 0.5 mm to a few millimeters. Alternatively, the interval between the lower portion of the vapor deposition reactor and the substrate may be about 1 mm. When the interval between the lower portion of the vapor deposition reactor and the substrate is sufficiently small (e.g., when the interval between the lower portion of the vapor deposition reactor and the substrate is about 1 mm or less), the amount of the reacting material leaked to the exterior from the vapor deposition reactor may be negligible. However, in order to minimize the amount of the leaked reacting material, an inert gas may be injected around the vapor deposition reactor, or pumping may be performed around the vapor deposition reactor. In this case, the inert gas may include one or more gas selected from the group consisting of N2, Ar and He.
The shapes of the first and second portions 10 and 20 affect effective desorption of the reacting material adsorbed on the substrate. Experiments were conducted using the first and second portions 10 and 20 having various shapes to derive parameters related to the desorption of the reacting material. For example, trimethylaluminum (TMA) is sufficiently adsorbed on a substrate maintained at about 250° C. for one second, and the substrate is then passed by the lower portion of the vapor deposition reactor. At this time, an inert gas such as Ar gas may be injected into the first portion 10. Since the pressure of the Ar gas is lowered while the substrate passes by a lower portion of the second portion 20, molecules of the TMA adsorbed on the substrate are desorbed, and the desorbed molecules of the TMA may be exhausted together with the Ar gas to the exterior via the third portion 30. In this case, the desorption is examined while changing the shapes of the first and second portions 10 and 20. Alternatively, the desorption may be examined using the thickness of an atomic-layer thin film formed by the vapor deposition reactor.
The correlation of the width WE of the first portion 10, the height z of the recess in the second portion 20 and the desorption are examined using a vapor deposition reactor in which the height H of the first portion 10 is greater than the width WE of the first portion 10. As a result, the results of the following Table 1 were obtained. At this time, the experiment is performed in a state where the width WE of the first portion 10 was identical to the width WX of the third portion 30 and the width WC of the second portion 20 was about ½ of the width WE of the first portion 10.
Also, the correlation of the width WC of the second portion 20, the height z of the second portion 20 and the desorption are examined using a vapor deposition reactor in which the height H of the first portion 10 is greater than the width WE of the first portion 10. As a result, following Table 2 was obtained. The experiment was performed in a state where WE of the first portion 10 is identical to the width WX of the third portion 30 and the height z of the second portion 20 is about ½ of the width WE of the first portion 10.
On the other hand, the correlation of the height H of the first portion 10, the height z of the second portion 20 and the desorption are examined using a vapor deposition reactor in which the height H of the first portion 10 is smaller than the width WE of the first portion 10. As a result, following Table 3 was obtained. The experiment is performed in a state where the width WC of the second portion 20 is about ½ of the width WX of the third portion 30.
In Tables 1 to 3, when the height z of the second portion 20 is zero, the reacting material is leaked and diffused around the vapor deposition reactor, and hence, the desorption caused by the second portion 20 cannot be assessed. The result obtained when the height z of the second portion 20 is zero is not represented in Tables 1 to 3.
As can be seen from the results of Tables 1 to 3, the desorption effect is increased as the height z of the second portion 20 is decreased. Also, it can be seen that the desorption effect is increased as the width WC of the second portion 20 is increased when the height z of the second portion 20 is constant. In an embodiment, the width WC of the second portion 20 may be greater than about ½ of the height z of the second portion 20. In another embodiment, the height z of the second portion 20 may be greater than zero and equal to or less than ⅔ of the width WE of the first portion 10. Alternatively, the height z of the second portion 20 may be greater than zero and equal to or less than ⅔ of the height H of the first portion 10. In still another embodiment, the height z of the second portion 20 may be equal to or less than the width WX of the third portion 30.
Referring to
In the second portion 20 shown in
Meanwhile, in case of a rotary type vapor deposition reactor in which a plurality of substrates are loaded and then deposited while being rotated, an angular velocity is varied depending on the radius of rotation. For example, when the substrates are loaded on a rotating table and the table is activated, the angular velocity at the outside of the rotating table is greater than that at the inside of the rotating table. In this case, the time during which a portion of the substrate at the outside of the rotating table is subject to the processing by the vapor deposition reactor is different from the time during which another portion of the substrate inside the rotating table is exposed to the vapor deposition reactor, and therefore, the desorption rates of the reacting material at both of the portions are different from each other.
Referring to
Referring to
Meanwhile, the shape of the vapor deposition reactor may be modified based on the type and property of a reacting material. Particularly, since adsorption and desorption characteristics differ depending on the shape of the second portion, the shape of the second portion may be optimized based the reacting material used. For example, when a precursor with a low vapor pressure and/or a high viscosity is used as the reacting material, a structure with a relatively high desorption rate is necessary. When, a precursor with a high vapor pressure and/or a low viscosity is used as the reacting material, a structure with a relatively low desorption rate is necessary. The characteristics of the second portion can be varied for different reacting materials in one vapor deposition reactor.
Meanwhile, when the adjustable wing 210 is positioned at the driving position as shown in
In the embodiment described with reference to
In still another embodiment, the adjustable wing 210 may change the distance z between the partition 200 and the substrate 40, i.e., the height z of the second portion 20. If the distance between the partition 200 and the substrate 40 is decreased, the height z of the second portion 20 is decreased, and the pressure in the second portion 20 is decreased. Therefore, the desorption rate of the reacting material from the substrate 40 may be increased. On the other hand, if the distance between the partition 200 and the substrate 40 is increased, the height z of the second portion 20 is increased, and the pressure in the second portion 20 is increased. Therefore, the desorption rate of the reacting material from the substrate 40 may be decreased.
