WO2008026237A1 - Matériaux à base de nanotubes de carbone, procédé de production et dispositif et composants électroniques - Google Patents

Matériaux à base de nanotubes de carbone, procédé de production et dispositif et composants électroniques Download PDF

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Publication number
WO2008026237A1
WO2008026237A1 PCT/JP2006/316834 JP2006316834W WO2008026237A1 WO 2008026237 A1 WO2008026237 A1 WO 2008026237A1 JP 2006316834 W JP2006316834 W JP 2006316834W WO 2008026237 A1 WO2008026237 A1 WO 2008026237A1
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carbon nanotube
based material
substance
modified
active species
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PCT/JP2006/316834
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English (en)
Japanese (ja)
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Koji Asano
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Fujitsu Limited
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Priority to PCT/JP2006/316834 priority Critical patent/WO2008026237A1/fr
Priority to PCT/JP2007/000825 priority patent/WO2008026304A1/fr
Publication of WO2008026237A1 publication Critical patent/WO2008026237A1/fr

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    • 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
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • 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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • 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
    • H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
    • H01L21/76879—Filling of holes, grooves or trenches, e.g. vias, with conductive material by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating
    • 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

  • Carbon nanotube material manufacturing method thereof, electronic member and electronic device
  • the present invention relates to a surface modification technique for a carbon nanotube-based material.
  • CNTs have various characteristics such as excellent chemical stability and unique physical and electrical properties, and are attracting attention as a material for forming semiconductor devices.
  • sheath length control various studies are ongoing, such as formation position control and chirality control.
  • electromagnetic wave components for electronic devices As specific applications, electromagnetic wave components for electronic devices, components, cooling bump materials for high-performance electronic devices such as VLSI, and wiring via structure members for semiconductor devices have attracted attention. Yes.
  • CNTs have extremely high thermal conductivity, making use of their properties to grow CNTs on a semiconductor process substrate at high density, and this is mounted on a part of a conductive circuit or an electronic device mounted on the process substrate
  • Applications such as bonding structure from (semiconductor device) and exhaust heat path for device heat generation (so-called “bump structure”) can be considered.
  • FIG. 5 shows an example of a structure (see, for example, Non-Patent Document 1) used as a cooling bump material for a high-performance electronic device using such CNTs.
  • a cooling bump structure for a high-performance electronic device has a catalyst metal supporting film (eg, TiN film) on an electrode 52 on a substrate (aluminum nitride (A1N, alumina, etc.) 51).
  • catalytic metal film (Co etc.) both are indicated by the number 53 together) are deposited by sputtering etc.
  • CNT54 by thermal CVD method (thermochemical vapor deposition method) using elemental gas (CH, CH, etc.)
  • a conductive material metal such as Cu, A1, etc.
  • plating wet treatment
  • the electronic device can be thermocompression-bonded (desirably about 250 to 450 ° C.) on the substrate to produce a highly thermally conductive electronic device.
  • FIG. 1 shows an example of a wiring via structure using the above-mentioned CNT (for example, see Patent Document 1 and Non-Patent Document 2).
  • a via structure has a base layer 2 and a Cu wiring layer 3 provided on a substrate 1, and a barrier film (Ta film or the like) that prevents Cu diffusion on the Cu wiring layer 3. 4)
  • barrier film Ta film or the like
  • catalytic metal supporting film for example, Ti film
  • catalytic metal film such as Co (or catalyst fine particle layer)
  • Fig. 1 also shows a filled resin 9 for fixing CNT8.
  • Patent Document 1 JP 2002-329723 A (Claims)
  • Non-Patent Document 1 Fujitsu Limited, Fujitsu Laboratories Ltd., “World's First! Utilizing Carbon Nanotubes as a Heat Dissipation Substrate for Semiconductor Chips”, December 5, 2005, [Search August 18, 2006], Internet ⁇ URL: http: ⁇ pr.fojitsu.com/jp/news/2005/12/5.html ⁇
  • Non-patent literature 2 Nibe et al., "Japanese 'Journal' Ob 'Applied' Physics Physics;) ”, 2005, No. 44, p. 1626 Disclosure of the Invention
  • CNTs are produced by conventional production methods ⁇ laser abrasion, chemical vapor deposition (CVD), HiPCO (high-pressure carbon monoxide), etc. ⁇ .
