This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2016-049710, filed Mar. 14, 2016, the entire contents of which are incorporated herein by reference.
Embodiments described herein relate generally to a semiconductor device which includes an interconnect employing a graphene layer (a graphene interconnect) and a method of manufacturing the same.
In recent years, miniaturization of interconnects has advanced in LSI interconnect structures. The miniaturization brings about problems such as an increasing of electric resistivity caused by interfacial inelastic scattering of electrons, an increasing of current density, and a reliability degradation due to stress migration or electromigration. To solve these problems, copper is mainly used as an LSI interconnect material, which is a low-resistance metal.
In general, according to one embodiment, a semiconductor device is disclosed. The device includes a substrate, and a first interconnect on the substrate. The first interconnect includes a first catalyst layer capable of growing graphene, a graphene layer in contact with a side surface of the first catalyst layer. The device further includes a non-catalyst layer in contact with a bottom surface of the graphene layer, and incapable of growing graphene.
According to another embodiment, a method of manufacturing a semiconductor device is disclosed. The method includes forming a non-catalyst layer on the substrate, forming a through hole in the non-catalyst layer. The method further includes forming a catalyst layer for graphene growth, on a region corresponding to the through hole of the non-catalyst layer; and forming a graphene layer on an upper surface of the non-catalyst layer.
Embodiments will be described hereinafter with reference to the accompanying drawings. The drawings are merely schematic and conceptual diagrams, and the dimensions of elements shown, the rations between the elements and the like in the drawings are not necessarily the same as those of actual implementations of the embodiments. Further, in the drawings, identical or corresponding portions are denoted by the same reference numerals, and their repetitive description will be repeated when necessary. In addition, as used in the description and the appended claims, the singular forms “a”, “an”, and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As mentioned above, copper is a low-resistance metal. However, if the interconnects are further miniaturized, the above-described problems may be caused even copper is employed.
Graphene exhibits quantized conductance (what is called Ballistic conductance), and may be an extremely low resistance material as an alternative to the existing metallic materials. In view of this, an interconnect comprising graphene (graphene interconnect) is used as an LSI interconnect in the following embodiments. It is noted that a copper interconnect or an aluminum interconnect may be used together with the graphene interconnect in the semiconductor device.
The semiconductor device of the present embodiment comprises graphene interconnects 10. Three linear graphene interconnects 10 are depicted in
Each graphene interconnect 10 includes one graphene layer 500, two catalyst layers (a first catalyst layer and a second catalyst layer) 400 and one underlayer (a non-catalyst layer) 201.
The graphene layer 500 is provided between the two catalyst layers 400. The two catalyst layers 400 are connected to each other by the graphene layer 500. The graphene layer 500 is in contact with side surfaces S1 and S2 of the two catalyst layers 400 opposed to each other. The underlayer 201 is provided under the graphene layer 500. The underlayer 201 is in contact with a lower surface of the graphene layer 500.
The graphene layer 500 is also provided in a region other than the region between side surfaces S1 and S2 of the two catalyst layers 400 opposed to each other. The graphene layer 500 in the above-described another region is formed due to a process for growing graphene. That is, in the process, the graphene grows from four side surfaces of catalyst layer 400 illustrated in a plan view of
Similarly, the underlayer 201 under the graphene layer 500 in the above-described another region is also formed due to the process for growing graphene. That is, in the process, the graphene is grown on an exposed underlayer 201 illustrated in the plan view of
The catalyst layer 400 has a function of catalyst for growing graphene. Note that, in the present disclosure, graphene includes at least one of a monolayer graphene, and a multilayer of monolayer graphene (stacked graphene). In addition, the graphene layer in the embodiments is a layer including the graphene.
The material of the catalyst layer 400 contains, for example, at least one of cobalt (Co), nickel (Ni), iron (Fe), ruthenium (Ru) or copper (Cu), and an alloy containing Co, Ni, Fe, Ru or Cu, and carbide of Co, Ni, Fe, Ru or Cu.
The catalyst layer 400 is a monolayer film or a stacked multilayer film containing the above-described material. In a state where the catalyst layer 400 is dispersed into fine particles, graphene does not grow appropriately, or a graphene layer may be formed discontinuously. Therefore, it is preferable that the catalyst layer 400 be a continuous film.
