US20150061131A1 - Semiconductor device and method of manufacturing the same - Google Patents
Semiconductor device and method of manufacturing the same Download PDFInfo
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- US20150061131A1 US20150061131A1 US14/202,683 US201414202683A US2015061131A1 US 20150061131 A1 US20150061131 A1 US 20150061131A1 US 201414202683 A US201414202683 A US 201414202683A US 2015061131 A1 US2015061131 A1 US 2015061131A1
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/481—Internal lead connections, e.g. via connections, feedthrough structures
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
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- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/5226—Via connections in a multilevel interconnection structure
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- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions
- Embodiments described herein relate generally to a semiconductor device and a method of manufacturing the same.
- CNTs carbon nanotubes
- a method for forming carbon nanotubes (CNTs) within a via between multilayer interconnects of a semiconductor device has been proposed with a view to reducing interconnect resistance. Because of their quantization conductivity, CNTs offer the possibility of forming low-resistance interconnects in an LSI and so replacing metal interconnects. Further, since the structure of a CNT is tubular, and vertical deposition by the CVD method is possible, this technique is excellently compatible with the conventional vertical interconnect formation process of a device.
- a CNT is a new material which is expected to have excellent electrical properties in vertically arranged interconnects. With such CNTs, it is possible to realize low-resistance interconnects, particularly when the distance between interconnects is great.
- a measure for increasing their mean free path is important. For example, the measure which can be taken is doping the CNTs with an element such as boron (Br) or nitrogen (N) and so increasing the carriers transported.
- FIG. 1 is a cross-sectional view showing a schematic structure of a semiconductor device according to a first embodiment
- FIGS. 2A and 2B are schematic diagrams for use in indicating an enlarged structure of a CNT used for the semiconductor device of FIG. 1 and a state of element doping;
- FIG. 3 is a characteristic diagram showing the relationship between the line width and the volume resistivity of graphene
- FIGS. 4A and 4B are cross-sectional views for use in showing an example of element doping for graphene
- FIG. 5 is a schematic diagram showing an example of element doping for a CNT.
- FIGS. 6A to 6F are cross-sectional views showing a manufacturing process of a semiconductor device according to a second embodiment.
- a semiconductor device in which CNTs are used for a contact via comprises a substrate comprising a contact via groove, a catalyst layer for CNT growth which is formed at the bottom of the groove, and a CNT via formed by filling the CNTs into the groove in which the catalyst layer is formed.
- Each of the CNTs is formed by stacking a plurality of graphene layers in a state in which they are inclined depthwise with respect to the groove, and formed such that ends of the graphene layers are exposed on a sidewall of the CNT. Further, the CNT is doped with at least one element from the sidewall of the CNT.
- FIG. 1 is a cross-sectional view showing a schematic structure of a semiconductor device according to a first embodiment.
- the present embodiment relates to a structure in which a contact layer for connecting between a semiconductor element and an interconnect layer or between interconnect layers is formed on a substrate on which semiconductor elements such as a transistor and a capacitor are formed.
- the aforementioned structure particularly relates to one which uses CNTs as the contact layer material. Further, this structure relates to doping the CNTs with at least one element and applying the CNTs comprising graphene wall ends exposed on the CNT layer sidewalls to a contact.
- Reference numeral 10 in the figure indicates an Si substrate (semiconductor substrate) on which elements such as a transistor and capacitor are formed.
- a cap layer 11 of SiO 2 , SiOC, etc. which functions as a stopper insulating film, and an interconnect layer insulating film 12 of SiO 2 , etc., are formed.
- an interconnect groove is formed in the insulating film 12 , and an underlayer interconnect 15 is formed by filling a metal film into the interconnect groove.
- a ground insulating film is a film resistant to RIE damage, which is made of, for example, TEOS or SiOC which does not include minute holes.
- a contact via groove 23 is formed in the interlayer insulation film 22 which is above the underlayer interconnect 15 .
- a plurality of CNTs 33 are formed by the intermediary of an auxiliary catalyst layer 31 of Ti, TiN, etc., and a catalyst layer 32 of Ni, Co, etc.
- a CNT via 30 for connecting between the upper and lower interconnect layers is thereby structured.
