WO2016035623A1 - Composite wiring and production method therefor - Google Patents

Composite wiring and production method therefor Download PDF

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Publication number
WO2016035623A1
WO2016035623A1 PCT/JP2015/073922 JP2015073922W WO2016035623A1 WO 2016035623 A1 WO2016035623 A1 WO 2016035623A1 JP 2015073922 W JP2015073922 W JP 2015073922W WO 2016035623 A1 WO2016035623 A1 WO 2016035623A1
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Prior art keywords
composite wiring
hfac
cvd
copper
carbon nanotubes
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PCT/JP2015/073922
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French (fr)
Japanese (ja)
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貴士 松本
伊藤　大輔
亮太 井福
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東京エレクトロン株式会社
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Publication of WO2016035623A1 publication Critical patent/WO2016035623A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • 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
    • H01L23/532—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 characterised by the materials
    • H01L23/53204—Conductive materials
    • H01L23/53276—Conductive materials containing carbon, e.g. fullerenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/10—Applying interconnections to be used for carrying current between separate components within a device
    • H01L2221/1068—Formation and after-treatment of conductors
    • H01L2221/1094—Conducting structures comprising nanotubes or nanowires
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a composite wiring and a manufacturing method thereof, and more particularly to a fine composite wiring and a manufacturing method thereof.
  • Nanocarbon materials different from metals such as graphene and carbon nanotubes
  • metals such as graphene and carbon nanotubes
  • nanocarbon material is used for wiring instead of metal, for example, for horizontal wiring formed by trenches. It has been studied to use a plurality of bundled graphene ribbons and use a plurality of bundled carbon nanotubes for the wiring in the depth direction formed by via holes.
  • a carbon nanotube is a cylindrical cluster of carbon atoms obtained by decomposing a carbon-containing gas using catalyst metal particles as a catalyst and bonding carbon atoms together, and grows in one direction from each catalyst metal particle. Therefore, it can be suitably used for wiring in the depth direction in a three-dimensional mounting device, for example, wiring for via holes.
  • a metal such as Cu.
  • a Cu filling method for example, a PVD (Physical Vapor Deposition) method using a sputtered Cu particle, a CVD (Chemical Vapor Deposition) method, and a plating method have been studied (for example, see Patent Document 1).
  • the aspect ratio of the gaps between the carbon nanotubes is high, and sputtered particles cannot enter the depths of the gaps.
  • the wettability between the metal and the carbon nanotube is low, Cu atoms cannot enter the back of the gap in the plating method.
  • the gaps 71 between the carbon nanotubes 70 are not completely filled with Cu 72, and the gaps 71 remain in the composite wiring composed of the Cu 72 and the carbon nanotubes 70.
  • the resistance of the composite wiring does not decrease so much and the structure may become brittle.
  • An object of the present invention is to provide a composite wiring and a method for manufacturing the same capable of greatly reducing the resistance and strengthening the structure.
  • another molecule having a conjugated system and a metal atom are bonded to a conductor having a microstructure including a molecule having a conjugated system by an interaction caused by ⁇ electrons.
  • a method of manufacturing a composite wiring that performs CVD using a complex is provided.
  • a composite wiring in which a metal atom is filled in a gap generated in a fine-structure conductor including a molecule having a conjugated system, and the metal atom has a conjugated system.
  • a composite wiring that is filled by subjecting the fine-structured conductor to CVD using a complex in which other molecules of the metal atom and the metal atom are bonded by an interaction caused by ⁇ electrons.
  • a metal atom of a complex from which another molecule is eliminated by heat or the like in CVD binds to the molecule by an interaction caused by a ⁇ electron of a molecule having a conjugated system of a fine structure conductor.
  • metal atoms can be arranged at locations where a conjugated system exists in a fine-structure conductor, even if the aspect ratio of the gap generated in the fine-structure conductor is high, as long as the conjugated system exists, the metal atoms Can be made to enter the depth of the gap, and the gap generated in the fine-structured conductor can be almost completely filled with metal atoms.
  • the resistance can be greatly reduced and the structure can be strengthened.
  • FIGS. 4A and 4B are process diagrams for explaining CVD performed in the CVD processing apparatus of FIG. FIG.
  • FIG. 5 is a cross-sectional view schematically showing a configuration of a composite wiring made of copper and carbon nanotubes manufactured by the composite wiring manufacturing method according to the first embodiment of the present invention.
  • FIGS. 6A to 6H are process diagrams for explaining a method of manufacturing a composite wiring according to the second embodiment of the present invention.
  • FIG. 7 is a cross sectional view schematically showing a configuration of a modified example of the CVD processing apparatus of FIG.
  • FIG. 8 is a cross-sectional view schematically showing a configuration of a composite wiring made of copper and carbon nanotubes manufactured by a conventional composite wiring manufacturing method.
  • 1A to 1E are process diagrams for explaining a method of manufacturing a composite wiring according to the present embodiment.
  • an insulating interlayer film 12 is formed on the substrate S through a lower electrode layer 10 and a hard mask 11 made of, for example, silicon nitride (SiN), and the insulating interlayer film 12 is etched to be perpendicular to the substrate S.
  • a via hole 13 is formed in the opening.
  • the lower electrode layer 10 is exposed at the bottom of the via hole 13, and then the surface of the insulating interlayer film 12 including the surface of the via hole 13 is made of, for example, titanium nitride (TiN), tantalum nitride (TaN), manganese oxide (MnO x ) is covered with a barrier metal layer 14.
  • a catalytic metal layer (not shown) made of, for example, nickel (Ni) is formed on the bottom of the via hole 13, and the size and shape are uniform from the catalytic metal layer using plasma or the like as shown in FIG. 1A. A large number of catalyst metal fine particles 15 are formed.
  • the metal constituting the catalyst metal layer is copper (Cu), iron (Fe), cobalt (Co), ruthenium (Ru), gold (Au), platinum (Pt), molybdenum (Mo).
  • Transition metals such as manganese (Mn), or alloys containing these transition metals may be used.
  • each catalytic metal fine particle 15 activation is performed by removing the oxide on the surface of each catalytic metal fine particle 15 using plasma or the like, and as shown in FIG. 1B, carbon generated by pyrolysis from a carbon-containing gas such as acetylene gas or ethylene gas. Atoms are bonded to each other using each catalytic metal fine particle 15 as a nucleus to generate a plurality of carbon nanotubes 16 (microstructured conductors). At this time, the carbon nanotubes 16 grow in one direction (upward in FIG. 1B) from the catalytic metal fine particles 15 so as not to collide with each other while maintaining the properties of the catalytic metal fine particles 15. Therefore, the plurality of carbon nanotubes 16 are oriented substantially perpendicular to the surface of the substrate S.
  • a carbon-containing gas such as acetylene gas or ethylene gas.
  • each carbon nanotube 16 grows from each catalytic metal fine particle 15, when forming the catalytic metal fine particle 15, the type of processing gas and the energy for exciting the processing gas are adjusted to make each catalytic metal fine particle 15 dense. When formed, high-density carbon nanotubes 16 are obtained. On the other hand, even if the catalyst metal fine particles 15 are formed at a high density, minute gaps remain between the catalyst metal fine particles 15. 17 occurs.
  • a metal for example, copper 18 is filled into the gaps 17 by CVD (FIG. 1C).
  • FIG. 2 is a cross-sectional view schematically showing a configuration of a CVD processing apparatus that performs CVD for filling the gaps between the carbon nanotubes with copper.
  • a CVD processing apparatus 19 includes a substantially cylindrical chamber 20, a lower stage heater 21 disposed at the bottom of the chamber 20, and an upper portion disposed on the ceiling of the chamber 20 and facing the lower stage heater 21.
  • a gas supply system 25 that supplies a carrier gas or the like into the chamber 20, a gas discharge system 26 that exhausts a residual gas or the like inside the chamber 20, and a control unit 27 that controls the operation of each component.
  • the substrate S is placed on the lower stage heater 21, and the atmosphere inside the chamber 20 is replaced with, for example, nitrogen gas.
  • the pressure is reduced to 3 Torr.
  • the temperature of the substrate S is set to any one of 200 ° C. to 250 ° C. by the lower stage heater 21, and a metal complex 28 made of, for example, COD-Cu-hfac molecules is disposed on the sample stage 24. Is heated by the upper stage heater 22. At this time, COD-Cu-hfac molecules scattered from the heated metal complex 28 float inside the chamber 20, pass through the through hole 23, reach the substrate S, and each carbon nanotube 16 formed on the substrate S.
  • the gap 17 is filled with copper 18.
  • FIG. 3 is a diagram for explaining the molecular structure of COD-Cu-hfac molecules constituting a metal complex used in CVD to fill gaps generated between the carbon nanotubes
  • FIGS. 4A and 4B are diagrams. It is process drawing for demonstrating CVD performed with the CVD processing apparatus of 2.
  • FIG. 3 is a diagram for explaining the molecular structure of COD-Cu-hfac molecules constituting a metal complex used in CVD to fill gaps generated between the carbon nanotubes
  • FIGS. 4A and 4B are diagrams. It is process drawing for demonstrating CVD performed with the CVD processing apparatus of 2.
  • FIG. 3 is a diagram for explaining the molecular structure of COD-Cu-hfac molecules constituting a metal complex used in CVD to fill gaps generated between the carbon nanotubes
  • FIGS. 4A and 4B are diagrams. It is process drawing for demonstrating CVD performed with the CVD processing apparatus of 2.
  • FIG. 3 is a diagram for explaining the molecular structure of COD
  • a COD-Cu-hfac molecule is composed of cyclooctadiene (hereinafter simply referred to as “COD”), a copper atom, and hexafluoroacetylacetone (hereinafter simply referred to as “hfac”).