The distance between the two catalyst layers 400 (the longitudinal dimension of the interconnection 10) is greater than or equal to a mean free path of electrons in graphene, for example, greater than or equal to 0.1 μm, more preferably, greater than or equal to 1 μm. Noted that a single catalyst layer may be used instead of the two graphene layers 400 as long as the single graphene layers 400 enables the graphene to grow into a graphene layer with a length not less than the mean free path.
An upper surface of the catalyst layer 400 is lower than an upper surface of the graphene layer 500 in the present embodiment, but the upper surface of the catalyst layer 400 may be higher than the upper surface of the graphene layer 500. Alternatively, the upper surface of the catalyst layer 400 may be as high as the upper surface of the graphene layer 500.
The catalyst layer 400 has a function for growing graphene. However, the underlayer 201 does not have the function for growing graphene. In the present embodiment, the underlayer 201 has an insulating property. A material of the underlayer 201 includes, for example, oxide of the material of the catalyst layer 400 such as copper oxide or nickel oxide, or metal oxide such as aluminum oxide (for example, Al2O3) which is more graphene-adsorptive than silicon oxide.
An interlayer insulating film 600 is provided on the graphene layer 500. The interlayer insulating film 600 may be provided with a plug (not shown) which is in contact with the catalytic layer 400.
In the present embodiment, as illustrated in
When employing a method of selective deposition of catalyst material onto a selected area to form the catalyst layer 400, the area of the lower surface of the catalyst layer 400 is approximately same as the area of the upper surface of the plug 202. However, there is no particular relationship between the area of the lower surface of the catalyst layer 400 and the area of the upper surface of the plug 202.
In the present embodiment, a lower surface of the plug 202 is connected to a substrate 100. More specifically, the lower surface of the plug 202 may be connected to a source or drain region of a MOS transistor (not shown) in the substrate 100, for instance. It is noted that the lower surface of the plug 202 may be connected to an element other than the MOS transistor in the substrate 100, for example, a capacitor. In addition, the lower surface of the plug 202 may be connected to a member (not show) such as an interconnect between the substrate 100 and the interconnect 10. The interconnect is, for example, a damascene interconnect which is formed in an interlayer insulating film on the substrate 100.
The semiconductor device of the present embodiment will be further described below in accordance with a method of manufacturing the same.
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An interlayer insulating film 200 is formed on the substrate 100. The substrate 100 includes, for example, a semiconductor substrate such as a silicon substrate. An element device such as a MOS transistor or a capacitor is formed on the semiconductor substrate.
The underlayer 201 is formed on the interlayer insulating film 200. Here, the underlayer 201 is formed of an insulating material, for example, aluminum oxide.
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Connection holes 203 are formed through the underlayer 201 and the interlayer insulating film 200 down to the substrate 100, and then a conductive film 202 to be processed into plugs is formed on a region including the underlayer 201 such that the connection holes 203 are filled with conductive film. A material of the interlayer insulating film 200 is, for example, tetraethyl orthosilicate (TEOS). A material of the conductive film 202 is, for example, Cu, Al or W, or an alloy including at least one of Cu, Al or W.
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A chemical mechanical polishing (CMP) process is applied to the conductive film 202 and the underlayer 201 in order to remove the conductive film 202 formed outside the connection holes 203, and planarize the surfaces of the conductive 201 and the underlayer film 202. After the CMP process, the conductive film 202 has a plug shape. The conductive film 202 after the CMP process will be hereinafter referred to as the plug 202
Note that, depending on the material of the plug 202, the material (for example, Cu) may be diffused into the interlayer insulating film 200. Such a diffusion is prevented by coating the bottom and the side surface of the plug 202 with a barrier metal film (for example, a TiN film).
After that, the interlayer insulating film (first insulating film) 300 is formed on a region including the underlayer 201 and the plug 202, and then a surface of the interlayer insulating film 300 is planarized by CMP process.
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A photolithography process and an etching process are performed to selectively remove the interlayer insulating film 300 in a region corresponding to a graphene interconnect which is to be formed later. As a result, the upper surfaces of the plug 200 and the underlayer 201 in the region corresponding to the graphene interconnect are exposed. The above-described etching process is, for example, a reactive ion etching (RIE) process.
In the present embodiment, the underlayers (non-catalyst layers) 201 of the graphene interconnects 10 are different portions of the same single underlayer.