According to the aforementioned embodiments, reacting materials with different viscosity can be used in the vapor deposition reactor having the same size by using the adjustable wing. Also, the deposition characteristic of an atomic-layer thin film and/or the desorption rate of adsorbed molecules can be changed by using the vapor deposition reactor.
As shown in
By using the vapor deposition reactors as described above, an inert gas can be injected together with a source precursor or reactant precursor into the recess of the first portion 10. The inert gas functions to purge the reacting material adsorbed on the substrate while the substrate passes by the second portion 20, and therefore, the amount of physisorbed layer that remains on the substrate is less than that of physisorbed layer that remains on the substrate when only the source precursor or reactant precursor is used. Thus, the vapor deposition reactor is advantageous in formation of an atomic mono-layer.
By using the vapor deposition reactor, the valves V1 to V3 are opened or closed so that two different materials (e.g., a reacting material and an inert gas) can be injected into the first portion 10 through the one injection portion 11 and the one channel 12. In this case, the reacting material and the inert gas can be simultaneously injected into the recess of the first portion 10 by simultaneously opening or closing the valves V1 and V2. Alternatively, the reacting material and the inert gas may be separately injected into the first portion 10 by alternately opening or closing the valves V1 and V2. Meanwhile, a plurality of first portions may be disposed in one vapor deposition reactor so that a source precursor and a reactant precursor are all injected onto a substrate in the one vapor deposition reactor.
Referring to
First injection portions 11 and 11′ may be formed in the respective first portions 10 and 10′. The first injection portions 11 and 11′ may be connected to channels 12 and 12′, respectively. A reacting material may be injected into the first portion 10 or 10′ through the first injection portion 11 or 11′. By using the vapor deposition reactor having the two first portions 10 and 10′ positioned in the vapor deposition reactor, the reacting material can be adsorbed twice on the substrate while a substrate passes by the one vapor deposition reactor.
As an example, a source precursor may be injected into the first portion 10, and a reactant precursor may be injected into the first portion 10′. While the substrate that passes by the vapor deposition reactor passes by the first portion 10, the source precursor is adsorbed on the substrate. While the substrate passes by the second portion 20, the third portion 30 and the second portion 20′, a physisorbed layer of the source precursor is desorbed and exhausted. While the substrate passes by the first portion 10′, the reactant precursor is reacted and/or replaced with the source precursor on the substrate, thereby forming an atomic-layer thin film. As described above, the formation of the atomic-layer thin film is described as an example. However, it will be apparent that chemical vapor deposition (CVD) may also be performed using the vapor deposition reactor.
Second injection portions 13 and 13′ may be further formed in the respective first portions 10 and 10′. The second injection portions 13 and 13′ may be connected to channels 14 and 14′, respectively. An inert gas may be injected into the first portion 10 or 10′ through the second injection portion 13 or 13′. When the inert gas is injected together with the source precursor or the reactant precursor, it functions to purge the physisorbed layer adsorbed on the substrate while the substrate passes by the second portion 20 and 20′ and the third portion 30 so that the desorption is more effectively performed. Thus, the amount of the physisorbed layer on the substrate is less than that of the physisorbed layer on the substrate when only the source precursor or reactant precursor is injected. Accordingly, it is advantageous in formation of an atomic mono-layer.
Meanwhile, the reactant precursor physisorbed after forming the atomic-layer thin film remains on the substrate that passes by the vapor deposition reactor. Subsequently, if the substrate is passed through another vapor deposition reactor, the reactant precursor physisorbed on the substrate is reacted and/or replaced with a source precursor injected from the new vapor deposition reactor, thereby forming a thin film. Thus, the deposition velocity of the thin film can be increased. This is referred to as a pseudo-ALD mode.
Meanwhile, as another example, a source precursor (or reactant precursor) may be injected as a reacting material into the recess of the first portion 10, and only an inert gas may be injected into the recess of the first portion 10′ with no reacting material. In this case, the reacting material is adsorbed on a substrate while the substrate passes by the first portion. While the substrate passes by the second portion 20, the third portion 30 and the second portion 20′, the reacting material is desorbed and exhausted. The desorption of the reacting material is accelerated by the inert gas injected into the first portion 10′, so that an adsorbed layer with a superior quality can be obtained. When an atomic-layer thin film is to be formed, an additional vapor deposition reactor is necessary for the purpose of the adsorbing the reactant precursor (or source precursor). However, an atomic-layer thin film with excellent characteristics can be formed.
The vapor deposition reactor shown in
Subsequently, a substrate is moved S12 with respect to the first portion so that the reacting material is adsorbed on a surface of the substrate. At this time, chemisorbed and physisorbed layers of the reacting material are formed on the substrate. The relative movement of the substrate with respect to the first portion may be performed by moving the substrate to be adjacent to the vapor deposition reactor in the state that the vapor deposition reactor is fixed. Alternatively, the vapor deposition reactor may be moved in the state that the substrate is fixed.
Subsequently, the substrate is moved S13 with respect to a second portion so that the physisorbed layer of the reacting material is desorbed from the substrate. To this end, the pressure in the second portion may be lower than that in the first portion. Also, the desorption amount of the physisorbed layer may be adjusted by controlling the position, width and height of the second portion and/or the position of an adjustable wing in the second portion. The entire physisorbed layer may be removed from the substrate. Alternatively, the deposition velocity may be increased by allowing a part of the physisorbed layer to remain on the substrate.
