JP5857830B2 - Carbon nanotube sheet and method for producing the same - Google Patents
Carbon nanotube sheet and method for producing the same Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73253—Bump and layer connectors
Description
本発明は、カーボンナノチューブシート及びその製造方法に関するものであり、例えば、半導体チップなどの発熱源とヒートスプレッダなど放熱部との間を機械的、熱的に接続するカーボンナノチューブシート及びその製造方法に関する。 The present invention relates to a carbon nanotube sheet and a method for manufacturing the same, for example, a carbon nanotube sheet for mechanically and thermally connecting a heat source such as a semiconductor chip and a heat radiating portion such as a heat spreader, and a method for manufacturing the carbon nanotube sheet.
サーバーやパーソナルコンピュータの中央処理装置（ＣＰＵ：ＣｅｎｔｒａｌＰｒｏｃｅｓｓｉｎｇ Ｕｎｉｔ）などに用いられる電子部品には、半導体素子から発する熱を効率よく放熱することが求められる。 Electronic components used in a central processing unit (CPU: Central Processing Unit) of a server or a personal computer are required to efficiently dissipate heat generated from a semiconductor element.
そのため、半導体素子を実装する際には、半導体素子の直上に設けられたインジウムシートなどの熱伝導性シートを介して、銅などの高い熱伝導度を有する材料のヒートスプレッダが配置された構造を採用している。 Therefore, when mounting a semiconductor element, a structure in which a heat spreader made of a material having a high thermal conductivity such as copper is arranged through a heat conductive sheet such as an indium sheet provided immediately above the semiconductor element is adopted. doing.
しかしながら、近年におけるレアメタルの大幅な需要増加によりインジウム価格は高騰しており、インジウムよりも安価な代替材料が待望されている。また、物性的に見てもインジウムの熱伝導度（５０Ｗ／ｍ・Ｋ）は高いとはいえず、半導体素子から生じた熱をより効率的に放熱させるために更に高い熱伝導度を有する材料が望まれている。 However, the price of indium has soared due to a significant increase in demand for rare metals in recent years, and an alternative material that is cheaper than indium is expected. In addition, in terms of physical properties, the thermal conductivity (50 W / m · K) of indium is not high, and a material having a higher thermal conductivity in order to dissipate the heat generated from the semiconductor element more efficiently. Is desired.
このような背景から、インジウムよりも高い熱伝導度を有する材料として、カーボンナノチューブに代表される炭素元素の線状構造体が注目されている。カーボンナノチューブは、非常に高い熱伝導度（１５００Ｗ／ｍ・Ｋ）を有するだけでなく、柔軟性や耐熱性に優れた材料であり、放熱材料として高いポテンシャルを有している。 Against this background, a carbon element linear structure typified by carbon nanotubes has attracted attention as a material having higher thermal conductivity than indium. Carbon nanotubes not only have a very high thermal conductivity (1500 W / m · K), but also have excellent flexibility and heat resistance, and have a high potential as a heat dissipation material.
カーボンナノチューブ（ＣＮＴ）を用いた熱伝導シートとしては、樹脂中にカーボンナノチューブを分散した熱伝導シートや、基板上に配向成長したカーボンナノチューブ束を樹脂等によって埋め込んだ熱伝導シートが提案されている。 As a heat conductive sheet using carbon nanotubes (CNT), a heat conductive sheet in which carbon nanotubes are dispersed in a resin, or a heat conductive sheet in which a bundle of carbon nanotubes that are oriented and grown on a substrate is embedded with a resin or the like has been proposed. .
しかし、ＣＮＴ樹脂シートのシート化工程において、基板上に垂直配向したＣＮＴに熱可塑性樹脂を含浸させる際に、熱可塑性樹脂が基板まで到達してしまうと、熱可塑性樹脂を固化させた時に、基板と樹脂シートが接着してしまう。その結果、ＣＮＴ樹脂シートの剥離が困難になってしまうという問題がある。 However, when the thermoplastic resin reaches the substrate when the CNT vertically aligned on the substrate is impregnated with the thermoplastic resin in the sheet forming step of the CNT resin sheet, the substrate is not solidified when the thermoplastic resin is solidified. And the resin sheet will adhere. As a result, there is a problem that peeling of the CNT resin sheet becomes difficult.