- each of the CNTs 33 grows upward from the bottom of the catalyst layer 32 .
- the insulating film 42 may be lamination of an interconnect layer insulating film and an interlayer insulating film, or formed by an interlayer insulating film alone.
- the upper interconnect layer 45 is formed by filling a metal film into the groove, and the interlayer insulating film is formed on the upper interconnect layer 45 and the interconnect layer insulating film.
- the interlayer insulating film may be formed in such a way as to cover the upper interconnect layer 45 .
- the auxiliary catalyst layer 31 is an auxiliary film for facilitating the formation of the CNTs, and prevents diffusion of the components of the catalyst layer 32 from the catalyst layer 32 to the insulating film and an underlayer contact.
- auxiliary catalyst layer 31 Ta, Ti, Ru, W, Al, and the like, may be adopted.
- a nitride or an oxide of a film made from these elements, or a laminating material including such films may also be used.
- the catalyst layer 32 is a layer necessary for forming the CNTs.
- a catalyst material of the catalyst layer 32 it is preferred that a single element metal, such as Co, Ni, Fe, Ru, and Cu, an alloy including at least one of the aforementioned elements, or a carbide thereof or the like be used.
- the catalyst layer of the CNT should preferably be a discontinuous film which is in a dispersion state.
- an insulating film or metal formed by the CVD method for example, may be filled.
- deposition may be carried out such that a diffusion barrier layer, which is not shown, covers the interconnect structure.
- a diffusion barrier layer SiN, for example, is used.
- the CNTs to be used are featured in that a plurality of graphene walls exist at the outermost part of each of the CNTs, and a constituent element is not C alone.
- Each of the CNTs 33 in the CNT via 30 is formed to be a cup-stacked CNT. That is, as shown in FIG. 2A , a plurality of graphene layers 33 a are stacked in a state in which they are inclined depthwise with respect to the contact via groove 23 , and ends of the graphene layers 33 a are exposed on the sidewall of the CNT. The height of one graphene layer 33 a is 5 nm or more. Further, as shown in FIG. 2B , from the sidewall of the CNT 33 , the graphene layers 33 a are doped with least one kind of element 51 .
- graphene is an extremely thin carbon material formed by stacking about 1 to 100 layers of film including benzene rings arranged regularly on a plane.
- an ordinary CNT has a tubular structure having a diameter of 10 to 100 nm and is made of graphene, which is a carbon material of stacked films each including benzene rings arranged regularly on a plane.
- a cup-stacked CNT As in the present embodiment, as the CNT in which graphene wall ends are exposed on the CNT layer sidewall, a cup-stacked CNT, for example, is known.
- the cup-stacked CNT has a stacked structure of graphene layers which is shaped like a test tube.
- a mean free path becomes small and the resistance becomes high with a single graphene layer.
- the end of the CNT is positioned at the sidewall, a doping path of an element exists at the sidewall of the CNT. Further, from the standpoint of structure, because the CNT extends longitudinally, it is possible to secure a stable position of allowing other elements to exist.
- the CNTs can be sufficiently doped with an element, and carriers to be transported can be increased. That is, the above structure enables to achieve low resistance of the contact via. Further, from the standpoint of the process, in the CNT in which the graphene wall ends are exposed on the CNT layer sidewall, growth of CNTs at low temperatures is possible. Accordingly, the present embodiment has an advantage of being able to realize a process which can be applied to various devices.
- FIG. 3 is a diagram showing the relationship between the volume resistivity and the line width of graphene, and representing low resistance realization by Br doping.
- the volume resistivity is reduced by two orders of magnitude in B with doping as compared to A without doping.
- the CNT via 30 is constituted not by an ordinary CNT but by the cup-stacked CNT 33 in which the graphene layers are stacked in a state in which they are inclined depthwise with respect to the groove for via. Accordingly, on the side surface of the CNT 33 , the ends of the graphene layers are exposed, and doping of the element 51 can be carried out stably from the side surface of the CNT 33 . In this way, it is possible to reduce the resistance of the CNT via 30 .
- each of the CNTs 33 which constitute the CNT via 30 has a cup-stacked structure. Therefore, an element, such as Br, can be efficiently doped from the side surface of each of the CNTs 33 , and thus, it is possible to further reduce the resistance of the CNT via 30 . Accordingly, in a semiconductor device which uses the CNT via 30 , it is possible to further reduce the interconnect resistance.