Next, the catalyst layer 400 is formed on the upper surface of the plug 202, and catalyst layer 400 is connected to the substrate via the plug 202. In the present embodiment, the catalyst layer 400 is also formed on the upper surface of the underlayer 201 around the upper surface of the plug 202. Therefore, the catalyst layer 400 is formed substantially selectively on the upper surfaces of the plugs 202. In other words, the catalyst layers 400 are formed on the regions corresponding to the connection holes 203 which are formed in a manner to penetrate through the catalyst layer 201 in the process of
The method of selectively forming the catalyst layer 400 will be described below.
In the case of employing a Ni layer as the catalyst layer 400, the catalyst layer (Ni layer) 400 is formed substantially selectively by a chemical vapor deposition process (CVD) using, for example, gaseous nickel amidinate as a source gas and gaseous ammonia as a reducing gas. The catalyst layer 400 is formed at a temperature, for example, in a range from 200 to 600° C. Further, The Ni layer is also formed substantially selectively by nickel plating using, for example, a Watts plating bath (an electroplating bath containing nickel sulfate, nickel chloride and boric acid).
It is noted that the material of the catalyst layer 400 is not necessarily deposited selectively on the specific area. For example, in the case of forming a catalyst layer 400 of the same material as that of the plug 202, the catalyst layer 400 may be formed in the following manner. That is, a conductive film to be processed into the catalyst layer 400 is formed, then a surface of the conductive film is planarized by a CMP process, and the conductive film is patterned by using photolithography process and etching process (for example, an RIE process), thereby obtaining the catalyst layer 400.
It is noted that the catalyst layer 400 may be formed in such a manner as to remain within the upper surface of the plug 202.
The catalyst layer 400 has a function to control the height (thickness) of the graphene layer. The height (thickness) of the catalyst layer 400 is, for example, about 10 to about 30 nm.
Here, the height of the upper surface of the catalyst layer 400 is substantially the same as that of the upper surface of the interlayer insulating film 300, but the upper surface of the catalyst layer 400 may be higher than the upper surface of the interlayer insulating film 300. Further, the upper surface of the catalyst layer 400 may be lower than the upper surface of the interlayer insulating film 300. That is, the height of the upper surface of the catalyst layer 400 and the height of the upper surface of the interlayer insulating film 300 may not be in any particular relationship as long as the graphene layer with a necessary height is obtained.
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A graphene layer 500 is formed on the underlayer by growing graphene from the side surfaces of the catalyst layer 400 at a low temperature, for example, 650° C. (the lower limit is, for example, 300° C.), by using a low-temperature CVD process with source gas including carbon.
The longitudinal dimension of the graphene layer 500 (interconnect length) may be controlled by the dimension of the long side of the linearly exposed surface of the underlayer 201 in the process of
Similarly, the lateral dimension (interconnect width) of the graphene layer 500 may be controlled by the dimension of the short side of the linearly exposed surface of the underlayer 201 in the process of
Therefore, according to the present embodiment, the graphene interconnect 10 including the graphene layer 500 of the long interconnect length and the narrow interconnect width may be easily realized.
Here, graphene does not have width-dependent resistance, ideally. Therefore, even though the interconnect width is reduced by the miniaturization, an increase in the resistance of the graphene interconnect 10 is suppressed. Further, graphene has a long ballistic wavelength of about 100 nm to about 1 μm. Therefore, even though the interconnect length is increased, the increase in the resistance of the graphene interconnect 10 is also suppressed. In order to suppress the increase in the resistance of the graphene interconnect 10, the interconnect width of the graphene interconnect 10 is, for example, one-tenth or less of the interconnect length of the graphene interconnect.
A bit line is an example of the interconnect with the narrow width and the long length. The graphene interconnect 10 is applicable to the bit line.
In order to further reduce the resistance of the graphene layer 500, impurities may be added to the graphene layer 500. For this purpose, the impurities may be added in the above-described source gas. Alternatively, a treatment such as annealing may be applied to the graphene layer 500 in an atmosphere containing the impurities, which is performed after the graphene layer 500 is formed. The impurities includes, for example, chemical element of group 14, group 15, group 16 or group 17. More specifically, the impurities includes N, Cl or Br, or chemical compound containing N, Cl or Br. The impurities may also contain metals such as Fe.
The catalyst layer 400 is not provided on the upper surface of the interlayer insulating film 300, and the graphene layer 500 is formed into the roll shape as described above, thus the graphene layer 500 is not formed on the upper surface of the interlayer insulating film 300.