このような問題を回避するために、樹脂を半分まで含浸させてから剥離しても良いが、これは、熱可塑性樹脂の融解温度と時間によって制御しているため技術的にも難しい上、工数的にもあまり有効な技術ではない。 In order to avoid such problems, the resin may be impregnated up to half and then peeled off, but this is technically difficult because it is controlled by the melting temperature and time of the thermoplastic resin, and the man-hours It is not very effective technology.
また、いずれの製造工程を採用しても、共通して言える一番の問題点は、ＣＮＴシートを基板から剥離する際に、ＣＮＴが切れて基板側に残ってしまうというケースが多く見受けられるという点である。これは熱伝導に寄与するＣＮＴが減少することを意味しており、ＣＮＴシート作製の際、大きな課題となっている。 In addition, regardless of which manufacturing process is adopted, the most common problem that can be said in common is that when the CNT sheet is peeled from the substrate, there are many cases where the CNT is cut and remains on the substrate side. Is a point. This means that CNTs contributing to heat conduction are reduced, which is a major issue when producing CNT sheets.
また、現状のＣＮＴ樹脂シートのもう１つの問題点としては、ＣＮＴ樹脂シートと発熱体との間及びＣＮＴ樹脂シートと放熱体との間の接触熱抵抗が高いという点が挙げられる。 Another problem of the current CNT resin sheet is that the contact thermal resistance between the CNT resin sheet and the heat generator and between the CNT resin sheet and the heat radiator is high.
したがって、カーボンナノチューブシート及びその製造方法において、基板からの剥離容易性と高熱伝導性を両立することを目的とする。 Accordingly, it is an object of the present invention to achieve both ease of peeling from the substrate and high thermal conductivity in the carbon nanotube sheet and the manufacturing method thereof.
開示する一観点からは、導電性の第１下地層と、前記第１下地層上に設けた酸化物からなる第２下地層と、前記第２下地層の表面に設けた触媒微粒子と、前記触媒微粒子を成長核として成長したカーボンナノチューブと、前記カーボンナノチューブの間隙を充填する充填層とを備えたことを特徴とするカーボンナノチューブシートが提供される。 From one aspect to be disclosed, a conductive first underlayer, a second underlayer made of an oxide provided on the first underlayer, catalyst fine particles provided on a surface of the second underlayer, There is provided a carbon nanotube sheet comprising carbon nanotubes grown using catalyst fine particles as growth nuclei and a packed layer filling a gap between the carbon nanotubes.
また、開示する別の観点からは、基板上に前記基板に接する導電性の第１下地層と、前記第１下地層に接する酸化物からなる第２下地層の２層構造の下地層を介して触媒微粒子を形成し、前記触媒微粒子を触媒として前記下地層上に複数のカーボンナノチューブを成長させる工程と、前記複数のカーボンナノチューブの間隙を充填層で充填する工程と、前記充填層を冷却固化する際に、冷却固化時に生じる圧縮歪みを利用して前記第１下地層と前記基板とを剥離する剥離工程とを有することを特徴とするカーボンナノチューブシートの製造方法が提供される。 From another point of view, a conductive first underlayer that is in contact with the substrate and a second underlayer composed of an oxide that is in contact with the first underlayer are provided on a substrate via a two-layer underlayer. Forming catalyst fine particles, using the catalyst fine particles as a catalyst, growing a plurality of carbon nanotubes on the underlayer, filling a gap between the plurality of carbon nanotubes with a filling layer, and cooling and solidifying the filling layer In this case, there is provided a method for producing a carbon nanotube sheet, comprising a peeling step of peeling the first base layer and the substrate using compressive strain generated during cooling and solidification.
開示のカーボンナノチューブシート及びその製造方法によれば、基板からの剥離容易性と高熱伝導性を両立することが可能になる。 According to the disclosed carbon nanotube sheet and the manufacturing method thereof, it is possible to achieve both ease of peeling from the substrate and high thermal conductivity.