  • the surface properties of CNTs produced by these methods depend on the graphite-like surface molecular structure, that is, the nature of the electronic superconjugated structure in which the benzene rings are connected, and wettability with other materials. Also shows properties like graphite. That is, as-manufactured (eg powdered) molecular surfaces are usually poorly dispersible in any solvent and when treated under specific conditions (eg sonicated with ethanol) The limit was that a dispersed state of several weeks at most could be obtained.
  • the decrease in electrical properties refers to, for example, an increase in specific resistance, a decrease in reliability of maintaining medium- and long-term electrical properties, an increase in specific resistance per weight and a deterioration in electromagnetic shielding performance, and the same reliability.
  • deterioration of mechanical strength refers to a decrease in rigidity, fracture strength, deterioration of their long-term performance, and the like.
  • deterioration of chemical properties refers to deterioration of material properties (for example, hygroscopicity, solvent resistance, oxidation by oxygen in the air) due to the environment.
  • CMP Chemical Mechanical Polishing
  • Xiao ij needs to be removed.
  • the bundle of CNTs is fixed, or it flows into the abrasive and polishing fluid CNT bundles during CMP to prevent contamination inside the CNTs.
  • a bundle of CNTs is used. This insulating material is not sufficiently filled, so the fine volume around the CNT bundle may prevent other substances from entering the CNT bundle.
  • An object of the present invention is to solve the above problems and provide a carbon nanotube-based material having improved affinity when in contact with other materials. Still other objects and advantages of the present invention will become apparent from the following description.
  • a surface-modified carbon nanotube-based material is produced.
  • carbon nanotube materials For carbon nanotube materials,
  • group material including this is provided.
  • a novel carbon nanotube-based material having improved affinity when in contact with other materials can be obtained.
  • novel carbon nanotube-based material having improved affinity when in contact with other materials obtained by the embodiment of the present invention is suitably used for all electronic members such as electronic parts and the like. can do.
  • the surface of the carbon nanotube-based material can be modified.
  • the substance is a substance that can be activated by vacuum ultraviolet rays to generate chemically active species such as radicals, and the carbon nanotube-based material whose surface should be modified is produced by the CVD method.
  • the carbon nanotube-based material whose surface is to be modified is grown on a substrate, and is composed of a conductive substance, an insulating substance, a hydrophilic substance, a lipophilic substance, and a substance having a specific group.
  • the surface-modified carbon nanotube-based material has improved affinity as compared with that before the surface modification when in contact with at least one substance selected from the group, and chemically active such as radicals.
  • Seed force including at least one of a chemically active species such as a radical of an electron-donating group and a chemically active species such as a radical of an electron-withdrawing group;
  • the material capable of modifying the surface of the base material contains oxygen, amines, halogenated alkyls, alcohols, ethers, and a mixture of these, and includes at least one selected material. It is preferable that the substance capable of modifying the surface of the carbon nanotube-based material is diluted with an inert substance that does not modify the surface of the carbon nanotube-based material even when irradiated with the vacuum ultraviolet rays.
  • an electronic member comprising the surface-modified carbon nanotube-based material described above, in particular, a via, a heat dissipation bump, a conductive sheet, an electromagnetic wave sheer material. Sheets, pre-preparers for producing these sheets, and electronic devices comprising the surface-modified carbon nanotube-based material are provided.
  • a novel carbon nanotube material having improved affinity when in contact with other materials can be obtained.
  • Such a material can be suitably used for an electronic device or an electronic member.
  • FIG. 1 is a schematic cross-sectional view of a wiring via structure using CNTs.
  • FIG. 2 is a schematic diagram showing the main part of an apparatus for irradiating VUV and supplying a specific substance according to the present invention.
  • ⁇ 3 Another schematic diagram showing the main part of the apparatus for irradiating VUV and supplying a specific substance according to the present invention.