- FIGS. 6A to 6F are cross-sectional views showing a manufacturing process of a semiconductor device according to a second embodiment.
- the semiconductor device manufactured in the present embodiment has a structure similar to that shown in FIG. 1 . Further, in order to facilitate the explanation, a cap layer is omitted.
- an interconnect layer insulating film 12 and an underlayer interconnect layer 15 are formed on an Si substrate 10 on which semiconductor elements, such as transistors and capacitors.
- a TEOS film for example, is used for the interconnect layer insulating film 12
- metal such as W, Cu, and Al, is used for the material of the underlayer interconnect layer 15 . It is assumed that the underlayer interconnect layer 15 is formed in various thicknesses and widths.
- an interlayer insulation film 22 is formed on the insulating film 12 and the interconnect layer 15 .
- the insulating film 22 is an SiOC film, for example, and formed by the CVD method or coating method, for example.
- the insulating film 22 may be a film which includes pores for the purpose of reducing the dielectric constant.
- an auxiliary catalyst layer 31 which serves as an auxiliary film for facilitating the manufacturing of the CNTs, is formed in the via hole 23 and on the insulating film 22 . It is preferred that the auxiliary catalyst layer 31 be formed evenly at the bottom and the side of the via hole.
- the CVD method for example, may be used.
- typical materials of the auxiliary catalyst layer 31 Ta, Ti, Ru, W, Al, and the like, may be adopted.
- a nitride or an oxide of a film made from these elements, or a laminating material including such films, can also be used.
- a catalyst layer 32 for CNT growth is formed on the auxiliary catalyst layer 31 .
- the auxiliary catalyst layer 31 and the catalyst layer 32 are formed at the bottom and the sidewall.
- the CVD method for example, is used.
- the material of the catalyst layer 32 it is preferred that a single element metal, such as Co, Ni, Fe, Ru, and Cu, an alloy including at least one of the aforementioned elements, or a carbide thereof or the like be used.
- the catalyst layer 32 should preferably be a discontinuous film which is in a dispersion state.
- CNTs 33 which serve as electrical interconnect layers are formed.
- the CVD method is used for the formation of the CNTs 33 .
- a carbon source a hydrocarbon-based gas, such as methane and acetylene, or a mixture thereof is used, and for a carrier gas, hydrogen or an inert gas is used.
- the CNTs 33 are characterized in that they are formed on only the catalyst layer 32 which has become the discontinuous film.
- the temperature when the CNTs 33 are grown and the concentration of the raw material of the CNTs 33 , and the carrier gas species and the concentration of the carrier gas are controlled.
- the temperature for CNT growth to be 400° C. or less, the CNT 33 will have the cup-stacked structure.
- the height of each of the graphene layers and the inclination of each of the graphene layers with respect to the longitudinal dimension of the CNT can be changed.
- the CNTs 33 are doped with atoms such as Br.
- the doping elements apart from Br, Group 14 to 17 elements such as N and Cl are desired, and at least one of the above elements is used. In order to generate more carriers, several elements from the above may be used.
- Doping in the present step is intended to increase carriers caused by the increase in Fermi energy, in particular.
- metal atoms of Cr and Fe for example, and a complex thereof can be used.
- a raw material including the doping element may be mixed as the raw material gas when the CNTs are to be grown by the CVD.
- a method which can be used is to expose a substrate including the CNTs manufactured in a reduced-pressure and high-temperature state and a material including an element to be used for the intercalation to a same atmosphere. For example, performing exposure of doping element gas to the substrate at room temperature, performing doping gas exposure in a high-temperature or plasma atmosphere, and the like, can be applied. In particular, in order to obtain sufficient doping quantity at low temperature, an element gas exposure in the plasma atmosphere is preferred. Further, this doping may be performed simultaneously with the CNT forming step.
- the CNTs 33 are grown, as shown in FIG. 6E , the CNTs 33 , the catalyst layer 32 , the auxiliary catalyst layer 31 , etc., of a field region are removed by CMP. At this time, the CNTs may be impregnated with an insulating film or metal for immobilizing the CNTs 33 .