  • COD cyclooctadiene
  • hfac hexafluoroacetylacetone
  • the copper atom is single-bonded to each of the two oxygen atoms of hfac by a bond
  • COD has a conjugated system consisting of a single bond and a double bond. Specifically, it bonds to a copper atom by sharing ⁇ electrons.
  • each carbon nanotube 16 is constituted by a carbon six-membered ring (benzene ring) continuous over the entire area. Since each benzene ring has a conjugated system composed of a single bond and a double bond, ⁇ electrons exist in each benzene ring.
  • Cu-hfac molecule the copper atom of the COD-Cu-hfac molecule (hereinafter referred to as “Cu-hfac molecule”) from which COD has been eliminated is in a state where it can share an electron, the copper atom is responsible for the ⁇ electron of each benzene ring. Share and actively bond to each benzene ring.
  • the copper atom of the Cu-hfac molecule shares the ⁇ electron of the benzene ring of the carbon nanotube 16 and actively bonds to each benzene ring. That is, since the copper atoms can be arranged over the entire surface of the carbon nanotubes 16 due to the presence of ⁇ electrons in the benzene ring, even if the aspect ratio of the gaps 17 between the carbon nanotubes 16 is high, the copper atoms As shown in FIG. 5, the gaps 17 between the carbon nanotubes 16 can be almost completely filled with the copper 18.
  • the CVD processing apparatus 19 by continuing the CVD by the CVD processing apparatus 19 for a predetermined time, not only the gaps 17 between the carbon nanotubes 16 are filled with the copper 18, but also the copper 18 is used to form the substrate S. Cover the entire surface.
  • the surface of the substrate S is covered with an upper electrode layer 29 formed by CVD or PVD.
  • the upper electrode layer 29 and the tips of the carbon nanotubes 16 are in contact with each other, and the lower electrode layer 10 and the upper electrode layer 29 are electrically connected to each other through the carbon nanotubes 16, the catalytic metal fine particles 15, and the barrier metal layer 14. (FIG. 1E). Thereafter, the method ends.
  • the copper atoms of COD-Cu-hfac molecules (Cu-hfac molecules) from which COD has been desorbed by heat or the like in CVD are formed on the benzene ring of each carbon nanotube 16. It binds to the benzene ring by interaction caused by ⁇ electrons. That is, Cu-hfac molecules can be arranged at locations where benzene rings are present in each carbon nanotube 16, and each carbon nanotube 16 has a benzene ring over the entire surface.
  • ⁇ electrons are used for bonding between the copper atom of the Cu-hfac molecule and the benzene ring of each carbon nanotube 16, so that the gap 17 between each carbon nanotube 16 is made of copper 18 by CVD.
  • the temperature of the substrate S is set to only 200 ° C. to 250 ° C., which is relatively low, and even if the applied energy is small, the copper atoms of the Cu-hfac molecules and the carbon nanotubes 16 Can be bonded to the benzene ring.
  • the wiring composed of the carbon nanotubes 16 and the copper 18 manufactured by the above-described composite wiring manufacturing method is also applied to wiring of a nonvolatile memory element such as a magnetoresistive memory (MRAM) or a resistance change memory (ReRAM). can do.
  • MRAM magnetoresistive memory
  • ReRAM resistance change memory
  • each carbon nanotube 16 conducts the lower electrode layer 10 and the upper electrode layer 29 to each other in the via hole 13, but the carbon nanotube 16 has high thermal conductivity.
  • heat can be prevented from staying in the lower electrode layer 10, the upper electrode layer 29, or the like.
  • This embodiment is basically the same in configuration and operation as the first embodiment described above, and the first embodiment described above in that a plurality of carbon nanotubes are oriented substantially horizontally with respect to the surface of the substrate S. This is different from the embodiment. Therefore, the description of the duplicated configuration and operation is omitted, and the description of the different configuration and operation is given below.
  • 6A to 6H are process diagrams for explaining the method of manufacturing the composite wiring according to the present embodiment.
  • an insulating interlayer film 30 is formed on the substrate S, the insulating interlayer film 30 is etched to form a trench 31, and a part of the bottom of the trench 31 is etched to form a wiring hole 32.
  • the lower electrode 33 is formed by filling the wiring hole 32 with a conductor.
  • the surfaces of the trench 31 and the wiring hole 32 are covered with a barrier metal layer 34 made of, for example, titanium nitride.
  • a catalytic metal layer (not shown) made of, for example, nickel is formed on one side surface of the trench 31, and, as shown in FIG. 6A, a large number of uniform sizes and shapes are formed from the catalytic metal layer using plasma or the like.
  • the catalyst metal fine particles 35 are formed.
  • each catalytic metal fine particle 35 is activated using plasma or the like, and as shown in FIG. 6B, carbon atoms generated by pyrolysis from the carbon-containing gas are bonded to each other using each catalytic metal fine particle 35 as a nucleus.
  • a plurality of carbon nanotubes 36 (fine conductors) are generated.
  • Each carbon nanotube 36 grows in one direction (left side in FIG. 6B) from each catalytic metal fine particle 35 so as not to collide with each other. Therefore, the plurality of carbon nanotubes 36 are aligned substantially horizontally with respect to the surface of the substrate S. At this time, a gap 37 having a small and high aspect ratio is generated between the carbon nanotubes 36.
  • the CVD processing apparatus 19 performs CVD on the substrate S using the metal complex 28 made of COD-Cu-hfac molecules.
  • COD is desorbed from each COD-Cu-hfac molecule, and the ⁇ -electron bond is formed between the copper atom of the Cu-hfac molecule and the benzene ring of each carbon nanotube 36.
  • the surface of each carbon nanotube 36 is covered with copper atoms through the heterogeneous reaction of two adjacent Cu-hfac molecules, and the copper 18 is filled into the gap 37 (FIG. 6C).
  • the gaps 37 between the carbon nanotubes 36 are filled with the copper 18, but the entire surface of the substrate S is covered with the copper 18.
  • the copper atom of the Cu-hfac molecule is bonded to the benzene ring of each carbon nanotube 36 by the sharing of ⁇ electrons. That is, also in the manufacturing method of the composite wiring according to the present embodiment, Cu-hfac molecules can be arranged at locations where benzene rings exist in each carbon nanotube 36, and the aspect ratio of the gap 37 of each carbon nanotube 36 is Even if it is high, the gaps 37 between the carbon nanotubes 36 can be almost completely filled with the copper 18.
  • the carbon nanotube is used as a fine conductor.
  • any conductor containing a molecule having a conjugated system can be used as a fine conductor.
  • a high aspect ratio graphene ribbon may be disposed in the via hole 13 or the trench 31 as a fine-structured conductor.
  • the gap between the graphene ribbons has a high aspect ratio, but the graphene ribbon is also composed of a continuous benzene ring over the entire region, so that CVD using a metal complex 28 made of COD-Cu-hfac molecules is used.
  • the gaps between the graphene ribbons can be almost completely filled with the copper 18.
  • the metal complex having a conjugated system to which the present invention can be applied includes, for example, any of copper, platinum, iridium (Ir), nickel, cobalt, and molybdenum in addition to the metal complex 28 composed of COD-Cu-hfac molecules.
  • a ligand having a conjugated system of 5-cyclooctadiene, 1,5-hexadiene, 1,3-pentadiene, 4-vinyl-1-cyclohexene and norbornadiene, and a single bond by the above metal atom and a bond For example, hexafluoroacetylacetonate (hfac), acetylacetonate (acac) and 1,1,1-trimethyl This corresponds to a metal complex having any ligand of ruacetylacetonate.
  • the CVD processing apparatus for performing the CVD for filling the gaps 17 between the carbon nanotubes 16 with the copper 18 is not limited to the CVD processing apparatus 19 shown in FIG. 2, but for example, a shower head as shown in FIG. It may be a type of CVD processing apparatus 42.
  • FIG. 7 is a cross-sectional view schematically showing a configuration of a modified example of the CVD processing apparatus of FIG.
  • a CVD processing apparatus 42 includes a substantially cylindrical chamber 43, a table-like stage heater 44 disposed at the bottom of the chamber 43, and a ceiling portion of the chamber 43 facing the stage heater 44.
  • a metal complex gas supply system 46 for supplying a metal complex 28, for example, a gas of COD-Cu-hfac molecule, together with a carrier gas made of argon (Ar) or helium (He) into the shower head 45 and the chamber 43, for example.
  • An additive gas supply system 47 for supplying an additive gas, for example, COD or hfac gas, into the chamber 43; and a dilution gas supply system 48 for supplying a diluent gas, for example, argon or helium gas, into the chamber 43. And a cleaning gas for supplying a cleaning gas such as hfac or HCOOH into the chamber 43.
  • Ngugasu supply system 49 purge gas into the interior of the chamber 43, for example, nitrogen (N 2) and a purge gas supply system 50 for supplying a gas, evacuating the interior of the chamber 43, for example, a pressure adjusting variable valve 51 and the exhaust pump 52 And a stage heater control unit 54 for controlling the operation of the stage heater 44.
  • the metal complex gas supply system 46, the additive gas supply system 47, the dilution gas supply system 48, and the cleaning gas supply system 49 supply each gas to the inside of the chamber 43 via the shower head 45, and the purge gas supply system 50 supplies the purge gas to the chamber. It supplies directly to the inside of 43.
  • the substrate S is placed on the stage heater 44, the atmosphere inside the chamber 43 is evacuated by the gas exhaust system 53, and the additive gas is supplied from the additive gas supply system 47 or the dilution gas supply system.
  • a dilution gas is supplied from 48 to adjust the pressure inside the chamber 43 to 3 Torr.