  • FIG. 5 is a schematic diagram showing an example of an outline of the structure of an electronic device including a high thermal conductive bump, in which a carbon nanotube-based material is applied to a cooling bump material for a high-performance electronic device.
  • Carbon according to the present invention FIG. 5 is a schematic diagram showing an outline of a manufacturing method when a nanotube-based material is applied to a material with high-performance electromagnetic waves.
  • the surface-modified carbon nanotube material according to the present invention is different from the carbon nanotube material in vacuum ultraviolet (VUV).
  • VUV vacuum ultraviolet
  • a substance capable of modifying the surface of the carbon nanotube-based material by combination with the VUV (“substance capable of modifying the surface of the carbon nanotube-based material by combination with VUV”) (Hereinafter also referred to as “specific substances”).
  • this carbon nanotube-based material is modified by irradiating the carbon nanotube-based material with VUV and supplying this specific material. This material is probably activated by VUV. It is thought that this may be due to generation of chemically active species such as radicals that are trapped and the chemical species acting on the surface of the carbon nanotube material.
  • the mechanism is presumed to be as follows (however, the remedy is not related to the essence of the present invention). That is, upon receiving VUV irradiation, the bond of a specific substance floating in the vicinity of the nanotube molecule is cleaved, and active oxygen such as singlet oxygen, Chemical species such as amino radicals, alkyl radicals, and alkoxy radicals are generated. Because these radicals are unstable and highly reactive, they have relatively reactive defects on the graph nanotube sheet of nearby nanotubes (5-membered ring, 7-membered ring, usually called dangling bonds) To a binding state part or the like) to form a covalent bond. Alternatively, it does not directly bond to nanotubes, but chemically active species such as radicals react and recombine, resulting in higher boiling (low volatility) products. This is a mechanism that adsorbs to the surface of nanotube molecules.
  • this substance or a part thereof is adsorbed on the surface of the carbon nanotube material and is chemically active such as radicals by the action of VUV.
  • Other mechanisms may exist, such as acting on the surface of carbon nanotube materials without passing through seeds.
  • the force that is thought to be mainly composed of chemical bonds as the above action is not known. However, these mechanisms and modes of action are not related to the essence of the present invention.
  • Such surface modification specifically includes changes in surface tension, changes in wettability to a specific solvent, and introduction of specific groups (for example, polar groups) onto the surface of a carbon nanotube-based material.
  • specific groups for example, polar groups
  • the surface of the carbon nanotube-based material is modified in any way due to changes in the adhesion with a specific material, the amount of adsorption of a specific substance, etc., or when the modification does not use VUV This can be confirmed by the improvement.
  • the affinity with other substances is improved.
  • VUV since the substance that can generate chemically active species such as radicals by VUV as described above often corresponds to the specific substance, VUV does not depend on the specific change as described above. Substances that can generate chemically active species such as radicals may be considered as specific substances. This is because if a chemically active species such as a radical is generated, This is the force that is the answer that the change is occurring on the surface of the carbon nanotube material.
  • Chemically active species such as radicals include chemically active species such as radicals of electron-donating groups and chemically active species such as radicals of electron-absorbing group I. It is preferable that at least one of these is included.
  • a chemically active species such as a radical is involved, a polar group is introduced into the carbon nanotube material, and the affinity with a polar substance is improved.
  • surface means a surface in a so-called surface modification, and may include not only the outermost surface of a carbon nanotube-based material but also a recessed surface and an inner surface. In the context of the present invention, it is not important where the carbon nanotube-based material is specifically modified! /.
  • any substance force without particular limitation can be selected. Specifically, it is preferable to select according to what kind of surface modification is desired. For example, in order to improve the affinity for polar solvents, we prefer substances that can introduce polar groups onto the surface of carbon nanotube materials. In order to improve the affinity for a solvent having a specific structure, a substance capable of introducing the specific chemical structure or a chemical structure close to it onto the surface of the carbon nanotube material is preferable. It may be possible to adjust the degree of hydrophilicity or lipophilicity of the carbon nanotube-based material by adjusting the type or amount of hydrophilic group or lipophilic group.