In general, the underlayer 201 does not have a completely flat surface but has an uneven surface as shown in
The graphene layer 500a is grown in planar directions using a facet of the underlayer 201a as starting point of growth. However, there is a case where the graphene layer 500a is not formed on projected portions 210 of the uneven surface of the underlayer 201a, which provides the possibility that the graphene layer 500a is formed discontinuously. When the graphene layer 500a constituting the interconnect is formed discontinuously, the interconnect will have a break. Such a breaking is suppressed in the present embodiment because the underlayer 202 of the present embodiment does not have the function of catalyst for graphene.
After the graphene layer 500 is formed, the interlayer insulating film (second insulating film) 600 is then formed on the interlayer insulating film 300 and the graphene layer 500, thereby obtaining the semiconductor device depicted in
As described above, according to the present embodiment, the graphene layer 500 having the long interconnect length and the short interconnect width is easily formed by using the catalyst layer 400 as a starting point of the growth of graphene and by using the underlayer 201 without catalyst function for graphene as an underlayer for the graphene which grows from the catalyst layer 400, thereby providing the semiconductor device comprising the low-resistance graphene interconnect 10.
The present embodiment is different from the first embodiment in that a cavity 700 is provided between a side surface of the graphene layer 500 and an interlayer insulating film 300. That is, the cavity 700 is provided around the graphene layer.
A capacitance between adjacent graphene interconnects 10 (parasitic capacitance) is reduced by the cavity 700, thereby reducing signal delay (RC delay) in the graphene interconnect 10.
In order to reduce capacitance between the interconnects, the cavities 700 shown in the sections of
In order to form the cavity 700, the interlayer insulating film 300 requires poor adherence to graphene. For example, an SiO2 film is used as the interlayer insulating film 300. Further, as an interlayer insulating film 600, an insulating film with small embedding properties is used, for example, a silicon oxycarbide (SiOC) film or an SiO2 film formed by spin on direct (SOD) method is used. In this way, it is possible to prevent the interlayer insulating film 600 from being formed in the cavities 700. Still further, an insulating layer such as an Al2O3 layer may be used as the underlayer 201 for instance. Still further, an SiO2 film may be used as the interlayer insulating film 200 for instance, which is formed by a CVD process using tetraethyl orthosilicate (TEOS) as a source gas. Still further, a W plug may be used as a plug 202 for instance.
The present embodiment is different from the first embodiment in that a catalyst layer (third catalyst layer) 401 is further provided between two catalyst layers 400. The reason will be described below.
Graphene is grown from the catalyst layer 400 to form a graphene layer 500. Therefore, as the distance between two plugs 202 increases, it requires more time for graphene to grow into the graphene layer 500 which connects the two plugs 202.
Further, depending on process conditions of the device using the graphene layer 500, it is necessary to grow graphene at a low temperature (for example, lower than 300° C.). Again, it requires more time for graphene to grow into the graphene layer 500.
In view of this, the third catalyst layer 401 capable of growing graphene is provided between the two catalyst layers 400, thereby shortening the time required for graphene to grow into the graphene layer 500
Note that, in the present embodiment, the dimension of the third catalyst layer 401 in the longitudinal direction of the interconnect is less than the dimension of the catalyst layer 400 in the longitudinal direction of the interconnect. In this way, an increase in the resistance of the graphene interconnect 10 is suppressed. Further, in the present embodiment, the volume of the third catalyst layer 401 is less than the volume of the catalyst layer 400.
When an increase in the resistance of the third catalyst layer 401 is not too serious to cause an undesirable effect, the dimension of the third catalyst layer 401 in the longitudinal direction of the interconnect may be the same as the dimension of the catalyst layer 400 in the longitudinal direction of the interconnect, or the dimension of the third catalyst layer 401 in the longitudinal direction of the interconnect may be greater than the dimension of the catalyst layer 400 in the longitudinal direction of the interconnect.
The semiconductor device of the present embodiment comprises a dummy plug (third plug) 202d provided under the catalyst layer 401. The dummy plug 202d does not penetrate through the interlayer insulating film 200, and the lower surface of the dummy plug 202d is not connected to the substrate 100. That is, the dummy plug 202d fails to connect the catalyst layer 401 with the substrate 100, and thus the dummy plug 202d does not have a function to electrically connect a layer below the dummy plug 202d and .a layer above the dummy plug 202d. In the present embodiment, the catalyst layer 401 is provided on the upper surface of the dummy plug 202d, and the upper surface of the underlayer 201 around the upper surface of the dummy plug 202d.