Subsequently, the substrate is moved with respect to a third portion so that the desorbed reacting material is exhausted S14 to the exterior of the vapor deposition reactor through an exhaust portion. As a result, the reacting material physisorbed on the substrate can be at least partially removed. Through the aforementioned processes, a thin film including the chemisorbed layer of the reacting material can be formed on the substrate.
When the aforementioned processes S11 to S14 are repeatedly performed while exchanging the reacting material, e.g., when the aforementioned processes S11 to S14 are performed by alternately using the source precursor and the reactant precursor as the reacting material in process S11, an atomic-layer thin film can be formed on the substrate. Alternatively, the source precursor and the reactant precursor may be injected alternately into the first portion as the reacting material in the single process S11. As a result, an atomic layer thin film may be formed on the substrate when the aforementioned processes S11 to S14 are performed once. In this case, an inert gas may be injected as a purge gas after the injection of each of the source precursor and the reactant precursor.
Referring to
The substrate is moved S22 with respect to a second portion of the first reactor. At this time, the pressure in the second portion may be lower than that in the first portion. Then, the substrate is move S23 with respect to a third portion of the first reactor. While the substrate passes by the second and third portions, a physisorbed layer of the source precursor adsorbed on the substrate is at least partially desorbed from the substrate and exhausted to the exterior of the first reactor.
A reactant precursor and an inert gas are injected into a first portion of a second reactor, and the substrate is moved S24 with respect to the first portion of the second reactor. As a result, the reactant precursor is adsorbed on the surface of the substrate, and the source precursor adsorbed on the substrate is reacted with the reactant precursor adsorbed on the substrate, thereby forming an atomic-layer thin film. Meanwhile, in another embodiment, only the reactant precursor may be injected S24 with no inert gas in the process.
The substrate is moved with respect to a second portion S25 of the second reactor (S25). At this time, the pressure in the second portion may be lower than that in the first portion. Then, the substrate is moved S26 with respect to a third portion of the second reactor. While the substrate passes by the second and third portions, a portion of the reactant precursor may be desorbed from the substrate and then exhausted to the exterior of the second reactor.
The aforementioned processes (S21 to S26) are performed until an atomic-layer thin film with a final thickness is formed S27, thereby forming an atomic-layer thin film with a desired thickness.
Referring to
The substrate is moved S32 with respect to a primary second portion. At this time, the pressure in the second portion may be lower than that in the first portion. Then, the substrate is moved S33 with respect to a third portion. Then, the substrate is move S34 with respect to secondary second portion. While the substrate passes by the two second portions and the third portion, a physisorbed layer of the source precursor adsorbed on the substrate is at least partially desorbed and exhausted to the exterior of the vapor deposition reactor.
A reactant precursor and an inert gas are injected S35 into a secondary first portion of the vapor deposition reactor, and the substrate is moved S35 with respect to the secondary first portion. As a result, the reactant precursor is adsorbed on the surface of the substrate, and the source precursor adsorbed while the substrate passes by the primary first portion is reacted with the reactant precursor, thereby forming an atomic-layer thin film on the substrate. In another embodiment, only the reactant precursor may be injected S35 with no inert gas in the process.
The aforementioned processes (S31 to S35) are performed until an atomic-layer thin film with a final thickness is formed S36, thereby obtaining an atomic-layer thin film with a desired thickness.
In the ALD equipment, a source precursor and an inert gas may be filled in a first portion of a first vapor deposition reactor 1. Also, a reactant precursor and an inert gas may be filled in a first portion 10 of a second vapor deposition reactor 2. As the substrate 40 passes by the first portion 10 of the first vapor deposition reactor 1, the source precursor may be adsorbed on the substrate 40. Subsequently, as the substrate 40 passes by second and third portions 20 and 30 of the first vapor deposition reactor 1, pressure is lowered. Thus, a physisorbed layer of the source precursor adsorbed on the substrate 40 is desorbed from the substrate 40 and exhausted to the exterior of the first vapor deposition reactor 1.
Subsequently, as the substrate passes by the first portion 10 of the second vapor deposition reactor 2, the reactant precursor may be adsorbed on the substrate 40. The reactant precursor is reacted with the source precursor adsorbed on the substrate, thereby forming an atomic-layer thin film. Subsequently, as the substrate 40 passes by second and third portions 20 and 30 of the second vapor deposition reactor 2, the reactant precursor is at least partially desorbed from the substrate 40 and exhausted to the exterior of the second vapor deposition reactor 2. At this time, the source precursor and the reactant precursor are injected into and exhausted from the first and second vapor deposition reactors 1 and 2, respectively. Therefore, the source precursor and the reactant precursor do not come in contact with each other. Thus, it is possible to minimize a reactant byproduct such as powder or gum or reactant product generated in an exhaust pipe.
In the ALD equipment shown in
The ALD equipment using the vapor deposition reactor shown in
While a substrate 40 passes by the first vapor deposition reactor 1, the following processes are performed. First, while the substrate 40 passes by the primary first portion 10, the source precursor may be adsorbed on the substrate. While the substrate 40 passes by the primary second portion 20 and the third portion 30, a physisorbed layer of the source precursor may be desorbed and exhausted. Subsequently, while the substrate 40 passes by the secondary second portion 20′, the inert gas injected into the secondary first portion 10′ passes by the secondary second portion 20′. Therefore, pressure is lowered, and accordingly, additional desorption occurs. Through the aforementioned processes, only a pure chemisorbed layer can remain on the substrate 40 that passes by the first vapor deposition reactor 1.