  • the carbon nanotube-based material preferably contains at least one substance selected from the group power consisting of oxygen, amines, alkyl halides, alcohols, ethers and mixtures thereof. If these substances are used, the polarity of the surface of the carbon nanotube-based material can be generally improved.
  • the specific substance is supplied to bring the specific substance into contact with the carbon nanotube-based material. This supply is performed in the gas phase.
  • a specific substance as a vapor
  • some vapor pressures are low or difficult to evaporate at normal pressure and room temperature, so this can be avoided by adopting reduced pressure as described below or diluting with an inert substance described later. It may be preferable to entrain the active substance or heat a specific substance.
  • the specific substance itself is not necessarily vaporized. Therefore, spray It may be useful to supply a specific substance in a state of being suspended in another gas. In this case, it is also known that the suspended specific substance may contribute to the modification of the carbon nanotube-based material in the liquid state.
  • the modification characteristics and degree of the carbon nanotube-based material are affected by the type of the specific substance supplied. For example, when many hydroxyl groups are introduced on the surface of a carbon nanotube material, the affinity for alcohol solvents such as ethanol and ethylene glycol (diol) glycerin (triol) is improved. In addition, when an amino group is introduced or an amino group or a compound containing an amino group is adsorbed, the affinity for a solvent having an amino group functional group such as dimethylformamide (DMF) tends to be improved. .
  • DMF dimethylformamide
  • UV-A in the range of more than 315 nm and less than 400 nm
  • UV-B in the wavelength of more than 280 nm and in the range of 315 nm and less
  • UV-C in the wavelength of more than 200 nm and in the range of 280 nm and less
  • the carbon nanotube-based material in the present invention generally has high surface stability (chemical stability, etc.) of UV-A to UV-C. It was found that the surface could not be sufficiently modified by UV irradiation, but it was possible when VUV was combined with the above specific substances.
  • the means for obtaining VUV is not particularly limited.
  • a Xe excimer UV lamp having a narrow width and a center wavelength of 172 nm can be preferably exemplified.
  • an Xe-sealed excimer UV lamp showing a wavelength distribution of about 160 to 200 nm is preferable, but not necessarily limited thereto.
  • the bond energy of organic compound bonds is directly related to the wavelength of the VUV, so if you want to eliminate specific bond breaks, the wavelength range of the VUV can be narrowly limited depending on the purpose. It is also useful to do.
  • VUV There are no restrictions on the output of VUV, and commercially available ones with an output of about several tens of mWZcm 2 can be preferably used. However, if there is no problem with cooling or placement of equipment that can generate VUV (excimer UV lamp, etc.), use a higher power equipment, or place multiple UV lamps in close proximity, and the actual irradiation dose per surface. Increasing production can lead to improved productivity.
  • VUV is generally used in a vacuum or under reduced pressure, but in the present invention, it can be used under normal pressure. That is, the VUV irradiation in the present invention is performed on a single-bonn nanotube-based material placed in a reduced pressure or normal pressure atmosphere.
  • the inert substance is not particularly limited. However, since the environment of the present invention is a gas phase, a gas substance or a volatile substance is generally appropriate. An inert gas such as neon or argon or nitrogen gas is preferred.
  • VUV As the distance between the carbon nanotube material to be irradiated and the VUV irradiation source, VUV is easily absorbed, and therefore a smaller one is often preferable. Force depending on the type and concentration (or vapor pressure or partial pressure) of the substance existing between the carbon nanotube material and the VUV irradiation source Generally, this distance is, for example, 0.1 ⁇ : LOOmm Good. Furthermore, in many cases, a 0.2 mm force of about several centimeters is preferable.
  • VUV irradiation There is no particular limitation on the method of VUV irradiation. It may not be necessary to supply the specific substance at the same time.
