This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2010-068430, filed Mar. 24, 2010; the entire contents of which are incorporated herein by reference.
Embodiments described herein relate generally to a semiconductor device using carbon nanotubes, and a method of manufacturing this semiconductor device.
In recent years, there has been proposed a method of reducing a wiring resistance by forming carbon nanotubes (CNTs) in a via hole of a multilayer wiring. In this method, TaN/Ti(N)/Co, which functions as a catalyst layer of CNTs, is formed in advance in the via hole, and then a film of CNTs is formed by a chemical vapor deposition (CVD) method. At this time, since the catalyst layer is formed not only within the via hole, but also on the entire surface of the wafer, the CNTs are grown not only in the via hole but also on the entire surface of the wafer. Subsequently, in order to leave the CNTs only in the via hole, the excess CNTs, which are present outside the via hole, are removed by chemical mechanical polishing (CMP). The CNT has such properties that the CNT flexibly bends in the lateral direction, that is, in the horizontal direction, relative to the via hole. Thus, in order to perform CMP, it is necessary to solidify the CNTs by impregnating, a SiO2 film of Spin on Direct (SOD), into the CNTs.
However, if the CNTs are grown at high density, the CNTs transition to the state in which that amount of the SOD film, which can fully solidify the CNTs, cannot be impregnated in the CNTs. In this case, the CMP process cannot be performed. In order to reduce the via resistance, the realization of the high density of CNTs is indispensable. Thus, it is difficult to make compatible the reduction in via resistance and the CMP process. Moreover, since the CNT itself has a very high resistance to chemical treatment, it is very difficult to etch the CNT itself by CMP.
Besides, when CNTs are grown on the entire surface, there occurs growth of CNTs from the side surface of the via hole. The CNTs, which are grown from the side surface of the via hole, greatly increase the via resistance. In worst cases, the top face of the via is buried by the CNTs that are grown from the side wall, and thus the via is, in fact, broken.
In general, according to one embodiment, there is provided a semiconductor device using carbon nanotubes. A via hole for connection to a Cu wiring is formed in an interlayer insulation film provided on a substrate including the Cu wiring. A first metal film is formed on the Cu wiring in the via hole, the first metal film functioning as a barrier to the Cu wiring, and functioning as a co-catalyst (promoter) of carbon nanotube growth, and being in contact with a side wall surface of the via hole of the first interlayer insulation film. A second metal film is formed at least on the first metal film in the via hole, the second metal film functioning as a catalyst of the carbon nanotube growth. Carbon nanotubes are formed in the via hole in which the first metal film and the second metal film are formed.
A CNT has such properties that the CNT grows in a direction substantially perpendicular to a catalyst, and it is proposed that the CNT is applied to a contact material of a via of an LSI device. Specifically, after a contact is opened, a film of a catalyst metal is grown, and then CNTs are grown. Subsequently, in order to leave CNTs only in the via, excess CNTs are removed. However, since a CMP process of CNTs is very difficult, a process method which is a substitute for CMP, or a structure which does not use CMP is needed.
Reference numeral 10 in
A first wiring layer insulation film 15, which is formed of SiOC, is deposited on the insulation film 12 and contacts 13 via a stopper insulation film 14 which is formed of SiCN. A wiring groove, which is continuous with the contact 13, is provided in the insulation film 15. A first wiring 17 of, e.g. Cu, is buried in the wiring groove via a barrier metal 16.
An interlayer insulation film (first interlayer insulation film) 19 of, e.g. TEOS is formed on the insulation film 15 and first wiring 17 via a stopper insulation film 18 which is formed of SiCN. A via hole, which is continuous with the first wiring 17, is formed in the insulation film 19. A first metal film 21, which is formed of Ta or a nitride thereof and functions as a promoter of CNT growth, is selectively formed at a bottom part of the via hole. For example, a TaN film is grown on a Cu film serving as the first wiring 17 by a selective CVD method. A second metal film 22, which functions as a catalyst of CNT growth, is formed on the metal film 21 and on side surfaces of the via hole. Carbon nanotubes (CNTs) 23 are buried in the via hole.
The first metal film 21 is in contact with a lower part of the interlayer insulation film 18 and 19. The first metal film 21 is not formed on the side wall surface of the via hole of the first interlayer insulation film 18 and 19. In this embodiment, as shown in
As shown in
As has been described above, in the present embodiment, the first metal film 21, which is formed of Ta or a nitride thereof and is selectively formed on only the Cu wiring 17 at the bottom of the via hole, functions as the promoter of CNT growth. Thus, all the CNTs 23 grow basically from the bottom part of the via hole, and growth of CNTs from side surfaces of the via hole is suppressed. Since CNTs, which grow from the side wall, become electrically conductive via a barrier metal, it is desirable, from the standpoint of reduction in via resistance, that there is no growth from the side wall. By growing the CNTs from only the bottom surface of the via, the number of CNTs, which directly contribute to electrical conductance, becomes remarkably larger than in the prior art, and the reduction in via resistance can be realized.