- FIG. 6F by forming an upper interconnect layer 45 , an insulating film 42 , and the like, the structure shown in FIG. 1 is completed.
- the CNT via 30 is formed by cup-stacked CNTs 33 .
- a CNT in which the graphene wall ends, which are formed from only a single element C, are exposed on the CNT layer sidewall has lower conductivity than a CNT of a hollow structure. This results from the fact that the dimension of the graphene layer in the direction of electron flow is less than that of the hollow structure CNT.
- an advantage of realizing low resistance by the doping for such cup-stacked CNTs is similar to that of the graphene shown in FIG. 3 . That is, also in the CNTs having the cup-stacked structure, it has been reported that the doping brings about an advantage of reducing resistivity by two orders of magnitude.
- the temperature when the CNTs are grown and the concentration of the raw material of the CNTs, and the carrier gas species and the concentration of the carrier gas species, for example, are controlled. More specifically, in order to structure the CNTs such that the graphene wall ends are exposed on the CNT layer sidewalls, a temperature in the deposition condition is controlled to be a low temperature of 400° C. or less, or control is performed such as supplying a raw material excessively. In this way, a CNT 33 having the cup-stacked structure as shown in FIG. 2 is obtained.
- the present invention is not limited to each of the embodiments described above.
- An element which is used to dope the CNTs is not limited to Br. It is possible to use N or Cl as well. Further, several kinds of the above elements may be used for doping. Furthermore, the deposition condition of the CNTs can be changed as appropriate according to a specification, and may be any kind of condition as long as it defines the height of each of the graphene layers which constitute the CNTs to be 5 nm or greater.
- a catalyst layer is formed at the bottom and the side of the contact via groove.
- a catalyst layer on a side surface is not necessarily required, and a catalyst layer may be formed on only the bottom.
- the auxiliary catalyst layer is formed as a ground of the catalyst layer, if diffusion of a component from the catalyst layer 32 to a lower layer contact does not become an issue, the auxiliary catalyst layer can be omitted.
- the element doping is performed after the CNT via has been formed, it is possible to perform the element doping while the CNT via is being formed.
- the element doping can be performed for the CNTs being manufactured.
- CNTs in which the graphene wall ends are exposed on the CNT layer sidewalls can be formed by controlling the supply of the doping element.
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Abstract
Description
- This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2013-178713, filed Aug. 29, 2013, the entire contents of which are incorporated herein by reference.
- Embodiments described herein relate generally to a semiconductor device and a method of manufacturing the same.
- Recently, a method for forming carbon nanotubes (CNTs) within a via between multilayer interconnects of a semiconductor device has been proposed with a view to reducing interconnect resistance. Because of their quantization conductivity, CNTs offer the possibility of forming low-resistance interconnects in an LSI and so replacing metal interconnects. Further, since the structure of a CNT is tubular, and vertical deposition by the CVD method is possible, this technique is excellently compatible with the conventional vertical interconnect formation process of a device.
- As described above, a CNT is a new material which is expected to have excellent electrical properties in vertically arranged interconnects. With such CNTs, it is possible to realize low-resistance interconnects, particularly when the distance between interconnects is great. On the other hand, to apply CNTs to contacts, a measure for increasing their mean free path is important. For example, the measure which can be taken is doping the CNTs with an element such as boron (Br) or nitrogen (N) and so increasing the carriers transported.
-
FIG. 1 is a cross-sectional view showing a schematic structure of a semiconductor device according to a first embodiment; -
FIGS. 2A and 2B are schematic diagrams for use in indicating an enlarged structure of a CNT used for the semiconductor device ofFIG. 1 and a state of element doping; -
FIG. 3 is a characteristic diagram showing the relationship between the line width and the volume resistivity of graphene; -
FIGS. 4A and 4B are cross-sectional views for use in showing an example of element doping for graphene; -
FIG. 5 is a schematic diagram showing an example of element doping for a CNT; and -
FIGS. 6A to 6F are cross-sectional views showing a manufacturing process of a semiconductor device according to a second embodiment. - In general, according to one embodiment, a semiconductor device in which CNTs are used for a contact via comprises a substrate comprising a contact via groove, a catalyst layer for CNT growth which is formed at the bottom of the groove, and a CNT via formed by filling the CNTs into the groove in which the catalyst layer is formed. Each of the CNTs is formed by stacking a plurality of graphene layers in a state in which they are inclined depthwise with respect to the groove, and formed such that ends of the graphene layers are exposed on a sidewall of the CNT. Further, the CNT is doped with at least one element from the sidewall of the CNT.