  • the surface modification of the carbon nanotube-based material occurs only in the part where the VUV is directly irradiated. For example, when the lifetime of chemically active species such as the generated radicals is long, it is considered that surface modification can also occur at the site when directly irradiated to VUV. Therefore, if the carbon nanotube-based material is irradiated to the VUV as a whole and as a result surface-modified, it meets the gist of the present invention, but in general, individual carbon nanotube-based materials are directly applied to the VUV as much as possible. It is preferable to be irradiated. In this sense, it is preferable that the carbon nanotube-based material rises from the substrate and is aligned in the aligned direction or is dispersed on the substrate, but is not limited to this.
  • the "carbon nanotube-based material” in the present invention means CNT or a material in which CNT is modified in some sense.
  • CNT which is a carbon tube having a nano-sized cross section (for example, a cross-sectional diameter of 0.3 to 10 nm).
  • the length it is possible to preferably illustrate a length of several tens of nanometers to several millimeters. /.
  • CNTs have a band structure that satisfies the conditions for exhibiting metallic properties and a band structure that satisfies the conditions for exhibiting semiconducting (semimetallic) properties.
  • the CNTs according to the present invention it is possible to use a deviation between those showing metallic properties and those showing semiconductor properties!
  • the "carbon nanotube-based material” in the present invention has a so-called peapod structure in which CNTs are packed with nanostructures other than nanotubes that exhibit metallic properties as a whole, such as fullerene encapsulating metal. These nanotubes are also included. That is, “modification” in the above includes such cases.
  • a peapod-shaped nanotube including such another nanostructure By using a peapod-shaped nanotube including such another nanostructure, it may be possible to enhance, for example, electrical conductivity characteristics or mechanical strength of a via.
  • electrical conductivity characteristics or mechanical strength of a via For example, in the case of CNTs containing metal-encapsulated fullerenes, it is known from first-principles calculations that the charge of the encapsulated metal appears outside the fullerene and further outside the nanotube, which leads to the electrical conductivity of the via. Characteristics can be improved.
  • arc discharge and laser ablation have been used to form CNTs and other carbon nanotube-based materials.
  • plasma CVD plasma chemical vapor deposition
  • thermal CVD are often used. Yes.
  • the CVD method is expected to be applied to the manufacture of integrated circuits because nanotubes can be formed directly on the substrate.
  • the present invention is not limited to the CNT production method used.
  • the carbon nanotube-based material according to the present invention is often preferably produced by CVD in this way. In that case, a carbon nanotube-based material is generated on the substrate.
  • the formation of the carbon nanotube-based material on the substrate itself is not an essential requirement of the present invention, but when the carbon nanotube-based material is formed on the substrate, direct irradiation with VUV is easy as described above. In addition, it is often preferred because of its good adhesion to the substrate.
  • the material for forming this substrate is not particularly limited and can be appropriately selected. However, in order to obtain conductivity, the material is electrically conductive. In order to obtain thermal conductivity, it is preferable to select one having good thermal conductivity.
  • an apparatus for irradiating a carbon nanotube material with VUV and supplying a specific substance there is no particular limitation on an apparatus for irradiating a carbon nanotube material with VUV and supplying a specific substance.
  • a device having the structure shown in FIGS. In FIG. 2 there are a supply path 23 of a gas 22 obtained by diluting a specific substance with an inert substance under a VUV source 21, and a blowout opening 24 for the specific substance.
  • VUV source 21 is cooled by cooling medium 25.
  • a substrate 27 having a bundle 26 of CNTs arranged vertically below the outlet 24 moves to the left force right of the page.
  • FIG. 3 is the same as FIG.
  • the vertically aligned CNT bundle 26 can be realized, for example, as a CNT bundle grown in a via hole.
  • the arrows with solid lines in Figs. 2 and 3 indicate the flow of gas 22 and cooling medium 25 in which a specific substance is diluted with an inert substance, and the arrows with wavy lines indicate VUV irradiation.
  • a novel carbon nanotube material having improved affinity when in contact with other materials can be obtained.
  • Such a material can be suitably used for an electronic member.
  • “Improvement of affinity” means improvement of surface tension, contact with other substances, improvement of adhesiveness, increase of adsorption amount, interlayer between other substances. It means the reduction of foreign matter (moisture, etc.) and cavities (micro space).