Processes performed while the substrate 40 passes by the second vapor deposition reactor 2 are performed similarly to those performed while the substrate passes by the first vapor deposition reactor 1. However, the second vapor deposition reactor 2 is different from the first vapor deposition reactor 1 in that the reactant precursor is injected into the primary first portion 10 of the second vapor deposition reactor 2. The reactant precursor is reacted with a chemisorbed layer of the source precursor adsorbed on the substrate 40, so that an atomic-layer thin film of a mono molecular-layer can be formed on the substrate that passes by all of the first and second vapor deposition reactors 1 and 2.
As described above, the shape of the vapor deposition reactors included in the ALD equipments described with reference to
In the embodiments described with reference to
Meanwhile, the problem that the movement velocities of the substrate 40, respectively rotated at the inside and outside of the rotating table 410, are different from each other may be solved by modifying the shape of the vapor deposition reactor.
Example of Forming TiN Thin Film Using Vapor Deposition Reactor
Referring to
The experimental apparatus may further include a quartz tube 63 and a coil 64 so as to apply ICP (inductive coupled plasma) type remote-plasma. A radio frequency (RF) voltage of about 5 to 100 watt may be applied to the coil 64 so as to generate NH3 plasma. However, in another embodiment, a TiN atomic-layer thin film may be formed by a simple thermal reaction without generating plasma. At this time, in the experimental apparatus, an additional vapor deposition reactor may be installed in the portion in which the quartz tube 63 and the coil 64 are to be installed, and NH3 may be injected as a reactant precursor into the additional vapor deposition reactor. TiCl4 may be supplied as a source precursor to the vapor deposition reactor 1 using an Ar bubbling method. In the vapor deposition reactor, the deposition efficiency, i.e., the ratio of the source precursor used in the formation of a thin film with respect to the source precursor supplied, is high, and hence, TiCl4 is supplied from a canister which is cooled down to about −4° C.
The height of a first portion of the vapor deposition reactor 1 is about 20 mm, the width of the first portion is about 10 mm, and the length of the first portion is about 100 mm. The width of a third portion of the vapor deposition reactor 1 is about 16 mm. From the results obtained in Tables 1, 2 and 3, the vapor deposition reactor 1 may be configured so that the height of a second portion is about 2 mm and the width of the second portion is about 4 mm. When the substrate 40 passes by a lower portion of the vapor deposition reactor 1, the time at which the substrate 40 is exposed to the first portion is about 105 msec at an inside of the substrate 40 close to the center of the rotating table 410 when the rotation velocity of the rotating table 410 is about 10 rpm, and the time is about 60 msec when the rotation velocity of the rotating table 410 is about 18 rpm. Meanwhile, the angular velocity of an outside of the substrate 40 distant from the center of the rotating table 410 is greater than that of the inside of the substrate 40. As a result, when the rotation velocity of the rotating table 410 is about 10 rpm and about 18 rpm, the times at which the outside of the substrate 40 is exposed to the first portion are about 80 msec and about 44 msec, respectively.
The time at which the inside of the substrate 40 passes by the second and third portions is about 210 msec when the rotation velocity of the rotating table 410 is about 10 rmp, and the time is about 120 msec when the rotation velocity of the rotating table 410 is about 18 rpm. Also, the time at which the inside of the substrate 40 completely passes by the vapor deposition reactor 1 is about 315 msec when the rotation velocity of the rotating table 410 is about 10 rmp, and the time is about 180 msec when the rotation velocity of the rotating table 410 is about 18 rpm.
The experimental apparatus may further include a coaxial remote plasma generator 2 as illustrated in
In one embodiment, reactant gas such as O2, H2 or NH3 is provided via pipes 2202, 2204, 2206 and valves Va, Vb and Vc to the cylindrical space. By applying voltage across the electrodes 12A and 12B in the presence of the reactance gas, the coaxial capacitive plasma is generated. The top surface of the substrate is exposed to O* radical, N* radical or H* radicals obtained from the coaxial capacitive plasma to form an ALD layer. Remaining O* radical, N* radical or H* radicals are discharged via a second portion 20, a third portion 30 and an exhaust portion 310.
Meanwhile, the experimental apparatus may include a halogen lamp (not shown) installed between the vapor deposition reactors 1 or at the last position of the substrate 40 so that additional thermal treatment can be performed during or after a thin film is deposited. In addition, before an atomic-layer thin film is deposited, cleaning or removing of a natural oxide film may be performed with respect to the substrate 40. In this case, a gas for removing an oxide film, such as ClF3 or NF3, may be injected into the vapor deposition reactor 1, or hydrogen remote-plasma may be generated in the vapor deposition reactor 1. Thus, the atomic layer thin film may be deposited through in-situ by performing a surface treatment or pre-processing process before the atomic layer thin film is deposited. Alternatively, after the natural oxide thin film is removed, nitriding may be performed with respect to the substrate using nitrogen radical by nitrogen remote-plasma. Then, a high-k thin film may be deposited through in-situ.
The TiN thin films shown in
In the TiN thin film shown in
The TiN thin films shown in
In the conventional methods of atomic layer deposition, a precursor is injected into the chamber, and a thin film is obtained using only a molecule layer adsorbed on the surface of the substrate. Therefore, in the formation of an atomic layer, the deposition efficiency, i.e., the ratio of a source used in the deposition with respect to a total source injected, has a close relationship with the size of the chamber.