- The semiconductor device and a method of manufacturing the same according to the embodiment will be hereinafter described with reference to the accompanying drawings.
-
FIG. 1 is a cross-sectional view showing a schematic structure of a semiconductor device according to a first embodiment. - The present embodiment relates to a structure in which a contact layer for connecting between a semiconductor element and an interconnect layer or between interconnect layers is formed on a substrate on which semiconductor elements such as a transistor and a capacitor are formed. Above all, the aforementioned structure particularly relates to one which uses CNTs as the contact layer material. Further, this structure relates to doping the CNTs with at least one element and applying the CNTs comprising graphene wall ends exposed on the CNT layer sidewalls to a contact.
-
Reference numeral 10 in the figure indicates an Si substrate (semiconductor substrate) on which elements such as a transistor and capacitor are formed. On thesubstrate 10, acap layer 11 of SiO2, SiOC, etc., which functions as a stopper insulating film, and an interconnectlayer insulating film 12 of SiO2, etc., are formed. Further, an interconnect groove is formed in theinsulating film 12, and anunderlayer interconnect 15 is formed by filling a metal film into the interconnect groove. - The
cap layer 11 andcap layers - On the
substrate 10 on which theunderlayer interconnect 15 is formed, thecap layer 21 of SiN, etc., and aninterlayer insulation film 22 of SiO2, etc., are formed. In theinterlayer insulation film 22 which is above theunderlayer interconnect 15, a contact viagroove 23 is formed. - In the contact via
groove 23, a plurality ofCNTs 33 are formed by the intermediary of anauxiliary catalyst layer 31 of Ti, TiN, etc., and acatalyst layer 32 of Ni, Co, etc. A CNT via 30 for connecting between the upper and lower interconnect layers is thereby structured. Here, each of theCNTs 33 grows upward from the bottom of thecatalyst layer 32. - As described above, on the substrate on which the CNT via 30 is formed, a
cap layer 41 of SiN, etc., aninsulating film 42 of SiO2, etc., and anupper interconnect layer 45 of Cu, etc., are formed. - The
insulating film 42 may be lamination of an interconnect layer insulating film and an interlayer insulating film, or formed by an interlayer insulating film alone. In the case of lamination, after forming the interconnect layer insulating film including a groove for interconnection, theupper interconnect layer 45 is formed by filling a metal film into the groove, and the interlayer insulating film is formed on theupper interconnect layer 45 and the interconnect layer insulating film. In the case where theinsulating film 42 is not formed as a laminated structure, after forming theupper interconnect layer 45, the interlayer insulating film may be formed in such a way as to cover theupper interconnect layer 45. - The
auxiliary catalyst layer 31 is an auxiliary film for facilitating the formation of the CNTs, and prevents diffusion of the components of thecatalyst layer 32 from thecatalyst layer 32 to the insulating film and an underlayer contact. As typical materials of theauxiliary catalyst layer 31, Ta, Ti, Ru, W, Al, and the like, may be adopted. A nitride or an oxide of a film made from these elements, or a laminating material including such films may also be used. - The
catalyst layer 32 is a layer necessary for forming the CNTs. As a catalyst material of thecatalyst layer 32, it is preferred that a single element metal, such as Co, Ni, Fe, Ru, and Cu, an alloy including at least one of the aforementioned elements, or a carbide thereof or the like be used. The catalyst layer of the CNT should preferably be a discontinuous film which is in a dispersion state. Here, for the purpose of immobilizing the CNTs formed in the contact via, an insulating film or metal formed by the CVD method, for example, may be filled. - Further, deposition may be carried out such that a diffusion barrier layer, which is not shown, covers the interconnect structure. For the diffusion barrier layer, SiN, for example, is used. Further, the CNTs to be used are featured in that a plurality of graphene walls exist at the outermost part of each of the CNTs, and a constituent element is not C alone.