  • the “other substances” are at least one substance selected from the group power that is also a conductive substance, an insulating substance, a hydrophilic substance, a lipophilic substance and a substance having a specific group. It is preferable.
  • carbon nanotube-based materials as components for electronic devices, etc., it is possible to improve electrical connection, thermal connection, mechanical coupling, wetting to solvents and adhesives, etc.
  • Examples of such conductive materials include copper, aluminum, and other electrically conductive materials such as metals used in electronic wiring sections
  • insulating materials include SOG, TEOS (tetra Insulating resin for sealing semiconductors such as ethoxysilane, polyimide resin, etc., or the so-called “Low-k resin” (NCS, SiLK, MSQ, etc.), or fluorine-based resin such as PFA, FEP, Teflon (registered trademark), that is, electrically insulating materials suitable for fixing CNTs in general
  • hydrophilic substances include water, ethanol, Alcohol solvents such as methanol, phenol, dioxanes, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, etc.
  • lipophilic substances include petroleum ether, n-hexane, Paraffinic solvents such as chlorohexane, aromatic solvents such as benzene, toluene, xylene and talesol, or THF
  • the substance having a specific group is basically a substance (preferably a low-viscosity gas or liquid) containing a functional group that is contained in a large amount in the above-mentioned insulating substance, hydrophilic substance, and lipophilic substance.
  • Typical examples include the following: — OH, —COOH, —NH 2, 1 NR (where R is an aliphatic, aromatic alkyl group or its
  • —CO—, —C 0, substances having at least one of an imide bond and an ether bond, that is, alcohols and phenols, carboxylic acids, amines, ketones and quinones, and the like.
  • the carbon nanotube-based material according to the present invention is used for any application where the carbon nanotube-based material is used or is likely to be used, such as an electric product, an electronic product, and a mechanical product, according to needs. Although it may be used, in view of the excellent electrical and thermal properties of carbon nanotube-based materials, it can be used especially for medical, aerospace, or portable electronic devices that can generate electromagnetic waves (cell phones, Including portable electronic device terminals such as personal computers) or electronic devices (for example, semiconductor devices and printed wiring boards) The semiconductor integrated circuit device can be suitably used.
  • conductive materials used for electronic devices with high performance, light weight and little deterioration in long-term use
  • electromagnetic wave-resistant members sheets, etc.
  • electronic devices with less problems such as peeling or disconnection It can be expected to realize electronic devices.
  • Examples of such electronic members include heat dissipation bumps for mounting electronic devices and wiring vias for electronic devices.
  • the present invention is not limited to the above-described electronic component, electronic device element, or the like.
  • Electronic devices that generate electromagnetic waves including electronic devices, medical devices, mobile phones, personal computers, etc., conductive sheets, high-frequency electromagnetic shielding materials for electronic terminals, and precursors for producing these components (so-called pre-preparers) Include).
  • FIG. 4 is a cross-sectional view schematically showing a semiconductor integrated circuit device using the carbon nanotube material according to the present invention for an LSI wiring via.
  • a plurality of elements such as the transistor 42 are formed on the silicon substrate 41, and a plurality of insulating layers (interlayer insulating films) 43a to 43f are formed so as to cover them.
  • a wiring layer is located across the insulating layer, and the wiring 45 of a predetermined wiring layer is connected to the wiring 45 of another layer by a via 46 formed through the insulating layer.
  • Reference numeral 47 denotes a contact connected to the wiring 45 that connects the elements.
  • the uppermost wiring layer is covered with a protective layer 48.
  • the carbon nanotube-based material according to the present invention is applied to the via 46, and the nanotube is dissolved in this by improving the wettability with respect to a specific solvent.
  • the upper end of the carbon nanotube-based material grown in the beer is improved by improving the permeability of CNTs around the CNT and, as a result, closing the cavity around the CNT and fixing the CNT bundle. Can be satisfactorily scraped off by CMP, and therefore a good electrical connection with the wiring part can be realized.