  • the temperature of the substrate S is set to any one of 200 ° C. to 250 ° C. by the stage heater 44, and the gas of the metal complex 28 is supplied into the chamber 43 together with the additive gas, the dilution gas, and the carrier gas.
  • the COD-Cu-hfac molecules in 28 reach the heated substrate S, and the gaps 17 between the carbon nanotubes 16 formed on the substrate S are filled with copper 18 (see FIG. 1C and the like).
  • An object of the present invention is to supply a computer, for example, the control unit 27, with a storage medium storing software program codes that implement the functions of the above-described embodiments, and the CPU of the control unit 27 is stored in the storage medium. It is also achieved by reading and executing the program code.
  • the program code itself read from the storage medium realizes the functions of the above-described embodiments, and the program code and the storage medium storing the program code constitute the present invention.
  • Examples of the storage medium for supplying the program code include RAM, NV-RAM, floppy (registered trademark) disk, hard disk, magneto-optical disk, CD-ROM, CD-R, CD-RW, DVD (DVD). -ROM, DVD-RAM, DVD-RW, DVD + RW) and other optical disks, magnetic tapes, non-volatile memory cards, other ROMs, etc., as long as they can store the program code.
  • the program code may be supplied to the control unit 27 by downloading from another computer or database (not shown) connected to the Internet, a commercial network, a local area network, or the like.
  • the program code read from the storage medium is written in the memory provided in the function expansion board inserted into the control unit 27 or the function expansion unit connected to the control unit 27, the program code is read based on the instruction of the program code.
  • the CPU of the function expansion board or function expansion unit performs part or all of the actual processing, and the functions of the above-described embodiments are realized by the processing.
  • the form of the program code may be in the form of object code, program code executed by an interpreter, script data supplied to the OS, and the like.

Abstract

Provided is a production method for composite wiring, allowing the resistance to be decreased greatly, and allowing the structure to be strong. On each carbon nanotube (16) formed inside a via hole (13) and containing successive benzene rings, CVD is performed using a metal complex (28) comprising a COD-Cu-hfac molecule.

Description

複合配線及びその製造方法Composite wiring and manufacturing method thereof
　本発明は、複合配線及びその製造方法に関し、特に微細な複合配線及びその製造方法に関する。 The present invention relates to a composite wiring and a manufacturing method thereof, and more particularly to a fine composite wiring and a manufacturing method thereof.
　金属とは異なるナノカーボン材料、例えば、グラフェンやカーボンナノチューブは極めて長い平均自由行程や高移動度を有し、極微細配線構造に適用した場合、金属よりも低抵抗の配線の実現の可能性が示されている。これに応じて、微細な配線構造を実現する必要がある次世代の三次元実装デバイスでは、金属の代わりにナノカーボン材料を配線に用いること、例えば、トレンチによって形成される水平方向の配線には束ねられた複数のグラフェンリボンを用い、ビアホールによって形成される深さ方向の配線には束ねられた複数のカーボンナノチューブを用いることが検討されている。 Nanocarbon materials different from metals, such as graphene and carbon nanotubes, have extremely long mean free paths and high mobility, and when applied to ultrafine wiring structures, there is a possibility of realizing wiring with lower resistance than metals. It is shown. Accordingly, in next-generation three-dimensional mounting devices that need to realize a fine wiring structure, a nanocarbon material is used for wiring instead of metal, for example, for horizontal wiring formed by trenches. It has been studied to use a plurality of bundled graphene ribbons and use a plurality of bundled carbon nanotubes for the wiring in the depth direction formed by via holes.
　特に、カーボンナノチューブは、触媒金属の微粒子を触媒として炭素含有ガスを分解し、炭素原子同士を結合させることによって得られる円筒状の炭素原子のクラスターであり、触媒金属の各微粒子から一方向に成長するため、三次元実装デバイスにおける深さ方向の配線、例えば、ビアホールの配線へ好適に用いることができる。 In particular, a carbon nanotube is a cylindrical cluster of carbon atoms obtained by decomposing a carbon-containing gas using catalyst metal particles as a catalyst and bonding carbon atoms together, and grows in one direction from each catalyst metal particle. Therefore, it can be suitably used for wiring in the depth direction in a three-dimensional mounting device, for example, wiring for via holes.
　ところで、各カーボンナノチューブの配置密度は触媒金属の各微粒子の配置密度に依存するため、各カーボンナノチューブの間には隙間が生じることがある。この隙間を埋めるために、ＳＯＧ（Ｓｐｉｎ　ｏｎ　Ｇｌａｓｓ）を充填することが提案されているが、ＳＯＧは絶縁性材料であるため、配線の低抵抗化に寄与することがなく、ＳＯＧは誘電率が高いため、寧ろ、配線の寄生容量を増大させるおそれがある。 Incidentally, since the arrangement density of the carbon nanotubes depends on the arrangement density of the fine particles of the catalyst metal, a gap may be formed between the carbon nanotubes. In order to fill this gap, it has been proposed to fill with SOG (Spin on Glass). However, since SOG is an insulating material, it does not contribute to lower resistance of wiring, and SOG has a dielectric constant. Rather, it may increase the parasitic capacitance of the wiring.
　そこで、近年、各カーボンナノチューブの間の隙間を金属、例えば、Ｃｕで充填することが提案されている。Ｃｕの充填方法としては、例えば、Ｃｕのスパッタ粒子を用いるＰＶＤ（Ｐｈｙｓｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ）法やＣＶＤ（Ｃｈｅｍｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ）法、さらにはめっき法が検討されている（例えば、特許文献１参照。）。 Therefore, in recent years, it has been proposed to fill the gaps between the carbon nanotubes with a metal such as Cu. As a Cu filling method, for example, a PVD (Physical Vapor Deposition) method using a sputtered Cu particle, a CVD (Chemical Vapor Deposition) method, and a plating method have been studied (for example, see Patent Document 1).
特開２００５−２７７０９６号公報JP 2005-277096 A
　しかしながら、各カーボンナノチューブの間の隙間のアスペクト比は高く、スパッタ粒子が隙間の奥まで進入できない。また、金属とカーボンナノチューブの濡れ性は低いため、めっき法においてＣｕ原子が隙間の奥まで進入できない。これにより、図８に示すように、各カーボンナノチューブ７０の間の隙間７１はＣｕ７２によって完全に充填されず、Ｃｕ７２とカーボンナノチューブ７０からなる複合配線において隙間７１が残存する。その結果、複合配線の抵抗がさほど低下せず、構造も脆くなるおそれがある。 However, the aspect ratio of the gaps between the carbon nanotubes is high, and sputtered particles cannot enter the depths of the gaps. In addition, since the wettability between the metal and the carbon nanotube is low, Cu atoms cannot enter the back of the gap in the plating method. As a result, as shown in FIG. 8, the gaps 71 between the carbon nanotubes 70 are not completely filled with Cu 72, and the gaps 71 remain in the composite wiring composed of the Cu 72 and the carbon nanotubes 70. As a result, the resistance of the composite wiring does not decrease so much and the structure may become brittle.
　本発明の目的は、抵抗を大幅に低下させることができるとともに、構造を強固にすることができる複合配線及びその製造方法を提供することにある。 An object of the present invention is to provide a composite wiring and a method for manufacturing the same capable of greatly reducing the resistance and strengthening the structure.
　上記目的を達成するために、本発明によれば、共役系を有する分子を含む微細構造の導電体へ、共役系を有する他の分子と金属原子とがπ電子に起因する相互作用によって結合する錯体を用いるＣＶＤを施す複合配線の製造方法が提供される。 In order to achieve the above object, according to the present invention, another molecule having a conjugated system and a metal atom are bonded to a conductor having a microstructure including a molecule having a conjugated system by an interaction caused by π electrons. A method of manufacturing a composite wiring that performs CVD using a complex is provided.
　上記目的を達成するために、本発明によれば、共役系を有する分子を含む微細構造の導電体に生じる隙間に金属原子が充填された複合配線であって、前記金属原子は、共役系を有する他の分子と前記金属原子とがπ電子に起因する相互作用によって結合する錯体を用いるＣＶＤを前記微細構造の導電体に施すことによって充填される複合配線が提供される。 In order to achieve the above object, according to the present invention, there is provided a composite wiring in which a metal atom is filled in a gap generated in a fine-structure conductor including a molecule having a conjugated system, and the metal atom has a conjugated system. Provided is a composite wiring that is filled by subjecting the fine-structured conductor to CVD using a complex in which other molecules of the metal atom and the metal atom are bonded by an interaction caused by π electrons.
　本発明によれば、ＣＶＤにおいて熱等によって他の分子が脱離した錯体の金属原子が、微細構造の導電体の共役系を有する分子のπ電子に起因する相互作用によって当該分子と結合する。すなわち、微細構造の導電体において共役系が存在する箇所へ金属原子を配置することができるため、微細構造の導電体に生じる隙間のアスペクト比が高くても、共役系が存在する限り、金属原子を隙間の奥まで進入させることができ、もって、微細構造の導電体に生じる隙間を金属原子でほぼ完全に充填することができる。その結果、金属原子及び微細構造の導電体からなる複合配線において、抵抗を大幅に低下させることができるとともに、構造を強固にすることができる。 According to the present invention, a metal atom of a complex from which another molecule is eliminated by heat or the like in CVD binds to the molecule by an interaction caused by a π electron of a molecule having a conjugated system of a fine structure conductor. In other words, since metal atoms can be arranged at locations where a conjugated system exists in a fine-structure conductor, even if the aspect ratio of the gap generated in the fine-structure conductor is high, as long as the conjugated system exists, the metal atoms Can be made to enter the depth of the gap, and the gap generated in the fine-structured conductor can be almost completely filled with metal atoms. As a result, in the composite wiring composed of the metal atoms and the fine-structure conductor, the resistance can be greatly reduced and the structure can be strengthened.