In addition, the TaN film, which serves as the first metal film 21, is not formed on the side surfaces of the via hole, and only the Ti/Co layer, which serves as the second metal film 22, is formed on the side surfaces of the via hole. In this case, it is indispensable that the TaN film is a continuous film, from the standpoint of ensuring barrier properties, and a certain thickness of the TaN film is needed. On the other hand, the Ti/Co layer is a discontinuous film in a dispersed state, and may have a very small thickness of about 0.5 nm. Although there is a case in which the Ti layer becomes a discontinuous film, the thickness of the Ti layer may be small at any case. Accordingly, the reduction in opening area of the via due to the Ti/Co layer, which is formed on the side surfaces of the via hole, can be decreased, and the area of occupation by the CNTs, which contribute to electrical conduction, increases. Therefore, further reduction in via resistance is possible.
Since the first metal film 21 must have a promoter function, TiN may be used in place of TaN as the material of the first metal film 21. In addition, a single-layer film of Co may be used in place of the multilayer film of Ti/Co as the material of the second metal film 22.
To start with, as shown in
Subsequently, although not shown, a cap film of, e.g. SiO2, which functions as a protection film for protection from damage due to RIE or CMP, is formed on the insulation film 15. Then, after performing a resist coating/lithography step (not illustrated), a single damascene wiring structure is formed by RIE.
Thereafter, a Ta film 16 is formed as a barrier metal in the damascene wiring structure. Further, after forming a Cu seed film which becomes a cathode electrode of electrolytic plating, a Cu film (first wiring) 17 which functions as an electrically conductive material is formed by, e.g. an electrolytic plating method. Then, an excess portion of the Cu film 17 is polished and removed by CMP. At last, a diffusion prevention film 18, which prevents surface diffusion of Cu and serves as a process stopper layer of the upper wiring structure, is formed, and a lower wiring is completed. The structure, which has been fabricated up to the lower wiring, is used as an underlying substrate.
The above-described process is not different from the conventional process of Cu wiring formation. Thus, the materials and fabrication methods of the insulation films 12, 14, 15 and 18, contacts 13, barrier metal 16 and first wiring 17 may properly be varied according to specifications.
Next, as shown in
Next, as shown in
To cope with this problem, in the present embodiment, as shown in
As regards Co, the Co in an elemental metal state has the same composition as Co which functions as a catalyst metal, and has no barrier properties to the Co of the catalyst metal, and, as a result, a film of the catalyst metal Co cannot dispersedly be formed. Thus, when Co is selectively grown, a nitriding process is performed after a Co film is formed or while a Co film is being formed. Thereby, the surface or the entirety of the selectively grown Co film is nitrided, and a Co nitride is formed. As regards the nitriding process, the nitriding process may be replaced with an oxidizing process, and an oxide of Co may be formed. Although Ta, Ru and W can be used as elemental metals, these metals may be subjected to a nitriding process or an oxidizing process, like Co, from the standpoint of an improvement of barrier properties. When a nitride film is formed, nitrogen may be introduced in a gas during the selective growth of a metal film by CVD, or the surface of a metal film, after selective growth, may be nitrided. A metal film, which is selectively grown, needs to be, at least, a continuous film, from the standpoint of diffusion barrier properties, and the metal film needs to have a film thickness of 1 nm or more. Moreover, it is also possible to use the TiN film that has the promoter operation as the first metal film 21.
Next, as shown in
Next, as shown in
A hydrocarbon gas, such as methane or acetylene, or a mixture gas thereof, is used as a carbon source of CVD for forming the CNTs, and hydrogen or a noble gas is used as a carrier gas. The upper limit of the process temperature is about 1000° C., the lower limit of the process temperature is about 200° C., and it is particularly desirable that the temperature for growth be about 350° C. It is effective to use a remote plasma, and further to apply a voltage by disposing an electrode at an upper part of the substrate in order to eliminate ions and electrons. The application voltage in this case should preferably be about 0 to ±100 V. By controlling the temperature for growth and the application voltage, a clear difference can be made in CNT growth speed between the inside of the via hole and the upper planar part, and the CNT 23 can selectively be grown only in the via hole.