- Each of the
CNTs 33 in the CNT via 30 is formed to be a cup-stacked CNT. That is, as shown inFIG. 2A , a plurality ofgraphene layers 33 a are stacked in a state in which they are inclined depthwise with respect to the contact viagroove 23, and ends of thegraphene layers 33 a are exposed on the sidewall of the CNT. The height of onegraphene layer 33 a is 5 nm or more. Further, as shown inFIG. 2B , from the sidewall of theCNT 33, thegraphene layers 33 a are doped with least one kind ofelement 51. - Here, graphene is an extremely thin carbon material formed by stacking about 1 to 100 layers of film including benzene rings arranged regularly on a plane. Further, an ordinary CNT has a tubular structure having a diameter of 10 to 100 nm and is made of graphene, which is a carbon material of stacked films each including benzene rings arranged regularly on a plane.
- As in the present embodiment, as the CNT in which graphene wall ends are exposed on the CNT layer sidewall, a cup-stacked CNT, for example, is known. The cup-stacked CNT has a stacked structure of graphene layers which is shaped like a test tube. As the feature, because of the fact that one graphene layer is not connected from end to end of the CNT, it is known that a mean free path becomes small and the resistance becomes high with a single graphene layer. However, since the end of the CNT is positioned at the sidewall, a doping path of an element exists at the sidewall of the CNT. Further, from the standpoint of structure, because the CNT extends longitudinally, it is possible to secure a stable position of allowing other elements to exist.
- By virtue of the above feature, the CNTs can be sufficiently doped with an element, and carriers to be transported can be increased. That is, the above structure enables to achieve low resistance of the contact via. Further, from the standpoint of the process, in the CNT in which the graphene wall ends are exposed on the CNT layer sidewall, growth of CNTs at low temperatures is possible. Accordingly, the present embodiment has an advantage of being able to realize a process which can be applied to various devices.
-
FIG. 3 is a diagram showing the relationship between the volume resistivity and the line width of graphene, and representing low resistance realization by Br doping. The volume resistivity is reduced by two orders of magnitude in B with doping as compared to A without doping. - As regards the doping for the graphene, as shown in
FIG. 4A , if the graphene layers 62 are stacked on asubstrate 61, Br is to be doped from a transverse direction as shown inFIG. 4B . In this way,atoms 51 enter from sidewalls or defects of the graphene layers 62, which increase the space between the graphene layers so that the resistance can be reduced. - Meanwhile, as shown in
FIG. 5 , in the case of (multi-walled)hollow structure CNTs 63,atoms 51 can enter only from the distal end. Accordingly, the diameter is not increased, and it is extremely difficult to achieve low resistance as in the stacked graphene layers. That is, if the doping is applied to such hollow structured CNTs, doping paths to places other than the outermost CNT layer are only the distal ends of the CNTs or defective parts of an outer shell CNT, and so the diameters of the CNTs are barely widened. Accordingly, element doping cannot be performed for the CNTs stably, and it is difficult to obtain a sufficient advantage. - In contrast, in the present embodiment, as shown in
FIGS. 2A and 2B , the CNT via 30 is constituted not by an ordinary CNT but by the cup-stackedCNT 33 in which the graphene layers are stacked in a state in which they are inclined depthwise with respect to the groove for via. Accordingly, on the side surface of theCNT 33, the ends of the graphene layers are exposed, and doping of theelement 51 can be carried out stably from the side surface of theCNT 33. In this way, it is possible to reduce the resistance of the CNT via 30. - As described above, according to the present embodiment, each of the
CNTs 33 which constitute the CNT via 30 has a cup-stacked structure. Therefore, an element, such as Br, can be efficiently doped from the side surface of each of theCNTs 33, and thus, it is possible to further reduce the resistance of the CNT via 30. Accordingly, in a semiconductor device which uses the CNT via 30, it is possible to further reduce the interconnect resistance. -
FIGS. 6A to 6F are cross-sectional views showing a manufacturing process of a semiconductor device according to a second embodiment. - Note that the semiconductor device manufactured in the present embodiment has a structure similar to that shown in
FIG. 1 . Further, in order to facilitate the explanation, a cap layer is omitted. - First of all, as shown in