　［図１Ａ乃至図１Ｅ］本発明の第１の実施の形態に係る複合配線の製造方法を説明するための工程図である。
　［図２］各カーボンナノチューブの間の隙間を銅で充填するためのＣＶＤを実行するＣＶＤ処理装置の構成を概略的に示す断面図である。
　［図３］各カーボンナノチューブの間に生じた隙間を埋めるためにＣＶＤで用いられる金属錯体を構成するＣＯＤ−Ｃｕ−ｈｆａｃ分子の分子構造を説明する図である。
　［図４Ａ及び図４Ｂ］図２のＣＶＤ処理装置で実行されるＣＶＤを説明するための工程図である。
　［図５］本発明の第１の実施の形態に係る複合配線の製造方法で製造された銅及びカーボンナノチューブからなる複合配線の構成を概略的に示す断面図である。
　［図６Ａ乃至図６Ｈ］本発明の第２の実施の形態に係る複合配線の製造方法を説明するための工程図である。
　［図７］図２のＣＶＤ処理装置の変形例の構成を概略的に示す断面図である。
　［図８］従来の複合配線の製造方法で製造された銅及びカーボンナノチューブからなる複合配線の構成を概略的に示す断面図である。 1A to 1E are process diagrams for explaining a method of manufacturing a composite wiring according to a first embodiment of the present invention.
FIG. 2 is a cross-sectional view schematically showing a configuration of a CVD processing apparatus that performs CVD for filling a gap between carbon nanotubes with copper.
FIG. 3 is a diagram for explaining the molecular structure of COD-Cu-hfac molecules constituting a metal complex used in CVD to fill a gap generated between carbon nanotubes.
[FIGS. 4A and 4B] FIGS. 4A and 4B are process diagrams for explaining CVD performed in the CVD processing apparatus of FIG.
FIG. 5 is a cross-sectional view schematically showing a configuration of a composite wiring made of copper and carbon nanotubes manufactured by the composite wiring manufacturing method according to the first embodiment of the present invention.
[FIGS. 6A to 6H] FIGS. 6A to 6H are process diagrams for explaining a method of manufacturing a composite wiring according to the second embodiment of the present invention.
FIG. 7 is a cross sectional view schematically showing a configuration of a modified example of the CVD processing apparatus of FIG.
FIG. 8 is a cross-sectional view schematically showing a configuration of a composite wiring made of copper and carbon nanotubes manufactured by a conventional composite wiring manufacturing method.
　以下、本発明の実施の形態について図面を参照しながら詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
　まず、本発明の第１の実施の形態に係る複合配線の製造方法について説明する。 First, the method for manufacturing the composite wiring according to the first embodiment of the present invention will be described.
　図１Ａ乃至図１Ｅは、本実施の形態に係る複合配線の製造方法を説明するための工程図である。 1A to 1E are process diagrams for explaining a method of manufacturing a composite wiring according to the present embodiment.
　まず、基板Ｓ上に下部電極層１０や、例えば、窒化珪素（ＳｉＮ）からなるハードマスク１１を介して絶縁層間膜１２を成膜し、さらに、絶縁層間膜１２をエッチングして基板Ｓに垂直に開口するビアホール１３を形成する。ビアホール１３の底部には下部電極層１０が露出するが、その後、ビアホール１３の表面を含めた絶縁層間膜１２の表面を、例えば、窒化チタン（ＴｉＮ）、窒化タンタル（ＴａＮ）や酸化マンガン（ＭｎＯｘ）からなるバリアメタル層１４で覆う。 First, an insulating interlayer film 12 is formed on the substrate S through a lower electrode layer 10 and a hard mask 11 made of, for example, silicon nitride (SiN), and the insulating interlayer film 12 is etched to be perpendicular to the substrate S. A via hole 13 is formed in the opening. The lower electrode layer 10 is exposed at the bottom of the via hole 13, and then the surface of the insulating interlayer film 12 including the surface of the via hole 13 is made of, for example, titanium nitride (TiN), tantalum nitride (TaN), manganese oxide (MnO x ) is covered with a barrier metal layer 14.
　次いで、ビアホール１３の底部に、例えば、ニッケル（Ｎｉ）からなる触媒金属層（図示しない）を形成し、さらに、図１Ａに示すように、プラズマ等を用いて触媒金属層から大きさや形状が均一の多数の触媒金属微粒子１５を形成する。なお、触媒金属層を構成する金属として、ニッケルの他に、銅（Ｃｕ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ルテニウム（Ｒｕ）、金（Ａｕ）、白金（Ｐｔ）、モリブデン（Ｍｏ）、マンガン（Ｍｎ）等の遷移金属、又はこれらの遷移金属を含む合金を用いてもよい。 Next, a catalytic metal layer (not shown) made of, for example, nickel (Ni) is formed on the bottom of the via hole 13, and the size and shape are uniform from the catalytic metal layer using plasma or the like as shown in FIG. 1A. A large number of catalyst metal fine particles 15 are formed. In addition to nickel, the metal constituting the catalyst metal layer is copper (Cu), iron (Fe), cobalt (Co), ruthenium (Ru), gold (Au), platinum (Pt), molybdenum (Mo). , Transition metals such as manganese (Mn), or alloys containing these transition metals may be used.
　次いで、プラズマ等を用いて各触媒金属微粒子１５の表面の酸化物を除去して活性化を行い、図１Ｂに示すように、アセチレンガスやエチレンガス等の炭素含有ガスから熱分解によって生じた炭素原子を、各触媒金属微粒子１５を核として互いに結合させて複数のカーボンナノチューブ１６（微細構造の導電体）を生成する。このとき、各カーボンナノチューブ１６は、触媒金属微粒子１５の性状を保ったまま、互いに衝突しないように各触媒金属微粒子１５から一方向（図１Ｂ中の上方）に成長する。したがって、複数のカーボンナノチューブ１６が基板Ｓの表面に対して略垂直に配向する。また、各カーボンナノチューブ１６は各触媒金属微粒子１５から成長するので、触媒金属微粒子１５を形成する際、処理ガスの種類や処理ガスを励起するエネルギーを調整して各触媒金属微粒子１５を高密度に形成すると、高密度のカーボンナノチューブ１６が得られる。一方、各触媒金属微粒子１５を高密度に形成しても、各触媒金属微粒子１５の間には微少な隙間が残存するため、各カーボンナノチューブ１６の間には微少であって高アスペクト比の隙間１７が生じる。 Next, activation is performed by removing the oxide on the surface of each catalytic metal fine particle 15 using plasma or the like, and as shown in FIG. 1B, carbon generated by pyrolysis from a carbon-containing gas such as acetylene gas or ethylene gas. Atoms are bonded to each other using each catalytic metal fine particle 15 as a nucleus to generate a plurality of carbon nanotubes 16 (microstructured conductors). At this time, the carbon nanotubes 16 grow in one direction (upward in FIG. 1B) from the catalytic metal fine particles 15 so as not to collide with each other while maintaining the properties of the catalytic metal fine particles 15. Therefore, the plurality of carbon nanotubes 16 are oriented substantially perpendicular to the surface of the substrate S. Further, since each carbon nanotube 16 grows from each catalytic metal fine particle 15, when forming the catalytic metal fine particle 15, the type of processing gas and the energy for exciting the processing gas are adjusted to make each catalytic metal fine particle 15 dense. When formed, high-density carbon nanotubes 16 are obtained. On the other hand, even if the catalyst metal fine particles 15 are formed at a high density, minute gaps remain between the catalyst metal fine particles 15. 17 occurs.
　次いで、各カーボンナノチューブ１６の間に生じた隙間１７を埋めるために、金属、例えば、銅１８をＣＶＤによって隙間１７へ充填する（図１Ｃ）。 Next, in order to fill the gaps 17 formed between the carbon nanotubes 16, a metal, for example, copper 18 is filled into the gaps 17 by CVD (FIG. 1C).
　図２は、各カーボンナノチューブの間の隙間を銅で充填するためのＣＶＤを実行するＣＶＤ処理装置の構成を概略的に示す断面図である。 FIG. 2 is a cross-sectional view schematically showing a configuration of a CVD processing apparatus that performs CVD for filling the gaps between the carbon nanotubes with copper.
　図２において、ＣＶＤ処理装置１９は、略円筒状のチャンバ２０と、該チャンバ２０の底部に配置される下部ステージヒータ２１と、チャンバ２０の天井部に配置されて下部ステージヒータ２１に対向する上部ステージヒータ２２と、下部ステージヒータ２１及び上部ステージヒータ２２の間においてチャンバ２０の内部を横断するように配置され、中心部に上下方向に貫通する貫通穴２３を有する棚状の試料ステージ２４と、チャンバ２０の内部へキャリアガス等を供給するガス供給系２５と、チャンバ２０の内部の残存ガス等を排気するガス排出系２６と、各構成要素の動作を制御する制御部２７とを備える。 In FIG. 2, a CVD processing apparatus 19 includes a substantially cylindrical chamber 20, a lower stage heater 21 disposed at the bottom of the chamber 20, and an upper portion disposed on the ceiling of the chamber 20 and facing the lower stage heater 21. A stage heater 22, a shelf-like sample stage 24 that is disposed between the lower stage heater 21 and the upper stage heater 22 so as to cross the inside of the chamber 20 and has a through hole 23 that penetrates in the vertical direction in the center portion; A gas supply system 25 that supplies a carrier gas or the like into the chamber 20, a gas discharge system 26 that exhausts a residual gas or the like inside the chamber 20, and a control unit 27 that controls the operation of each component.