An exemplary method of manufacturing the semiconductor device of the present embodiment will be described below.
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After the step of
Conversely, the connection holes 203 may be formed after the grooves 204 are formed.
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A conductive film to be processed into the plug 202 and the dummy plug 202d is formed to fill the connection holes 203 and the groove 204, and then a CMP process is performed to remove the conductive film on a region outside the connection holes 203 and the groove 204, thereby forming the plugs 202 and the dummy plug 202d in the connection holes 203 and the trench 204, respectively.
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Photolithography process and etching process are performed to remove a portion of the interlayer insulating film 300 corresponding to a region on which the graphene interconnect is to be formed. The removal of the portion of the interlayer insulating film 300 results in exposing the upper surfaces of the plugs 202, the dummy plug 202d and the underlayer 201 corresponding to a region on which the graphene interconnect is to be formed. After that, the catalyst layer 400 and the catalyst layer 401 are formed substantially selectively on the upper surface of the plug 202 and the upper surface of the dummy plug 202d, respectively. In the present embodiment, the catalyst layer 400 is also formed on the underlayer 201 around the upper surface of the plug 202, and the third catalyst layer 401 is also formed on the underlayer 201 around the upper surface of the dummy plug 202d. However, the catalyst layer 400 and the catalyst layer 401 may be formed in such a manner as to remain within the upper surface of the plug 202 and the upper surface of the dummy plug 202d.
In a case where the catalyst layers 400 and 401 are not formed selectively, the dummy plug 202d may be omitted. In this case, the catalyst layers 400 and 401 are obtained by forming a catalyst layer to be processed into the catalyst layers 400 and 401, and then patterning the catalyst layer by using photolithography process and etching process.
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With the use of a low-temperature CVD process using a source gas including carbon, graphene is grown form the side surfaces of the catalyst layers 400 and 401, thereby forming the graphene layer 500.
After the graphene layer 500 is formed, an interlayer insulating film 600 is formed on the interlayer insulating film 300 and the graphene layer 500, thereby obtaining the semiconductor device shown in
The present embodiment is different from the first to third embodiments in that an underlayer 201a has a conductive property. Therefore, a graphene layer 10a does not affect the parasitic capacitance and the breakdown voltage. In addition, the employment of the underlayer 201a having the conductive property, the resistance of the graphene interconnect 10a is reduced. A material of the underlayer 201a is, for example, titanium nitride or metal nitride, which more easily adheres to the graphene than silicon nitride does.
An exemplary method of manufacturing the semiconductor device of the present embodiment will be described below.
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An interlayer insulating film 200 is formed on a substrate 100, and a plug 202 is formed in the interlayer insulating film 200. After that, a conductive layer 201a is formed on the interlayer insulating film 200 and the plug 202.
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Photolithography process and etching process are applied to the conductive layer 201a to form through holes 205 which expose upper surfaces of the plugs 202 and, a plurality of regions of the upper surface of the interlayer insulating film 200 around the upper surfaces of the plugs 202, and then the conductive layer 201a is divide into layers such that the layers correspond to the graphene interconnects. The layers obtained by dividing the conductive layer 201a will be hereinafter referred to as underlayers 201a.
Here, if the graphene interconnects are formed on the conductive layer 201 with the shape in
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A catalyst layer 400 is formed on the upper surface of the plug 202 and the plurality of regions of the upper surface of the interlayer insulating film 200 around the upper surface of the plug 202. In other words, the catalyst layers 400 are formed on the regions corresponding to the through holes 205 which are formed in the process of
Subsequently, graphene is grown from the side surfaces of the catalyst layer 400, thereby forming a graphene layer 500.
After the graphene layer 500 is formed, an interlayer insulating film 600 is formed on the interlayer insulating film 200 and the graphene layer 500, thereby obtaining the semiconductor device depicted in
In the first to third present embodiments, the insulating layer to be processed into the underlayer 201 may be divided into layers corresponding to the graphene interconnects in a manner similar to that of the present embodiment. In this way, the parasitic capacitance between the graphene interconnects can be reduced.
While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the novel embodiments described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the embodiments described herein may be made without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the inventions.
Number | Date | Country | Kind |
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2016-049710 | Mar 2016 | JP | national |