FIG. 6A , on anSi substrate 10 on which semiconductor elements, such as transistors and capacitors, are formed, an interconnectlayer insulating film 12 and anunderlayer interconnect layer 15 are formed. Here, a TEOS film, for example, is used for the interconnectlayer insulating film 12, and metal, such as W, Cu, and Al, is used for the material of theunderlayer interconnect layer 15. It is assumed that theunderlayer interconnect layer 15 is formed in various thicknesses and widths. - Next, on the insulating
film 12 and theinterconnect layer 15, aninterlayer insulation film 22 is formed. The insulatingfilm 22 is an SiOC film, for example, and formed by the CVD method or coating method, for example. The insulatingfilm 22 may be a film which includes pores for the purpose of reducing the dielectric constant. After that, subsequent to a resist coating/lithography step which is not shown, for only at the place where a CNT via is to be formed, a viahole 23 is formed by RIE processing. - Next, as shown in
FIG. 6B , anauxiliary catalyst layer 31, which serves as an auxiliary film for facilitating the manufacturing of the CNTs, is formed in the viahole 23 and on the insulatingfilm 22. It is preferred that theauxiliary catalyst layer 31 be formed evenly at the bottom and the side of the via hole. As the method for deposition, the CVD method, for example, may be used. As typical materials of theauxiliary catalyst layer 31, Ta, Ti, Ru, W, Al, and the like, may be adopted. A nitride or an oxide of a film made from these elements, or a laminating material including such films, can also be used. - Next, as shown in
FIG. 6C , acatalyst layer 32 for CNT growth is formed on theauxiliary catalyst layer 31. Thus, in the viahole 23, theauxiliary catalyst layer 31 and thecatalyst layer 32 are formed at the bottom and the sidewall. As the method of forming thecatalyst layer 32, the CVD method, for example, is used. As the material of thecatalyst layer 32, it is preferred that a single element metal, such as Co, Ni, Fe, Ru, and Cu, an alloy including at least one of the aforementioned elements, or a carbide thereof or the like be used. Thecatalyst layer 32 should preferably be a discontinuous film which is in a dispersion state. - Next, as shown in
FIG. 6D ,CNTs 33 which serve as electrical interconnect layers are formed. For the formation of theCNTs 33, the CVD method is used. For a carbon source, a hydrocarbon-based gas, such as methane and acetylene, or a mixture thereof is used, and for a carrier gas, hydrogen or an inert gas is used. TheCNTs 33 are characterized in that they are formed on only thecatalyst layer 32 which has become the discontinuous film. Here, to achieve the structure of theCNTs 33, in particular, to be one that the graphene wall ends are exposed on the CNT layer sidewall in each of theCNTs 33, the temperature when theCNTs 33 are grown and the concentration of the raw material of theCNTs 33, and the carrier gas species and the concentration of the carrier gas are controlled. By controlling these, it is possible to obtain aCNT 33 having the cup-stacked structure as shown inFIGS. 2A and 2B . In particular, by controlling the temperature for CNT growth to be 400° C. or less, theCNT 33 will have the cup-stacked structure. Further, by changing the temperature, the height of each of the graphene layers and the inclination of each of the graphene layers with respect to the longitudinal dimension of the CNT can be changed. - After the
CNTs 33 have been grown, theCNTs 33 are doped with atoms such as Br. As the doping elements, apart from Br, Group 14 to 17 elements such as N and Cl are desired, and at least one of the above elements is used. In order to generate more carriers, several elements from the above may be used. - Doping in the present step is intended to increase carriers caused by the increase in Fermi energy, in particular. In addition, for the purpose of forming an energy level, metal atoms of Cr and Fe, for example, and a complex thereof can be used.
- As the method of doping Group 14 to 17 elements, metal atoms, or complex of these atoms, in the case of performing the doping simultaneously with the CNT growth, a raw material including the doping element may be mixed as the raw material gas when the CNTs are to be grown by the CVD. Further, in the case of intercalation after the CNT growth, a method which can be used is to expose a substrate including the CNTs manufactured in a reduced-pressure and high-temperature state and a material including an element to be used for the intercalation to a same atmosphere. For example, performing exposure of doping element gas to the substrate at room temperature, performing doping gas exposure in a high-temperature or plasma atmosphere, and the like, can be applied. In particular, in order to obtain sufficient doping quantity at low temperature, an element gas exposure in the plasma atmosphere is preferred. Further, this doping may be performed simultaneously with the CNT forming step.