　ＣＶＤ処理装置１９では、下部ステージヒータ２１に基板Ｓが載置され、チャンバ２０の内部の雰囲気が、例えば、窒素ガスで置換された後、ガス排出系２６によってチャンバ２０の内部の圧力が、例えば、３Ｔｏｒｒまで減圧される。下部ステージヒータ２１によって基板Ｓの温度が２００℃~２５０℃のいずれかに設定され、さらに、試料ステージ２４には、例えば、ＣＯＤ−Ｃｕ−ｈｆａｃ分子からなる金属錯体２８が配置され、金属錯体２８は上部ステージヒータ２２によって加熱される。このとき、加熱された金属錯体２８から飛散したＣＯＤ−Ｃｕ−ｈｆａｃ分子がチャンバ２０の内部を浮遊し、貫通穴２３を通過して基板Ｓへ到達し、基板Ｓに形成された各カーボンナノチューブ１６の間の隙間１７が銅１８で充填される。 In the CVD processing apparatus 19, the substrate S is placed on the lower stage heater 21, and the atmosphere inside the chamber 20 is replaced with, for example, nitrogen gas. The pressure is reduced to 3 Torr. The temperature of the substrate S is set to any one of 200 ° C. to 250 ° C. by the lower stage heater 21, and a metal complex 28 made of, for example, COD-Cu-hfac molecules is disposed on the sample stage 24. Is heated by the upper stage heater 22. At this time, COD-Cu-hfac molecules scattered from the heated metal complex 28 float inside the chamber 20, pass through the through hole 23, reach the substrate S, and each carbon nanotube 16 formed on the substrate S. The gap 17 is filled with copper 18.
　図３は、各カーボンナノチューブの間に生じた隙間を埋めるためにＣＶＤで用いられる金属錯体を構成するＣＯＤ−Ｃｕ−ｈｆａｃ分子の分子構造を説明する図であり、図４Ａ及び図４Ｂは、図２のＣＶＤ処理装置で実行されるＣＶＤを説明するための工程図である。 FIG. 3 is a diagram for explaining the molecular structure of COD-Cu-hfac molecules constituting a metal complex used in CVD to fill gaps generated between the carbon nanotubes, and FIGS. 4A and 4B are diagrams. It is process drawing for demonstrating CVD performed with the CVD processing apparatus of 2. FIG.
　図３において、ＣＯＤ−Ｃｕ−ｈｆａｃ分子は、シクロオクタジエン（ｃｙｃｌｏｏｃｔａｄｉｅｎｅ、以下、単に「ＣＯＤ」という。）と、銅原子と、ヘキサフルオロアセチルアセトン（ｈｅｘａｆｌｕｏｒｏａｃｅｔｙｌａｃｅｔｏｎｅ、以下、単に「ｈｆａｃ」という。）とからなり、銅原子はｈｆａｃの２つの酸素原子のそれぞれと結合手によって単結合するが、ＣＯＤは単結合及び二重結合からなる共役系を有し、共役系のπ電子に起因する相互作用、具体的には、π電子の共有によって銅原子と結合する。 In FIG. 3, a COD-Cu-hfac molecule is composed of cyclooctadiene (hereinafter simply referred to as “COD”), a copper atom, and hexafluoroacetylacetone (hereinafter simply referred to as “hfac”). The copper atom is single-bonded to each of the two oxygen atoms of hfac by a bond, while COD has a conjugated system consisting of a single bond and a double bond. Specifically, it bonds to a copper atom by sharing π electrons.
　通常、結合手による結合よりもπ電子の共有による結合の方が結合力は弱いため、基板Ｓが下部ステージヒータ２１によって加熱されると、該基板Ｓへ到達した各ＣＯＤ−Ｃｕ−ｈｆａｃ分子からＣＯＤ（他の分子）が脱離し、２つのＣＯＤが結合して気化する。 In general, since the bonding force of π electron sharing is weaker than that of bonding by a bond, when the substrate S is heated by the lower stage heater 21, each COD-Cu-hfac molecule that has reached the substrate S COD (another molecule) is desorbed, and the two CODs are combined and vaporized.
　ところで、各カーボンナノチューブ１６の表面は全域に亘って連続する炭素の六員環（ベンゼン環）によって構成される。各ベンゼン環は単結合及び二重結合からなる共役系を有するため、各ベンゼン環にはπ電子が存在する。ここで、ＣＯＤが脱離したＣＯＤ−Ｃｕ−ｈｆａｃ分子（以下、「Ｃｕ−ｈｆａｃ分子」という。）の銅原子は電子を共有可能な状態にあるため、銅原子は各ベンゼン環のπ電子を共有して積極的に各ベンゼン環と結合する。本実施の形態では、２つのＣＯＤが結合すべく、基板Ｓへ到達した２つのＣＯＤ−Ｃｕ−ｈｆａｃ分子が互いに隣接する傾向にあるため、結果として、隣接する２つのベンゼン環のそれぞれにＣｕ−ｈｆａｃ分子の銅原子が結合する（図４Ａ）。なお、このときの各銅原子は１価である。 By the way, the surface of each carbon nanotube 16 is constituted by a carbon six-membered ring (benzene ring) continuous over the entire area. Since each benzene ring has a conjugated system composed of a single bond and a double bond, π electrons exist in each benzene ring. Here, since the copper atom of the COD-Cu-hfac molecule (hereinafter referred to as “Cu-hfac molecule”) from which COD has been eliminated is in a state where it can share an electron, the copper atom is responsible for the π electron of each benzene ring. Share and actively bond to each benzene ring. In the present embodiment, since two COD-Cu-hfac molecules that have reached the substrate S tend to be adjacent to each other so that the two CODs are bonded to each other, as a result, Cu-- The copper atom of the hfac molecule binds (FIG. 4A). In addition, each copper atom at this time is monovalent.
　次いで、基板Ｓを下部ステージヒータ２１によって加熱しつづけると、熱エネルギーによって隣接する２つのＣｕ−ｈｆａｃ分子が不均一反応を起こして電子の授受が行われ、１つの銅原子は２価となり、２つのＣｕ−ｈｆａｃ分子のｈｆａｃと結合してＣｕ（ｈｆａｃ）２として気化する。一方、他の銅原子は０価となり、安定してベンゼン環と結合する（図４Ｂ）。これにより、各カーボンナノチューブ１６の表面を銅原子で覆うことができる。 Next, when the substrate S is continuously heated by the lower stage heater 21, two adjacent Cu-hfac molecules cause a heterogeneous reaction due to thermal energy, and electrons are exchanged, so that one copper atom becomes divalent, 2 It binds to hfac of two Cu-hfac molecules and vaporizes as Cu (hfac) 2. On the other hand, other copper atoms become zero-valent and are stably bonded to the benzene ring (FIG. 4B). Thereby, the surface of each carbon nanotube 16 can be covered with copper atoms.
　上述したＣＶＤ処理装置１９によるＣＶＤでは、Ｃｕ−ｈｆａｃ分子の銅原子がカーボンナノチューブ１６のベンゼン環のπ電子を共有して積極的に各ベンゼン環と結合する。すなわち、ベンゼン環のπ電子の存在により、カーボンナノチューブ１６の表面の全域に亘って銅原子を配置することができるため、各カーボンナノチューブ１６の間の隙間１７のアスペクト比が高くても、銅原子を隙間１７の奥まで進入させることができ、もって、図５に示すように、各カーボンナノチューブ１６の間の隙間１７を銅１８でほぼ完全に充填することができる。 In the above-described CVD by the CVD processing apparatus 19, the copper atom of the Cu-hfac molecule shares the π electron of the benzene ring of the carbon nanotube 16 and actively bonds to each benzene ring. That is, since the copper atoms can be arranged over the entire surface of the carbon nanotubes 16 due to the presence of π electrons in the benzene ring, even if the aspect ratio of the gaps 17 between the carbon nanotubes 16 is high, the copper atoms As shown in FIG. 5, the gaps 17 between the carbon nanotubes 16 can be almost completely filled with the copper 18.
　なお、本実施の形態では、ＣＶＤ処理装置１９によるＣＶＤを所定時間に亘って継続することにより、各カーボンナノチューブ１６の間の隙間１７を銅１８で充填するだけでなく、銅１８によって基板Ｓの全面を覆う。 In the present embodiment, by continuing the CVD by the CVD processing apparatus 19 for a predetermined time, not only the gaps 17 between the carbon nanotubes 16 are filled with the copper 18, but also the copper 18 is used to form the substrate S. Cover the entire surface.
　次いで、ＣＭＰ（Ｃｈｅｍｉｃａｌ　Ｍｅｃｈａｎｉｃａｌ　Ｐｏｌｉｓｈｉｎｇ）等によって基板Ｓを覆う余剰の銅１８を除去し、基板Ｓにおいて各カーボンナノチューブ１６の先端を露出させる（図１Ｄ）。 Next, excess copper 18 covering the substrate S is removed by CMP (Chemical Mechanical Polishing) or the like, and the tips of the carbon nanotubes 16 are exposed on the substrate S (FIG. 1D).
　次いで、基板Ｓの表面をＣＶＤやＰＶＤによって成膜される上部電極層２９で覆う。このとき、上部電極層２９と各カーボンナノチューブ１６の先端が接触し、各カーボンナノチューブ１６、各触媒金属微粒子１５及びバリアメタル層１４を介して下部電極層１０及び上部電極層２９が互いに導通される（図１Ｅ）。その後、本方法を終了する。 Next, the surface of the substrate S is covered with an upper electrode layer 29 formed by CVD or PVD. At this time, the upper electrode layer 29 and the tips of the carbon nanotubes 16 are in contact with each other, and the lower electrode layer 10 and the upper electrode layer 29 are electrically connected to each other through the carbon nanotubes 16, the catalytic metal fine particles 15, and the barrier metal layer 14. (FIG. 1E). Thereafter, the method ends.