Next, a SiO2 film of SOD, for example, is impregnated in the CNTs 23, and CMP of the CNTs 23 is performed. Since the CNTs 23 in the via hole are grown at high density, the SOD film is not easily impregnated in this CNTs 23. However, on the upper planar part, CNTs are not basically grown, or even if CNTs are grown, the speed of growth is low and the density of CNTs is low. Thus, as shown in
By this structure, the CMP process of the CNTs 23, which is difficult in the prior art, can easily be performed. In addition, by managing the speed of growth or the time of growth of the CNTs 23 in the via hole, the length of the CNTs 23, which excessively project to the upper part, can be decreased. Accordingly, the amount of CNTs, which is removed by CMP, decreases. Therefore, even the CNTs having high resistance to chemical treatment of CMP can easily be polished by CMP by mainly using a mechanical polishing component. In addition, by decreasing the length of the excessively projecting CNTs 23, almost the entirety of the CNTs 23 is fixed by the insulation film 19. Therefore, CMP can directly be performed, without impregnating SOD.
Next, as shown in
Thereafter, like the process of fabricating the lower wiring, metal films (barrier metal 26 and Cu film 27) are formed in the wiring groove, a thermal stabilization process and a CMP process are formed, and a diffusion barrier film 28 is formed. Thus, the structure shown in
In the present embodiment, as described above, in the stage preceding the formation of the CNTs 23, as shown in
The manufacturing process can be simplified by using TIN in place of TaN as the material of the first metal film 21 and using a single-layer film of Co in place of the multilayer film of Ti/Co as the material of the second metal film 22.
The third embodiment differs from the above-described second embodiment in that a metal film is formed in place of the SOD film, in a pre-process of CMP of the CNTs.
The fabrication steps up to
In this manner, in the present embodiment, the process condition of metal CMP can be used by using the metal film 51 in place of the SOD film which is the impregnation material of CMP. This increases the degree of freedom of process design, and reduces the manufacturing cost.
The fourth embodiment differs from the above-described first embodiment in that CNTs are grown up to an intermediate part of the via hole, and a metal film is formed in the other part of the via hole.
The fabrication steps up to
In addition, in the step of forming the metal film, an upper end portion of the CNTs 23 may be subjected to a pre-process, such as an ashing process by O2 or CO or a milling process by He or Ar. Thereby, the upper end portion of the CNTs 23 is opened, and all multi-walls of the CNTs can contribute to electrical conduction, and therefore the via resistance can further be reduced.
Subsequently, as shown in
As has been described above, in the present embodiment, the growth of the CNTs 23 is stopped at an intermediate part of the via hole, and the other part of the via hole is filled with the metal film 61. Thereby, the CMP of the CNTs 23 is unnecessary. Thus, the easiness of the process is improved, and the manufacturing cost can further be reduced.
In the present embodiment, unlike the process of separately fabricating the via structure and the upper wiring structure as in the second, third and third embodiments, a dual damascene process of simultaneously forming the via structure and the upper wiring structure is applied.
To begin with, as shown in
Next, as shown in
Subsequently, as shown in
As has been described above, in the present embodiment, since the CMP process in the via process is needless, the easiness of the process can be improved and the manufacturing cost can be reduced. After the growth of the CNTs, like the fourth embodiment, the step of opening the upper end portion of the CNTs may be performed prior to the process of forming the metal film. Thereby, the via resistance can further be reduced. Moreover, by using a metal (e.g. Ti), which forms a metal carbide, as a barrier metal of the upper wiring, a good interface contact structure of carbon nanotubes is formed, and the contact resistance can further be reduced.
The present invention is not limited to the above-described embodiments. The first metal film, which functions as a promoter for CNT growth, is not necessarily be limited to Ta or TaN, and use may be made of Ru, W, or a nitride thereof. Further, a nitride of Co may be used. The second metal film, which functions as a catalyst for CNT growth, is not limited to Co, and use may be made of Ni or Fe.
The second metal film may not necessarily be formed on the entire surface, and the second metal film may be selectively formed on only the surface of the first metal film. However, from the standpoint of the manufacturing process, it is easier to form the second metal film over the entire surface. In the present invention, the first metal film is formed on only the bottom part of the via hole. Thus, even if the second metal film is formed over the entire surface, the selective growth of CNTs from the bottom of the via hole is possible. Thus, the process can be made easier.
The conditions for forming the first and second metal films, and also the conditions for forming the CNTs (e.g. CVD gas, temperature, etc.) can properly be varied according to specifications.
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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2010-068430 | Mar 2010 | JP | national |