  • FIG. 5 is a schematic diagram showing an example of an outline of the structure of an electronic device including a high thermal conductive bump in which a carbon nanotube-based material is applied to a cooling bump material of a high-performance electronic device.
  • the carbon nanotube material according to the present invention can be applied to a cooling bump material for a high-performance electronic device.
  • the gas with oxygen diluted with nitrogen or the gas diluted with nitrogen with oxygen and a small amount of water is applied to the substrate with CNTs in Fig. 5.
  • VUV treatment is performed, followed by heat treatment and electrical conductive material (metal such as Cu, A1, etc.) on the CNT part of the substrate with CNT treated with metal (wet treatment).
  • a so-called CNT hybrid 'bump structure with sufficient penetration into the space between them can be produced.
  • an electronic device can be thermocompression-bonded (preferably about 250 to 450 ° C) on this treated substrate to produce a highly thermally conductive electronic device using CNT bumps infiltrated with metal or the like. .
  • FIG. 6 is a schematic diagram showing an electromagnetic shielding sheet or pre-preder according to the present invention. That is, by dispersing CNTs on a resin sheet and attaching this sheet to another resin sheet, an electromagnetic shielding sheet or its pre-preda can be obtained.
  • Example 1
  • a Si wafer ⁇ p-type, (100) surface ⁇ with Ni formed by sputtering to a thickness of 25 nm was used as a substrate.
  • thermal CVD using acetylene gas as a raw material at 650 ° C, Multiwall carbon nanotubes were grown to a length of about 1.5 m. When the surface density of the nanotube was measured, it was about 5 ⁇ 10 11 pieces Zcm 2 .
  • Example 2 A specific substance similar to that in Example 1 was used, and a sample obtained by generating single wall carbon nanotubes on a Si wafer ⁇ p-type, (100) plane ⁇ by an arc discharge method was used.
  • Example 1 The same treatment as in Example 1 was performed. However, the processing time was set to 10% of Example 1.
  • a cylindrical hole pattern with a diameter of 0.5 m and a depth of 1 m was formed on the Si substrate, a Ti thin film lOnm was formed by sputtering on the entire wafer surface including the bottom surface, and Ni fine particles with an average particle diameter lOnm were formed. Scattered over the entire surface of the wafer including the bottom, multi-wall carbon nanotubes with a length of 1500 nm were grown to the top of the holes by thermal CVD. When the surface density of the nanotube was measured, it was about 3 ⁇ 10 11 pieces Zcm 2 .
  • Example 1 The same apparatus as in Example 1 was used for this sample, the same specific material as in Example 1 was supplied in the same manner as in Example 1, and VUV was irradiated in the same manner as in Example 1.
  • the nanotubes are improved in hydrophilicity, and are expected to show a good affinity for substances such as hydrophilic solvents and adhesives.
  • the electrical resistance between the upper surface of the CNT bundled with ammonia water and the lower (substrate) surface in this example was 2 ⁇ (ohms), which was an extremely low value.
  • the wiring via structure of the transistor was formed in a simulated manner (when the surface density of the nanotube was measured, it was about 5 X 10 11 pieces Zcm 2 ). Nanotube carbonylation and hydroxylation were performed. However, as the reactive substance, oxygen diluted with N and HO were used in place of triethylamine.
  • a cylindrical hole pattern with a diameter of 0.5 m and a depth of lOOOnm was formed on the Si substrate, a Ti thin film lOnm was formed by sputtering on the entire wafer surface including the bottom surface, and Co fine particles with an average particle diameter of 7 nm.
  • Co fine particles with an average particle diameter of 7 nm was sprayed over the entire surface of the wafer including the bottom, and multiwall carbon nanotubes with a length of 1500 nm were grown above the holes by CVD, and then this sample was subjected to a carbolysis using the same method as in Example 1. -Fluorination and hydroxylation were performed.
  • a gas containing 0.5% by volume of oxygen, 0.1% by volume of H 2 O and the balance of nitrogen is included in the specific substance.
  • the gas was used as a gas and the flow rate of this gas was set at 5 L / min.