　本実施の形態に係る複合配線の製造方法によれば、ＣＶＤにおいて熱等によってＣＯＤが脱離したＣＯＤ−Ｃｕ−ｈｆａｃ分子（Ｃｕ−ｈｆａｃ分子）の銅原子が、各カーボンナノチューブ１６のベンゼン環のπ電子に起因する相互作用によってベンゼン環と結合する。すなわち、各カーボンナノチューブ１６においてベンゼン環が存在する箇所へＣｕ−ｈｆａｃ分子を配置することができ、各カーボンナノチューブ１６は表面の全域に亘ってベンゼン環を有するので、各カーボンナノチューブ１６の隙間１７のアスペクト比が高くても、カーボンナノチューブ１６の表面が露出する限り、Ｃｕ−ｈｆａｃ分子を隙間１７の奥まで進入させることができ、もって、各カーボンナノチューブ１６の間の隙間１７を銅１８でほぼ完全に充填することができる。その結果、銅１８及び各カーボンナノチューブ１６からなる複合配線の抵抗を大幅に低下させることができるとともに、複合配線の構造を強固にすることができる。 According to the method for manufacturing a composite wiring according to the present embodiment, the copper atoms of COD-Cu-hfac molecules (Cu-hfac molecules) from which COD has been desorbed by heat or the like in CVD are formed on the benzene ring of each carbon nanotube 16. It binds to the benzene ring by interaction caused by π electrons. That is, Cu-hfac molecules can be arranged at locations where benzene rings are present in each carbon nanotube 16, and each carbon nanotube 16 has a benzene ring over the entire surface. Even if the aspect ratio is high, as long as the surface of the carbon nanotubes 16 is exposed, Cu-hfac molecules can enter deep into the gaps 17, and the gaps 17 between the carbon nanotubes 16 are almost completely covered with copper 18. Can be filled. As a result, the resistance of the composite wiring composed of the copper 18 and each carbon nanotube 16 can be greatly reduced, and the structure of the composite wiring can be strengthened.
　また、上述した複合配線の製造方法では、Ｃｕ−ｈｆａｃ分子の銅原子と各カーボンナノチューブ１６のベンゼン環との結合にπ電子を利用するため、ＣＶＤによって各カーボンナノチューブ１６の隙間１７を銅１８で充填する際、基板Ｓの温度が比較的低温である、２００℃~２５０℃のいずれかにしか設定されず、付与されるエネルギーが少なくても、Ｃｕ−ｈｆａｃ分子の銅原子と各カーボンナノチューブ１６のベンゼン環とを結合することができる。これにより、基板Ｓの温度を高温に設定する必要を無くすことができ、もって、基板Ｓに形成される三次元実装デバイス等の有機系の低誘電率層間膜が熱によって破壊されるのを防止することができる。また、上述した複合配線の製造方法によって製造される各カーボンナノチューブ１６及び銅１８からなる配線は、磁気抵抗メモリ（ＭＲＡＭ）や抵抗変化型メモリ（ＲｅＲＡＭ）等の不揮発性メモリ素子の配線にも適用することができる。 Further, in the above-described composite wiring manufacturing method, π electrons are used for bonding between the copper atom of the Cu-hfac molecule and the benzene ring of each carbon nanotube 16, so that the gap 17 between each carbon nanotube 16 is made of copper 18 by CVD. At the time of filling, the temperature of the substrate S is set to only 200 ° C. to 250 ° C., which is relatively low, and even if the applied energy is small, the copper atoms of the Cu-hfac molecules and the carbon nanotubes 16 Can be bonded to the benzene ring. This eliminates the need to set the temperature of the substrate S to a high temperature, thereby preventing the organic low dielectric constant interlayer film such as a three-dimensional mounting device formed on the substrate S from being destroyed by heat. can do. Further, the wiring composed of the carbon nanotubes 16 and the copper 18 manufactured by the above-described composite wiring manufacturing method is also applied to wiring of a nonvolatile memory element such as a magnetoresistive memory (MRAM) or a resistance change memory (ReRAM). can do.
　また、本実施の形態に係る複合配線の製造方法によれば、ビアホール１３において各カーボンナノチューブ１６が下部電極層１０及び上部電極層２９を互いに導通するが、カーボンナノチューブ１６は高熱伝導性を有するので、基板Ｓに形成される三次元実装デバイス等において下部電極層１０や上部電極層２９等に熱が滞留するのを防止することができる。 Further, according to the method for manufacturing a composite wiring according to the present embodiment, each carbon nanotube 16 conducts the lower electrode layer 10 and the upper electrode layer 29 to each other in the via hole 13, but the carbon nanotube 16 has high thermal conductivity. In the three-dimensional mounting device or the like formed on the substrate S, heat can be prevented from staying in the lower electrode layer 10, the upper electrode layer 29, or the like.
　次に、本発明の第２の実施の形態に係る複合配線の製造方法の生成方法について説明する。 Next, a generation method of the composite wiring manufacturing method according to the second embodiment of the present invention will be described.
　本実施の形態は、その構成や作用が上述した第１の実施の形態と基本的に同じであり、複数のカーボンナノチューブを基板Ｓの表面に対して略水平に配向させる点で上述した第１の実施の形態と異なる。したがって、重複した構成、作用については説明を省略し、以下に異なる構成、作用についての説明を行う。 This embodiment is basically the same in configuration and operation as the first embodiment described above, and the first embodiment described above in that a plurality of carbon nanotubes are oriented substantially horizontally with respect to the surface of the substrate S. This is different from the embodiment. Therefore, the description of the duplicated configuration and operation is omitted, and the description of the different configuration and operation is given below.
　図６Ａ乃至図６Ｈは、本実施の形態に係る複合配線の製造方法を説明するための工程図である。 6A to 6H are process diagrams for explaining the method of manufacturing the composite wiring according to the present embodiment.
　まず、基板Ｓ上に絶縁層間膜３０を成膜し、絶縁層間膜３０をエッチングしてトレンチ３１を形成し、さらに、トレンチ３１の底部の一部をエッチングして配線穴３２を形成し、該配線穴３２に導電体を充填して下部電極３３を形成する。なお、トレンチ３１や配線穴３２の表面は、例えば、窒化チタンからなるバリアメタル層３４で覆われる。 First, an insulating interlayer film 30 is formed on the substrate S, the insulating interlayer film 30 is etched to form a trench 31, and a part of the bottom of the trench 31 is etched to form a wiring hole 32. The lower electrode 33 is formed by filling the wiring hole 32 with a conductor. The surfaces of the trench 31 and the wiring hole 32 are covered with a barrier metal layer 34 made of, for example, titanium nitride.
　次いで、トレンチ３１の一側面に、例えば、ニッケルからなる触媒金属層（図示しない）を形成し、さらに、図６Ａに示すように、プラズマ等を用いて触媒金属層から大きさや形状が均一の多数の触媒金属微粒子３５を形成する。 Next, a catalytic metal layer (not shown) made of, for example, nickel is formed on one side surface of the trench 31, and, as shown in FIG. 6A, a large number of uniform sizes and shapes are formed from the catalytic metal layer using plasma or the like. The catalyst metal fine particles 35 are formed.
　次いで、プラズマ等を用いて各触媒金属微粒子３５の表面の活性化を行い、図６Ｂに示すように、炭素含有ガスから熱分解によって生じた炭素原子を、各触媒金属微粒子３５を核として互いに結合させて複数のカーボンナノチューブ３６（微細構造の導電体）を生成する。各カーボンナノチューブ３６は、互いに衝突しないように各触媒金属微粒子３５から一方向（図６Ｂ中の左方）に成長する。したがって、複数のカーボンナノチューブ３６が基板Ｓの表面に対して略水平に配向する。このとき、各カーボンナノチューブ３６の間には微少であって高アスペクト比の隙間３７が生じる。 Next, the surface of each catalytic metal fine particle 35 is activated using plasma or the like, and as shown in FIG. 6B, carbon atoms generated by pyrolysis from the carbon-containing gas are bonded to each other using each catalytic metal fine particle 35 as a nucleus. Thus, a plurality of carbon nanotubes 36 (fine conductors) are generated. Each carbon nanotube 36 grows in one direction (left side in FIG. 6B) from each catalytic metal fine particle 35 so as not to collide with each other. Therefore, the plurality of carbon nanotubes 36 are aligned substantially horizontally with respect to the surface of the substrate S. At this time, a gap 37 having a small and high aspect ratio is generated between the carbon nanotubes 36.
　次いで、各カーボンナノチューブ３６の間に生じた隙間３７を埋めるために、ＣＶＤ処理装置１９においてＣＯＤ−Ｃｕ−ｈｆａｃ分子からなる金属錯体２８を用いて基板ＳにＣＶＤを施す。このとき、第１の実施の形態と同様に、各ＣＯＤ−Ｃｕ−ｈｆａｃ分子からのＣＯＤの脱離、Ｃｕ−ｈｆａｃ分子の銅原子と各カーボンナノチューブ３６のベンゼン環とのπ電子の共有による結合、並びに、隣接する２つのＣｕ−ｈｆａｃ分子の不均一反応を通じて各カーボンナノチューブ３６の表面が銅原子で覆われ、銅１８が隙間３７へ充填される（図６Ｃ）。なお、本実施の形態でも、各カーボンナノチューブ３６の間の隙間３７を銅１８で充填するだけでなく、銅１８によって基板Ｓの全面を覆う。 Next, in order to fill the gaps 37 generated between the carbon nanotubes 36, the CVD processing apparatus 19 performs CVD on the substrate S using the metal complex 28 made of COD-Cu-hfac molecules. At this time, as in the first embodiment, COD is desorbed from each COD-Cu-hfac molecule, and the π-electron bond is formed between the copper atom of the Cu-hfac molecule and the benzene ring of each carbon nanotube 36. In addition, the surface of each carbon nanotube 36 is covered with copper atoms through the heterogeneous reaction of two adjacent Cu-hfac molecules, and the copper 18 is filled into the gap 37 (FIG. 6C). In the present embodiment, not only the gaps 37 between the carbon nanotubes 36 are filled with the copper 18, but the entire surface of the substrate S is covered with the copper 18.