However, if one of the vapor deposition reactors according to the aforementioned embodiments are used, the reacting material is filled only in the first portion of the vapor deposition reactor, and hence, the deposition efficiency is very higher than that in the conventional vapor deposition reactors. Also, since the adsorption and desorption of the molecule layer are performed while passing the substrate through the lower portion of the vapor deposition reactor, the precursor is continuously supplied with no valve for ALD or driving unit, and thus, the configuration of the vapor deposition reactor can be simplified.
Also, since the injection, desorption and exhaustion of the reacting material are performed in the interior of the vapor deposition reactor, the deposition can be performed regardless of the atmosphere in the interior of the chamber. Also, since the source precursor and reactant precursor are injected into and exhausted from separate vapor deposition reactors, respectively, a reactant byproduct such as powder or gum is not produced in an exhaust line. Accordingly, the reliability, durability and economy of the apparatus can be improved in addition to the thin film.
While the present invention has been described in connection with certain exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims, and equivalents thereof.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3896244 | Ellis et al. | Jul 1975 | A |
| 4293326 | Terneu et al. | Oct 1981 | A |
| 4834020 | Bartholomew et al. | May 1989 | A |
| 4891247 | Shamshoian | Jan 1990 | A |
| 5063951 | Bard et al. | Nov 1991 | A |
| 5120568 | Schuurmans et al. | Jun 1992 | A |
| 5122391 | Mayer | Jun 1992 | A |
| 5136975 | Bartholomew et al. | Aug 1992 | A |
| 5275668 | Dell et al. | Jan 1994 | A |
| 5286295 | Sauvinet et al. | Feb 1994 | A |
| 5300189 | Kokaku et al. | Apr 1994 | A |
| 5368897 | Kurihara et al. | Nov 1994 | A |
| 5482557 | Kanai et al. | Jan 1996 | A |
| 5549780 | Koinuma et al. | Aug 1996 | A |
| 5560777 | Ahn | Oct 1996 | A |
| 5565249 | Kurihara et al. | Oct 1996 | A |
| 5578130 | Hayashi et al. | Nov 1996 | A |
| 5665640 | Foster et al. | Sep 1997 | A |
| 5683516 | DeDontney et al. | Nov 1997 | A |
| 5711814 | Mori | Jan 1998 | A |
| 5725668 | Foster et al. | Mar 1998 | A |
| 5820947 | Itoh | Oct 1998 | A |
| 5863337 | Neuman et al. | Jan 1999 | A |
| 5879459 | Gadgil et al. | Mar 1999 | A |
| 5935647 | DeDontney et al. | Aug 1999 | A |
| 5951771 | Raney et al. | Sep 1999 | A |
| 6022414 | Miller et al. | Feb 2000 | A |
| 6051150 | Miyakawa | Apr 2000 | A |
| 6079353 | Leksell et al. | Jun 2000 | A |
| 6083355 | Spence | Jul 2000 | A |
| 6099974 | Lenling | Aug 2000 | A |
| 6143077 | Ikeda et al. | Nov 2000 | A |
| 6195504 | Horie et al. | Feb 2001 | B1 |
| 6200389 | Miller et al. | Mar 2001 | B1 |
| 6206972 | Dunham | Mar 2001 | B1 |
| 6319615 | Jansen | Nov 2001 | B1 |
| 6354109 | Boire et al. | Mar 2002 | B1 |
| 6406590 | Ebata et al. | Jun 2002 | B1 |
| 6416822 | Chiang et al. | Jul 2002 | B1 |
| 6424091 | Sawada et al. | Jul 2002 | B1 |
| 6435428 | Kim et al. | Aug 2002 | B2 |
| 6521048 | Miller et al. | Feb 2003 | B2 |
| 6539891 | Lee et al. | Apr 2003 | B1 |
| 6569501 | Chiang et al. | May 2003 | B2 |
| 6634314 | Hwang et al. | Oct 2003 | B2 |
| 6641673 | Yang et al. | Nov 2003 | B2 |
| 6656284 | Hwang et al. | Dec 2003 | B1 |
| 6656831 | Lee et al. | Dec 2003 | B1 |
| 6730614 | Lim et al. | May 2004 | B1 |
| 6812157 | Gadgil | Nov 2004 | B1 |
| 6824816 | Aaltonen et al. | Nov 2004 | B2 |
| 6890386 | DeDontney et al. | May 2005 | B2 |
| 6926572 | Park et al. | Aug 2005 | B2 |
| 6972055 | Sferlazzo | Dec 2005 | B2 |
| 6997371 | Shabtay | Feb 2006 | B2 |
| 7087119 | Sandhu | Aug 2006 | B2 |
| 7118779 | Verghese et al. | Oct 2006 | B2 |
| 7384680 | Bi et al. | Jun 2008 | B2 |
| 7455884 | Sandhu | Nov 2008 | B2 |
| 7494545 | Lam et al. | Feb 2009 | B2 |
| 7615486 | Yoon et al. | Nov 2009 | B2 |
| 7754013 | Granneman | Jul 2010 | B2 |
| 7886688 | Takeuchi et al. | Feb 2011 | B2 |