- After the
CNTs 33 are grown, as shown inFIG. 6E , theCNTs 33, thecatalyst layer 32, theauxiliary catalyst layer 31, etc., of a field region are removed by CMP. At this time, the CNTs may be impregnated with an insulating film or metal for immobilizing theCNTs 33. - Finally, as shown in
FIG. 6F , by forming anupper interconnect layer 45, an insulatingfilm 42, and the like, the structure shown inFIG. 1 is completed. - According to the present embodiment described above, it is possible to manufacture a CNT via 30 whose interconnect resistance is extremely low, and resistance of a contact via in a semiconductor device can be reduced. Further, by only changing the deposition condition of the
CNTs 33, cup-stacked CNTs suited to doping with Br, etc., can be manufactured, and thus the manufacturing can be carried out without needing to drastically change the manufacturing process. - In the present embodiment, an optimal structure of CNTs to be used for a CNT via, and a method of manufacturing the same will be described.
- In the first and second embodiments, the CNT via 30 is formed by cup-stacked
CNTs 33. Here, it is known that a CNT in which the graphene wall ends, which are formed from only a single element C, are exposed on the CNT layer sidewall has lower conductivity than a CNT of a hollow structure. This results from the fact that the dimension of the graphene layer in the direction of electron flow is less than that of the hollow structure CNT. Meanwhile, an advantage of realizing low resistance by the doping for such cup-stacked CNTs is similar to that of the graphene shown inFIG. 3 . That is, also in the CNTs having the cup-stacked structure, it has been reported that the doping brings about an advantage of reducing resistivity by two orders of magnitude. - The via resistance in the present embodiment is determined by the conductivity resulting from the height of the graphene layer and the advantage of resistance reduction by the doping. Assuming that the resistance is reduced by two orders of magnitude by the doping, in order to realize lower resistance than in an average free length of 500 nm, which is the target of the current CNTs (producing approximately the same resistance as a W-plug), the height (average free length) of one graphene layer should be 5 nm or more (500 nm/100=5 nm). That is, in order to obtain the same advantage as that of the conventional metal via or hollow structure CNTs or a greater advantage than that, it is effective to stack graphene layers each having a height of 5 nm or more as shown in
FIGS. 2A and 2B . - In order to form such a structure, the temperature when the CNTs are grown and the concentration of the raw material of the CNTs, and the carrier gas species and the concentration of the carrier gas species, for example, are controlled. More specifically, in order to structure the CNTs such that the graphene wall ends are exposed on the CNT layer sidewalls, a temperature in the deposition condition is controlled to be a low temperature of 400° C. or less, or control is performed such as supplying a raw material excessively. In this way, a
CNT 33 having the cup-stacked structure as shown inFIG. 2 is obtained. - The present invention is not limited to each of the embodiments described above.
- An element which is used to dope the CNTs is not limited to Br. It is possible to use N or Cl as well. Further, several kinds of the above elements may be used for doping. Furthermore, the deposition condition of the CNTs can be changed as appropriate according to a specification, and may be any kind of condition as long as it defines the height of each of the graphene layers which constitute the CNTs to be 5 nm or greater.
- In the present embodiment, a catalyst layer is formed at the bottom and the side of the contact via groove. However, a catalyst layer on a side surface is not necessarily required, and a catalyst layer may be formed on only the bottom. Further, in the present embodiment, although the auxiliary catalyst layer is formed as a ground of the catalyst layer, if diffusion of a component from the
catalyst layer 32 to a lower layer contact does not become an issue, the auxiliary catalyst layer can be omitted. - In the second embodiment, although element doping is performed after the CNT via has been formed, it is possible to perform the element doping while the CNT via is being formed. To be specific, in the step shown in
FIG. 6D , by adding atoms such as Br, N, and Cl atoms to source gas of the CVD, the element doping can be performed for the CNTs being manufactured. When the doping is performed simultaneously, CNTs in which the graphene wall ends are exposed on the CNT layer sidewalls can be formed by controlling the supply of the doping element. - 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.
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