　次いで、ＣＭＰ等によって基板Ｓを覆う余剰の銅１８を除去し（図６Ｄ）、窒化珪素からなるハードマスク３８を介して他の層間絶縁膜３９を基板Ｓ上に成膜し（図６Ｅ）、さらに、エッチングによって他の層間絶縁膜３９及びハードマスク３８の一部を貫通する配線穴４０を形成し（図６Ｆ）、該配線穴４０の表面をバリアメタル層３４で覆った（図６Ｇ）後、配線穴４０に導電体を充填して上部電極４１を形成する。このとき、トレンチ３１内の各カーボンナノチューブ３６や銅１８、バリアメタル層３４を介して下部電極３３及び上部電極４１が互いに導通される（図６Ｈ）。その後、本方法を終了する。 Next, excess copper 18 covering the substrate S is removed by CMP or the like (FIG. 6D), and another interlayer insulating film 39 is formed on the substrate S through the hard mask 38 made of silicon nitride (FIG. 6E). Further, a wiring hole 40 penetrating a part of another interlayer insulating film 39 and the hard mask 38 is formed by etching (FIG. 6F), and the surface of the wiring hole 40 is covered with the barrier metal layer 34 (FIG. 6G). Then, the upper electrode 41 is formed by filling the wiring hole 40 with a conductor. At this time, the lower electrode 33 and the upper electrode 41 are electrically connected to each other through the carbon nanotubes 36, the copper 18, and the barrier metal layer 34 in the trench 31 (FIG. 6H). Thereafter, the method ends.
　本実施の形態に係る複合配線の製造方法によれば、Ｃｕ−ｈｆａｃ分子の銅原子が各カーボンナノチューブ３６のベンゼン環とπ電子の共有によって結合する。すなわち、本実施の形態に係る複合配線の製造方法においても、各カーボンナノチューブ３６においてベンゼン環が存在する箇所へＣｕ−ｈｆａｃ分子を配置することができ、各カーボンナノチューブ３６の隙間３７のアスペクト比が高くても、各カーボンナノチューブ３６の間の隙間３７を銅１８でほぼ完全に充填することができる。 According to the method for manufacturing a composite wiring according to the present embodiment, the copper atom of the Cu-hfac molecule is bonded to the benzene ring of each carbon nanotube 36 by the sharing of π electrons. That is, also in the manufacturing method of the composite wiring according to the present embodiment, Cu-hfac molecules can be arranged at locations where benzene rings exist in each carbon nanotube 36, and the aspect ratio of the gap 37 of each carbon nanotube 36 is Even if it is high, the gaps 37 between the carbon nanotubes 36 can be almost completely filled with the copper 18.
　以上、本発明について、上述した各実施の形態を用いて説明したが、本発明は上述した各実施の形態に限定されるものではない。 As mentioned above, although this invention was demonstrated using each embodiment mentioned above, this invention is not limited to each embodiment mentioned above.
　例えば、上述した各実施の形態では、カーボンナノチューブを微細構造の導電体として用いたが、共役系を有する分子を含む導電体であれば微細構造の導電体として用いることができる。例えば、微細構造の導電体として高アスペクト比のグラフェンリボンをビアホール１３やトレンチ３１に配置してもよい。この場合、各グラフェンリボンの間の隙間は高アスペクト比となるが、グラフェンリボンも全域に亘って連続するベンゼン環によって構成されるため、ＣＯＤ−Ｃｕ−ｈｆａｃ分子からなる金属錯体２８を用いたＣＶＤにより、各グラフェンリボンの間の隙間を銅１８でほぼ完全に充填することができる。なお、本発明を適用可能な共役系を有する金属錯体には、ＣＯＤ−Ｃｕ−ｈｆａｃ分子からなる金属錯体２８の他に、例えば、銅、白金、イリジウム（Ｉｒ）、ニッケル、コバルト及びモリブデンのいずれかからなる金属原子、該金属原子とπ電子の共有によって銅原子と結合（π共役結合）する、例えば、１，５−シクロオクタジエン、ジメチル−１，５−シクロオクタジエン、ジエチル−１，５−シクロオクタジエン、１，５−ヘキサジエン、１，３−ペンタジエン、４−ビニル−１−シクロヘキセン及びノルボルナジエンのいずれかの共役系を有する配位子、並びに、上記金属原子と結合手によって単結合する、例えば、ヘキサフルオロアセチルアセトネート（ｈｆａｃ）、アセチルアセトネート（ａｃａｃ）及び１，１，１−トリメチルアセチルアセトネートのいずれかの配位子を有する金属錯体が該当する。 For example, in each of the above-described embodiments, the carbon nanotube is used as a fine conductor. However, any conductor containing a molecule having a conjugated system can be used as a fine conductor. For example, a high aspect ratio graphene ribbon may be disposed in the via hole 13 or the trench 31 as a fine-structured conductor. In this case, the gap between the graphene ribbons has a high aspect ratio, but the graphene ribbon is also composed of a continuous benzene ring over the entire region, so that CVD using a metal complex 28 made of COD-Cu-hfac molecules is used. Thus, the gaps between the graphene ribbons can be almost completely filled with the copper 18. The metal complex having a conjugated system to which the present invention can be applied includes, for example, any of copper, platinum, iridium (Ir), nickel, cobalt, and molybdenum in addition to the metal complex 28 composed of COD-Cu-hfac molecules. A metal atom composed of the above, and bonded to a copper atom by sharing the π electron with the metal atom (π conjugated bond), for example, 1,5-cyclooctadiene, dimethyl-1,5-cyclooctadiene, diethyl-1, A ligand having a conjugated system of 5-cyclooctadiene, 1,5-hexadiene, 1,3-pentadiene, 4-vinyl-1-cyclohexene and norbornadiene, and a single bond by the above metal atom and a bond For example, hexafluoroacetylacetonate (hfac), acetylacetonate (acac) and 1,1,1-trimethyl This corresponds to a metal complex having any ligand of ruacetylacetonate.
　また、各カーボンナノチューブ１６の間の隙間１７を銅１８で充填するためのＣＶＤを実行するＣＶＤ処理装置は、図２に示すＣＶＤ処理装置１９に限られず、例えば、図７に示すようなシャワーヘッド型のＣＶＤ処理装置４２であってもよい。 Further, the CVD processing apparatus for performing the CVD for filling the gaps 17 between the carbon nanotubes 16 with the copper 18 is not limited to the CVD processing apparatus 19 shown in FIG. 2, but for example, a shower head as shown in FIG. It may be a type of CVD processing apparatus 42.
　図７は、図２のＣＶＤ処理装置の変形例の構成を概略的に示す断面図である。 FIG. 7 is a cross-sectional view schematically showing a configuration of a modified example of the CVD processing apparatus of FIG.
　図７において、ＣＶＤ処理装置４２は、略円筒状のチャンバ４３と、該チャンバ４３の底部に配置されるテーブル状のステージヒータ４４と、チャンバ４３の天井部に配置されてステージヒータ４４に対向するシャワーヘッド４５と、チャンバ４３の内部へ、例えば、アルゴン（Ａｒ）やヘリウム（Ｈｅ）からなるキャリアガスとともに金属錯体２８、例えば、ＣＯＤ−Ｃｕ−ｈｆａｃ分子のガスを供給する金属錯体ガス供給系４６と、チャンバ４３の内部へ添加ガス、例えば、ＣＯＤやｈｆａｃのガスを供給する添加ガス供給系４７と、チャンバ４３の内部へ希釈ガス、例えば、アルゴンやヘリウムのガスを供給する希釈ガス供給系４８と、チャンバ４３の内部へクリーニングガス、例えば、ｈｆａｃやＨＣＯＯＨのガスを供給するクリーニングガス供給系４９と、チャンバ４３の内部へパージガス、例えば、窒素（Ｎ２）ガスを供給するパージガス供給系５０と、チャンバ４３の内部を排気する、例えば、圧力調整用可変バルブ５１や排気ポンプ５２からなるガス排出系５３と、ステージヒータ４４の動作を制御するステージヒータ制御部５４とを備える。金属錯体ガス供給系４６、添加ガス供給系４７、希釈ガス供給系４８及びクリーニングガス供給系４９はシャワーヘッド４５を介して各ガスをチャンバ４３の内部へ供給し、パージガス供給系５０はパージガスをチャンバ４３の内部へ直接供給する。 In FIG. 7, a CVD processing apparatus 42 includes a substantially cylindrical chamber 43, a table-like stage heater 44 disposed at the bottom of the chamber 43, and a ceiling portion of the chamber 43 facing the stage heater 44. For example, a metal complex gas supply system 46 for supplying a metal complex 28, for example, a gas of COD-Cu-hfac molecule, together with a carrier gas made of argon (Ar) or helium (He) into the shower head 45 and the chamber 43, for example. An additive gas supply system 47 for supplying an additive gas, for example, COD or hfac gas, into the chamber 43; and a dilution gas supply system 48 for supplying a diluent gas, for example, argon or helium gas, into the chamber 43. And a cleaning gas for supplying a cleaning gas such as hfac or HCOOH into the chamber 43. And Ngugasu supply system 49, purge gas into the interior of the chamber 43, for example, nitrogen (N 2) and a purge gas supply system 50 for supplying a gas, evacuating the interior of the chamber 43, for example, a pressure adjusting variable valve 51 and the exhaust pump 52 And a stage heater control unit 54 for controlling the operation of the stage heater 44. The metal complex gas supply system 46, the additive gas supply system 47, the dilution gas supply system 48, and the cleaning gas supply system 49 supply each gas to the inside of the chamber 43 via the shower head 45, and the purge gas supply system 50 supplies the purge gas to the chamber. It supplies directly to the inside of 43.