| 7914847 | Verghese et al. | Mar 2011 | B2 |
| 7943527 | Kumar et al. | May 2011 | B2 |
| 7981472 | Dalton et al. | Jul 2011 | B2 |
| 8257799 | Lee | Sep 2012 | B2 |
| 8328982 | Babayan et al. | Dec 2012 | B1 |
| 20010047759 | Matsui et al. | Dec 2001 | A1 |
| 20020092616 | Kim | Jul 2002 | A1 |
| 20020100418 | Sandhu et al. | Aug 2002 | A1 |
| 20020112819 | Kamarehi et al. | Aug 2002 | A1 |
| 20020197864 | Sneh | Dec 2002 | A1 |
| 20030072881 | Yang et al. | Apr 2003 | A1 |
| 20030143328 | Chen et al. | Jul 2003 | A1 |
| 20030198587 | Kaloyeros et al. | Oct 2003 | A1 |
| 20030214043 | Saitoh et al. | Nov 2003 | A1 |
| 20040052972 | Schmitt | Mar 2004 | A1 |
| 20040067641 | Yudovsky | Apr 2004 | A1 |
| 20040083967 | Yuda et al. | May 2004 | A1 |
| 20040129212 | Gadgil et al. | Jul 2004 | A1 |
| 20040171280 | Conley et al. | Sep 2004 | A1 |
| 20040224527 | Sarigiannis et al. | Nov 2004 | A1 |
| 20040247787 | Mackie et al. | Dec 2004 | A1 |
| 20040261946 | Endoh et al. | Dec 2004 | A1 |
| 20040265195 | Lee | Dec 2004 | A1 |
| 20050016457 | Kawasaki et al. | Jan 2005 | A1 |
| 20050064207 | Senzaki et al. | Mar 2005 | A1 |
| 20050064236 | Lim et al. | Mar 2005 | A1 |
| 20050084610 | Selitser et al. | Apr 2005 | A1 |
| 20050092247 | Schmidt et al. | May 2005 | A1 |
| 20050106094 | Kondo | May 2005 | A1 |
| 20050183768 | Roscheisen et al. | Aug 2005 | A1 |
| 20060019033 | Muthukrishnan et al. | Jan 2006 | A1 |
| 20060068519 | Dunbar et al. | Mar 2006 | A1 |
| 20060183301 | Yeom et al. | Aug 2006 | A1 |
| 20060211243 | Ishizaka et al. | Sep 2006 | A1 |
| 20060213441 | Kobrin et al. | Sep 2006 | A1 |
| 20060237399 | Horner-Richardson et al. | Oct 2006 | A1 |
| 20060240665 | Kang et al. | Oct 2006 | A1 |
| 20070082500 | Norman et al. | Apr 2007 | A1 |
| 20070095286 | Baek et al. | May 2007 | A1 |
| 20070145023 | Holber et al. | Jun 2007 | A1 |
| 20070224348 | Dickey et al. | Sep 2007 | A1 |
| 20070237699 | Clark | Oct 2007 | A1 |
| 20070243325 | Sneh | Oct 2007 | A1 |
| 20070264488 | Lee | Nov 2007 | A1 |
| 20070281082 | Mokhlesi et al. | Dec 2007 | A1 |
| 20070281089 | Heller et al. | Dec 2007 | A1 |
| 20080026162 | Dickey et al. | Jan 2008 | A1 |
| 20080075881 | Won et al. | Mar 2008 | A1 |
| 20080092953 | Lee | Apr 2008 | A1 |
| 20080106202 | Du et al. | May 2008 | A1 |
| 20080124945 | Miya et al. | May 2008 | A1 |
| 20080241387 | Keto | Oct 2008 | A1 |
| 20080260940 | Yoon et al. | Oct 2008 | A1 |
| 20080260963 | Yoon et al. | Oct 2008 | A1 |
| 20080260967 | Yoon et al. | Oct 2008 | A1 |
| 20090017190 | Sferlazzo et al. | Jan 2009 | A1 |
| 20090044661 | Li et al. | Feb 2009 | A1 |
| 20090047775 | Yamazaki et al. | Feb 2009 | A1 |
| 20090064932 | Kim et al. | Mar 2009 | A1 |
| 20090068849 | Endo et al. | Mar 2009 | A1 |
| 20090081885 | Levy et al. | Mar 2009 | A1 |
| 20090098276 | Burrows et al. | Apr 2009 | A1 |
| 20090102385 | Wi | Apr 2009 | A1 |
| 20090130858 | Levy | May 2009 | A1 |
| 20090133714 | Yamazaki et al. | May 2009 | A1 |
| 20090165715 | Oh | Jul 2009 | A1 |
| 20090170345 | Akae et al. | Jul 2009 | A1 |
| 20090197406 | Cao et al. | Aug 2009 | A1 |
| 20090291211 | Ryu et al. | Nov 2009 | A1 |
| 20090304924 | Gadgil | Dec 2009 | A1 |
| 20090320749 | Yoon et al. | Dec 2009 | A1 |
| 20100037820 | Lee | Feb 2010 | A1 |
| 20100037824 | Lee | Feb 2010 | A1 |
| 20100041213 | Lee | Feb 2010 | A1 |
| 20100055347 | Kato et al. | Mar 2010 | A1 |
| 20100064971 | Lee | Mar 2010 | A1 |
| 20100068413 | Lee | Mar 2010 | A1 |
| 20100124618 | Kobayashi et al. | May 2010 | A1 |
| 20100132615 | Kato et al. | Jun 2010 | A1 |
| 20100140802 | Matsumoto et al. | Jun 2010 | A1 |
| 20100181566 | Lee | Jul 2010 | A1 |
| 20100189900 | Dickey et al. | Jul 2010 | A1 |
| 20100215871 | Lee | Aug 2010 | A1 |
| 20100221426 | Sferlazzo | Sep 2010 | A1 |
| 20100255625 | De Vries | Oct 2010 | A1 |
| 20100304047 | Yang et al. | Dec 2010 | A1 |
| 20110070380 | Shero et al. | Mar 2011 | A1 |
| 20110076421 | Lee | Mar 2011 | A1 |
| 20120021252 | Lee | Jan 2012 | A1 |