  • Example 1 The same apparatus as in Example 1 was used, and VUV was irradiated in the same manner as in Example 1. The reaction time was 15% of Example 1.
  • Ethanol, MIBK (methyl isobutyl ketone) and a 1: 1 (volume ratio) mixture of these were added dropwise to the treated samples, and after 10 minutes, they were thoroughly dried on a hot plate and scanned.
  • SEM electron microscope
  • the ratio of bundled CNTs was large in the order of ethanol> 1 to 1 mixture> MIBK (methyl isobutyl ketone). This is the same as the case of the ammonia water described above. It is thought that. That is, it was shown that the wettability with respect to these media was good.
  • the same treatment was applied to the nanotube sample in the untreated hole pattern, only a part of the nanotubes showed bundle defects.
  • a multi-wall carbon nano tube manufactured by the same method as in Example 4 (when the surface density of the nanotube was measured, it was about 5 X 10 11 Zcm 2 ).
  • VUV treatment was performed in exactly the same manner as in Example 4, taking 30% of the time of Example 1, and then immersed in an aqueous solution of Cu plating seed for 10 minutes. When this was observed with an optical microscope, SEM (scanning electron microscope), TEM (transmission electron microscope), and EDX, most of the CNTs were bundled and a large amount of Cu fine particles adhered to the surface. It was.
  • the CNT layer is bonded inside to form a planar or other shaped member.
  • resin can also be applied to a modified adhesive method.
  • CNT can be sprayed on a general pre-prepared material with low shape retention and VUV treatment can be performed!
  • the resin can be applied to anything including thermosetting.
  • the molding method can be applied to a variety of things if it does not flow during the CNT solidification process.
  • the present invention can be suitably used in a field (for example, the electronic equipment field) in which a novel carbon nanotube material having improved affinity when in contact with other materials can be used.

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Abstract

L'invention concerne de nouveaux matériaux à base de nanotubes de carbone, lesdits matériaux étant obtenus par un procédé comprenant l'exposition d'un matériau à base de nanotubes de carbone à des rayons ultraviolets sous vide et l'introduction d'une substance capable de modifier la surface du matériau en combinaison avec les rayons ultraviolets sous vide. L'affinité des nouveaux matériaux à base de nanotubes de carbone est améliorée lors de leur mise en contact avec d'autres matériaux.
PCT/JP2006/316834 2006-08-28 2006-08-28 Matériaux à base de nanotubes de carbone, procédé de production et dispositif et composants électroniques WO2008026237A1 (fr)

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PCT/JP2007/000825 WO2008026304A1 (fr) 2006-08-28 2007-07-31 Nanomatériau carboné, son procédé de fabrication, élément électronique et dispositif électronique

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JP2014187161A (ja) * 2013-03-22 2014-10-02 Toshiba Corp 半導体装置及びその製造方法
CN105441711A (zh) * 2015-12-28 2016-03-30 哈尔滨工业大学 一种三维结构CNTs增强Cu基复合材料的制备方法

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JP2009282865A (ja) * 2008-05-24 2009-12-03 Kuraray Co Ltd タッチパネル用透明電極基板、及びタッチパネル
WO2010122635A1 (fr) * 2009-04-21 2010-10-28 富士通株式会社 Procédé de traitement d'un matériau constitué de feuilles de graphène et procédé de fabrication d'un dispositif électronique
KR101736462B1 (ko) * 2009-09-21 2017-05-16 한화테크윈 주식회사 그래핀의 제조 방법
JP2012036040A (ja) * 2010-08-06 2012-02-23 Fujitsu Ltd グラフェンシート系材料の形成方法およびグラフェンシート系材料
US8476510B2 (en) * 2010-11-03 2013-07-02 Massachusetts Institute Of Technology Compositions comprising and methods for forming functionalized carbon-based nanostructures
CN102796991B (zh) * 2011-05-27 2014-08-20 清华大学 石墨烯碳纳米管复合膜结构的制备方法
JP5510522B2 (ja) * 2012-09-27 2014-06-04 富士通株式会社 グラフェンシート系材料の処理方法
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