　ＣＶＤ処理装置４２では、ステージヒータ４４に基板Ｓが載置され、チャンバ４３の内部の雰囲気がガス排出系５３によって真空排気され、さらに、添加ガス供給系４７から添加ガスを、または希釈ガス供給系４８から希釈ガスを供給してチャンバ４３の内部の圧力を３Ｔｏｒｒに調圧する。その後、ステージヒータ４４によって基板Ｓの温度が２００℃~２５０℃のいずれかに設定され、さらに、チャンバ４３の内部に添加ガス、希釈ガスやキャリアガスとともに金属錯体２８のガスが供給され、金属錯体２８中のＣＯＤ−Ｃｕ−ｈｆａｃ分子が加熱された基板Ｓへ到達し、基板Ｓに形成された各カーボンナノチューブ１６の間の隙間１７が銅１８で充填される（図１Ｃ等参照）。 In the CVD processing apparatus 42, the substrate S is placed on the stage heater 44, the atmosphere inside the chamber 43 is evacuated by the gas exhaust system 53, and the additive gas is supplied from the additive gas supply system 47 or the dilution gas supply system. A dilution gas is supplied from 48 to adjust the pressure inside the chamber 43 to 3 Torr. Thereafter, the temperature of the substrate S is set to any one of 200 ° C. to 250 ° C. by the stage heater 44, and the gas of the metal complex 28 is supplied into the chamber 43 together with the additive gas, the dilution gas, and the carrier gas. The COD-Cu-hfac molecules in 28 reach the heated substrate S, and the gaps 17 between the carbon nanotubes 16 formed on the substrate S are filled with copper 18 (see FIG. 1C and the like).
　本発明の目的は、上述した各実施の形態の機能を実現するソフトウェアのプログラムコードを記録した記憶媒体を、コンピュータ、例えば、制御部２７に供給し、制御部２７のＣＰＵが記憶媒体に格納されたプログラムコードを読み出して実行することによっても達成される。 An object of the present invention is to supply a computer, for example, the control unit 27, with a storage medium storing software program codes that implement the functions of the above-described embodiments, and the CPU of the control unit 27 is stored in the storage medium. It is also achieved by reading and executing the program code.
　この場合、記憶媒体から読み出されたプログラムコード自体が上述した各実施の形態の機能を実現することになり、プログラムコード及びそのプログラムコードを記憶した記憶媒体は本発明を構成することになる。 In this case, the program code itself read from the storage medium realizes the functions of the above-described embodiments, and the program code and the storage medium storing the program code constitute the present invention.
　また、プログラムコードを供給するための記憶媒体としては、例えば、ＲＡＭ、ＮＶ−ＲＡＭ、フロッピー（登録商標）ディスク、ハードディスク、光磁気ディスク、ＣＤ−ＲＯＭ、ＣＤ−Ｒ、ＣＤ−ＲＷ、ＤＶＤ（ＤＶＤ−ＲＯＭ、ＤＶＤ−ＲＡＭ、ＤＶＤ−ＲＷ、ＤＶＤ＋ＲＷ）等の光ディスク、磁気テープ、不揮発性のメモリカード、他のＲＯＭ等の上記プログラムコードを記憶できるものであればよい。或いは、上記プログラムコードは、インターネット、商用ネットワーク、若しくはローカルエリアネットワーク等に接続される不図示の他のコンピュータやデータベース等からダウンロードすることにより制御部２７に供給されてもよい。 Examples of the storage medium for supplying the program code include RAM, NV-RAM, floppy (registered trademark) disk, hard disk, magneto-optical disk, CD-ROM, CD-R, CD-RW, DVD (DVD). -ROM, DVD-RAM, DVD-RW, DVD + RW) and other optical disks, magnetic tapes, non-volatile memory cards, other ROMs, etc., as long as they can store the program code. Alternatively, the program code may be supplied to the control unit 27 by downloading from another computer or database (not shown) connected to the Internet, a commercial network, a local area network, or the like.
　また、制御部２７が読み出したプログラムコードを実行することにより、上記各実施の形態の機能が実現されるだけでなく、そのプログラムコードの指示に基づき、ＣＰＵ上で稼動しているＯＳ（オペレーティングシステム）等が実際の処理の一部又は全部を行い、その処理によって上述した各実施の形態の機能が実現される場合も含まれる。 Further, by executing the program code read by the control unit 27, not only the functions of the above-described embodiments are realized, but also an OS (operating system) running on the CPU based on an instruction of the program code. ) Etc. perform part or all of actual processing, and the functions of the above-described embodiments are realized by the processing.
　更に、記憶媒体から読み出されたプログラムコードが、制御部２７に挿入された機能拡張ボードや制御部２７に接続された機能拡張ユニットに備わるメモリに書き込まれた後、そのプログラムコードの指示に基づき、その機能拡張ボードや機能拡張ユニットに備わるＣＰＵ等が実際の処理の一部又は全部を行い、その処理によって上述した各実施の形態の機能が実現される場合も含まれる。 Further, after the program code read from the storage medium is written in the memory provided in the function expansion board inserted into the control unit 27 or the function expansion unit connected to the control unit 27, the program code is read based on the instruction of the program code. The CPU of the function expansion board or function expansion unit performs part or all of the actual processing, and the functions of the above-described embodiments are realized by the processing.
　上記プログラムコードの形態は、オブジェクトコード、インタプリタにより実行されるプログラムコード、ＯＳに供給されるスクリプトデータ等の形態から成ってもよい。 The form of the program code may be in the form of object code, program code executed by an interpreter, script data supplied to the OS, and the like.
　本出願は、２０１４年９月５日に出願された日本出願第２０１４−１８１２０４号に基づく優先権を主張するものであり、当該日本出願に記載された全内容を本出願に援用する。 This application claims priority based on Japanese Patent Application No. 2014-181204 filed on September 5, 2014, the entire contents of which are incorporated in this application.
Ｓ　基板
１３　ビアホール
１６，３６　カーボンナノチューブ
１７，３７　隙間
１８　銅
１９　ＣＶＤ処理装置
２８　金属錯体
３１　トレンチ S substrate 13 via hole 16, 36 carbon nanotube 17, 37 gap 18 copper 19 CVD processing device 28 metal complex 31 trench

Claims (6)

  1. 　共役系を有する分子を含む微細構造の導電体へ、共役系を有する他の分子と金属原子とがπ電子に起因する相互作用によって結合する錯体を用いるＣＶＤを施すことを特徴とする複合配線の製造方法。 A composite wiring characterized by subjecting a fine-structured conductor including a molecule having a conjugated system to CVD using a complex in which another molecule having a conjugated system and a metal atom are bonded by an interaction caused by π electrons. Production method.
  2. 　前記微細構造の導電体は基板に形成され、
    　前記ＣＶＤを前記微細構造の導電体に施す際、前記基板の温度を２５０℃以下に設定することを特徴とする請求項１記載の複合配線の製造方法。     The microstructured conductor is formed on a substrate;
    2. The method of manufacturing a composite wiring according to claim 1, wherein the temperature of the substrate is set to 250 [deg.] C. or lower when the CVD is applied to the fine-structure conductor.
  3. 　前記微細構造の導電体は、カーボンナノチューブ又はグラフェンリボンであることを特徴とする請求項１又は２記載の複合配線の製造方法。 3. The method of manufacturing a composite wiring according to claim 1, wherein the fine-structured conductor is a carbon nanotube or a graphene ribbon.
  4. 　前記錯体はＣＯＤ−Ｃｕ−ｈｆａｃ分子であることを特徴とする請求項１乃至３のいずれか１項に記載の複合配線の製造方法。 The method for manufacturing a composite wiring according to any one of claims 1 to 3, wherein the complex is a COD-Cu-hfac molecule.
  5. 　共役系を有する分子を含む微細構造の導電体に生じる隙間に金属原子が充填された複合配線であって、
    　前記金属原子は、共役系を有する他の分子と前記金属原子とがπ電子に起因する相互作用によって結合する錯体を用いるＣＶＤを前記微細構造の導電体に施すことによって充填されることを特徴とする複合配線。     It is a composite wiring in which metal atoms are filled in gaps generated in a finely structured conductor containing molecules having a conjugated system,
    The metal atom is filled by subjecting the fine-structured conductor to CVD using a complex in which another molecule having a conjugated system and the metal atom are bonded by an interaction caused by π electrons. Composite wiring.
  6. 　前記微細構造の導電体は、カーボンナノチューブ又はグラフェンリボンであることを特徴とする請求項５記載の複合配線。 6. The composite wiring according to claim 5, wherein the fine-structured conductor is a carbon nanotube or a graphene ribbon.
PCT/JP2015/073922 2014-09-05 2015-08-19 Composite wiring and production method therefor WO2016035623A1 (en)

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JP2010523452A (en) * 2007-05-30 2010-07-15 エルジー・ケム・リミテッド Carbon nanotube dispersant containing metal complex
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JP2005285821A (en) * 2004-03-26 2005-10-13 Fujitsu Ltd Semiconductor device and its manufacturing method
JP2006148063A (en) * 2004-10-22 2006-06-08 Renesas Technology Corp Wiring structure, semiconductor device, mram, and manufacturing method of semiconductor device
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