| 20120027953 | Lee | Feb 2012 | A1 |
| 20120094149 | Lee | Apr 2012 | A1 |
| 20120114877 | Lee | May 2012 | A1 |
| 20120125258 | Lee | May 2012 | A1 |
| 20120196050 | Vermeer et al. | Aug 2012 | A1 |
| 20120207926 | Lee | Aug 2012 | A1 |
| 20120207948 | Lee | Aug 2012 | A1 |
| 20120213945 | Lee | Aug 2012 | A1 |
| 20120225204 | Yudovsky | Sep 2012 | A1 |
| 20120225206 | Yudovsky | Sep 2012 | A1 |
| 20120225207 | Yudovsky | Sep 2012 | A1 |
| 20120301632 | Lee | Nov 2012 | A1 |
| 20130260539 | Lee | Oct 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| 1436602 | Aug 2003 | CN |
| 0188208 | Jul 1986 | EP |
| 0499524 | Feb 1992 | EP |
| 2159304 | Mar 2010 | EP |
| 2360293 | Aug 2011 | EP |
| 2736632 | Jan 1997 | FR |
| S62-081018 | Apr 1987 | JP |
| H01-096924 | Apr 1989 | JP |
| 1-161835 | Jun 1989 | JP |
| H01-223724 | Sep 1989 | JP |
| H02-187018 | Jul 1990 | JP |
| H04-092414 | Mar 1992 | JP |
| H09-064000 | Mar 1997 | JP |
| 09-167757 | Jun 1997 | JP |
| 09-199738 | Jul 1997 | JP |
| 10-507994 | Aug 1998 | JP |
| 11-092943 | Apr 1999 | JP |
| H11-285882 | Oct 1999 | JP |
| 2001-357780 | Dec 2001 | JP |
| 2002-018276 | Jan 2002 | JP |
| 2002-339075 | Nov 2002 | JP |
| 2003-049272 | Feb 2003 | JP |
| 2003-073835 | Mar 2003 | JP |
| 2003-174019 | Jun 2003 | JP |
| 2003-324070 | Nov 2003 | JP |
| 2004-010949 | Jan 2004 | JP |
| 2004091837 | Mar 2004 | JP |
| 2005-089781 | Apr 2005 | JP |
| 2005-116898 | Apr 2005 | JP |
| 2005-347245 | May 2005 | JP |
| 2006-236697 | Sep 2006 | JP |
| 2007-019460 | Jan 2007 | JP |
| 2007-191792 | Aug 2007 | JP |
| 2007-266093 | Oct 2007 | JP |
| 2007266093 | Oct 2007 | JP |
| 2008-108895 | May 2008 | JP |
| 2008108895 | May 2008 | JP |
| 2009-531535 | Sep 2009 | JP |
| 100175011 | Nov 1998 | KR |
| 10-2001-0040561 | May 2001 | KR |
| 10-2002-0078804 | Oct 2002 | KR |
| 10-2002-0083564 | Nov 2002 | KR |
| 10-2003-0086056 | Nov 2002 | KR |
| 10-0631972 | Aug 2003 | KR |
| 10-2004-0016779 | Feb 2004 | KR |
| 10-2004-0042209 | May 2004 | KR |
| 10-2005-0015931 | Feb 2005 | KR |
| 10-0542736 | Jan 2006 | KR |
| 10-631972 | Aug 2006 | KR |
| 10-0622609 | Sep 2006 | KR |
| 10-2006-104230 | Oct 2006 | KR |
| 10-2006-0117607 | Nov 2006 | KR |
| 10-0760428 | Nov 2006 | KR |
| 10-0673211 | Jan 2007 | KR |
| 10-2007-0051332 | May 2007 | KR |
| 10-2007-0076955 | Jul 2007 | KR |
| 10-2007-0096770 | Oct 2007 | KR |
| 10-2007-0101127 | Oct 2007 | KR |
| 10-2007-0101360 | Oct 2007 | KR |
| 10-0771926 | Oct 2007 | KR |
| 10-0791677 | Jan 2008 | KR |
| 10-0840897 | Jun 2008 | KR |
| 10-2008-0067042 | Jul 2008 | KR |
| 10-2008-0067042 | Jul 2008 | KR |
| WO 9939144 | Aug 1999 | WO |
| WO 2006054854 | May 2006 | WO |
| WO 2007106076 | Sep 2007 | WO |
| WO 2007134322 | Nov 2007 | WO |
| WO 2008130369 | Oct 2008 | WO |
| WO 2009031886 | Mar 2009 | WO |
| WO 2009042147 | Apr 2009 | WO |
| WO 2010138102 | Dec 2010 | WO |
| WO 2012028776 | Mar 2012 | WO |
| Entry |
|---|
| Dameron, A.A. et al., “Molecular Layer Deposition of Alucone Polymer Films Using Trimethylaluminum and Ethylene Glycol,” Chem. Mater., 2008, pp. 3315-3326, vol. 20. |
| PCT Invitation to Pay Additional Fees, PCT Application No. PCT/US12/25095, May 22, 2012, 2 pages. |
| PCT International Search Report and Written Opinion, PCT Application No. PCT/US12/25483, May 29, 2012, 10 pages. |
| U.S. Appl. No. 13/369,717, filed Feb. 9, 2012, Inventor: Sang In Lee. |
| U.S. Appl. No. 13/397,590, filed Feb. 15, 2012, Inventor: Sang In Lee. |
| PCT International Search Report and Written Opinion, PCT Application No. PCT/US11/45199, Dec. 6, 2011, 10 pages. |
| PCT International Search Report and Written Opinion, PCT Application No. PCT/US2011/056285, Mar. 8, 2012, 11 pages. |
| PCT International Search Report and Written Opinion, PCT Application No. PCT/US11/58552, Mar. 14, 2012, 12 pages. |
| PCT International Search Report and Written Opinion, PCT Application No. PCT/US2011/060474, Mar. 22, 2012, 12 pages. |
| U.S. Appl. No. 13/190,104, filed Jul. 25, 2011, Inventor: Sang In Lee. |
| PCT International Search Report, PCT Application No. PCT/US12/24451, May 21, 2012, 12 pages. |
| PCT Written Opinion, PCT Application No. PCT/KR2010/001076, Sep. 27, 2010, 8 pages. |
| PCT International Search Report and Written Opinion, PCT Application No. PCT/US2010/037660, Aug. 3, 2010, 9 pages. |
| PCT International Search Report and Written Opinion, PCT/US2010/050358, Dec. 1, 2010, 10 pages. |
| “Atomic Layer Deposition,” Cambridge NanoTech Inc., 2005, 40 pages, [Online] Retrieved from the Internet<URL:http://www.pascaltechnologies.com/files%5CTech.Docs%5CAtomic%20Layer%20Deposition%20Tutorial.pdf>. |
| Puurunen, R.L. et al., “Surface Chemistry of Atomic Layer Deposition: A Case Study for the Trimethylaluminum/Water Process,” Journal of Applied Physics, 2005, pp. 121301-1-121301-52, vol. 97. |
| European Extended Search Report, European Application No. 10786646.9, Nov. 29, 2012, 17 pages. |
| PCT International Search Report and Written Opinion, PCT Application No. PCT/US11/44470, Dec. 7, 2011, 13 pages. |
| PCT International Search Report and Written Opinion, PCT Application No. PCT/US12/25095, Aug. 3, 2012, 18 pages. |
| U.S. Appl. No. 13/185,793, filed Jul. 19, 2011, Inventor: Sang In Lee. |
| U.S. Appl. No. 13/273,076, filed Oct. 13, 2011, Inventor: Sang In Lee. |
| U.S. Appl. No. 13/285,417, filed Oct. 31, 2011, Inventor: Sang In Lee. |
| U.S. Appl. No. 13/295,012, filed Nov. 11, 2011, Inventor: Sang In Lee. |
| European Examination Report, European Application No. 10821080.8, Apr. 17, 2013, 11 pages. |
| Choi, J. M. et al., “Ultraviolet Enhanced Si-Photodetector Using p-NiO Films,” Applied Surface Science, May 15, 2005, pp. 435-438, vol. 244, No. 1-4. |
| European Extended Search Report, European Application No. 10733634.9, Jan. 30, 2013, 5 pages. |
| Hermle, M. et al., “Analyzing the Effects of Front-Surface Fields on Back-Junction Silicon Solar Cells Using the Charge-Collection Probability and the Reciprocity Theorem,” Journal of Applied Physics, Mar. 10, 2008, 7 pages, vol. 103, No. 5. |
| Kymakis, E. et al., “Bi-Layer Photovoltaic Devices with PPQ as the Electron Acceptor Layer,” Solar Energy Materials & Solar Cells, Jul. 24, 2006, pp. 1705-1714, vol. 90, No. 12. |
| Verlinden, P. et al., “Measurement of Diffusion Length and Surface Recombination Velocity in Interdigitated Back Contact (IBC) and Front Surface Field (FSF) Solar Cells,” Physica, 1985, pp. 317-321, vol. 129, No. 1-3. |
| Yoshikawa. O. et al., “Enhanced Efficiency and Stability in P3HT:PCBM Bulk Heterojunction Solar Cell by Using TiO2 Hole Blocking Layer,” Mater. Res. Soc. Symp. Proc., Materials Research Society, Jan. 2007, 6 pages. |
| Chinese First Office Action, Chinese Application No. 201080025311.3, Jun. 25, 2013, 14 pages. |
| Japanese First Office Action, Japanese Application No. 2012-514229, Jul. 17, 2013, 8 pages. |
| Japanese Office Action, Japanese Application No. 2012-532219, Sep. 10, 2013, 7 pages. |
| U.S. Appl. No. 13/904,825, filed May 29, 2013, Inventor: Sang In Lee. |
| He, G. et al., “Metal-Organic Chemical Vapor Deposition of Aluminum Oxynitride from Propylamine-Dimethylaluminum Hydride and Oxygen: Growth Mode Dependence and Performance Optimization,” Journal of Materials Chemistry, 2012, pp. 7468-7477, vol. 22. |
| Zhu, M. et al., “Aluminum Oxynitride Interfacial Passivation Layer for High-Permittivity Gate Dielectric Stack on Gallium Arsenide,” Applied Physics Letters, 202903, 2006, pp. 1-3, vol. 89. |
| European Examination Report, European Patent Application No. 10786646.9, Oct. 24, 2013, 5 pages. |
| Maydannik, P.S. et al., “An Atomic Layer Deposition Process for Moving Flexible Substrates,” Chemical Engineering Journal, 2011, pp. 345-349, vol. 171. |
| Taiwan Office Action, Taiwan Application No. 100126066, Oct. 8, 2013, 14 pages. |
| Japanese Office Action, Japanese Application No. 2012-514229, Nov. 12, 2013, 4 pages. |
| Number | Date | Country | |
|---|---|---|---|
| 20100310771 A1 | Dec 2010 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61185076 | Jun 2009 | US |