ここで、図１を参照して、本発明の実施の形態のカーボンナノチューブシートを説明する。図１は、本発明の実施の形態のカーボンナノチューブシートの説明図であり、図１（ａ）は、基板から剥離前の側面図であり、図１（ｂ）はカーボンナノチューブシートを用いた実装構造を示す断面図である。カーボンナノチューブシート１は、下地層の上に触媒微粒子４を設け、この触媒微粒子４を触媒として成長させた複数のカーボンナノチューブ５の間隙を充填層６で充填したものである。この場合、充填層６の冷却固化時に発生する圧縮歪によりカーボンナノチューブシート１は基板７から自然と剥離する。 Here, with reference to FIG. 1, the carbon nanotube sheet | seat of embodiment of this invention is demonstrated. FIG. 1 is an explanatory view of a carbon nanotube sheet according to an embodiment of the present invention, FIG. 1 (a) is a side view before peeling from the substrate, and FIG. 1 (b) is a mounting using the carbon nanotube sheet. It is sectional drawing which shows a structure. In the carbon nanotube sheet 1, catalyst fine particles 4 are provided on a base layer, and a gap between a plurality of carbon nanotubes 5 grown using the catalyst fine particles 4 as a catalyst is filled with a filling layer 6. In this case, the carbon nanotube sheet 1 naturally peels from the substrate 7 due to the compressive strain generated when the packed layer 6 is cooled and solidified.
この場合の基板７としては、表面にＳｉＯ２膜等の絶縁膜８を設けたシリコン基板、Ａｌ２Ｏ３基板、ＭｇＯ基板或いはガラス基板を用いる。また、下地層は第１下地層２と第２下地層３の２層構造とする。 As the substrate 7 in this case, a silicon substrate, an Al 2 O 3 substrate, an MgO substrate or a glass substrate provided with an insulating film 8 such as a SiO 2 film on the surface is used. The underlayer has a two-layer structure of a first underlayer 2 and a second underlayer 3 .
第１下地層２としては、熱伝導性に優れ且つ酸化膜が形成されづらいＡｕ，Ａｇ或いはＰｔが好適である。また、第２下地層３としては、カーボンナノチューブ５を成長させるためにＳｉＯ２或いはＡｌ２Ｏ３等の酸化物が好適であり、特に、熱伝導性の観点からはＡｌ２Ｏ３が好適である。また、第２下地層３を絶縁物とすることで、発熱体となる半導体ベアチップ等の電子デバイス１１の薄層化に伴って結晶欠陥が発生してもカーボンナノチューブシート１を介して放熱体１４にリーク電流が流れることがない。 As the first underlayer 2, Au, Ag, or Pt, which has excellent thermal conductivity and is difficult to form an oxide film, is preferable. The second underlayer 3 is preferably an oxide such as SiO 2 or Al 2 O 3 for growing the carbon nanotubes 5, and particularly preferably Al 2 O 3 from the viewpoint of thermal conductivity. is there. Further, by using the second underlayer 3 as an insulator, even if crystal defects occur with the thinning of the electronic device 11 such as a semiconductor bare chip serving as a heating element, the heat radiating body 14 is passed through the carbon nanotube sheet 1. There is no leakage current.
この場合の第１下地層２の厚さは、５０ｎｍ〜１００ｎｍ以上とし、第２下地層３の厚さは１ｎｍ〜５０ｎｍとする。また、成膜方法としては、蒸着法、スパッタ法、或いは、ＡＬＤ法等を用いることができる。 In this case, the thickness of the first underlayer 2 is 50 nm to 100 nm or more, and the thickness of the second underlayer 3 is 1 nm to 50 nm. As a film formation method, an evaporation method, a sputtering method, an ALD method, or the like can be used.
触媒微粒子４は、触媒金属膜を形成したのち加熱により微粒子化しても良いし、或いは、微分型静電分級器（ＤＭＡ：ｄｉｆｆｅｒｅｎｔｉａｌｍｏｂｉｌｉｔｙ ａｎａｌｙｚｅｒ）等を用い、予めサイズを制御して作製した金属微粒子を用いても良い。触媒微粒子４の材料としては、Ｆｅ、Ｃｏ、Ｎｉ、Ａｕ、Ａｇ、Ｐｔ又はこれらのうち少なくとも一つの材料を含む合金を用いても良い。 The catalyst fine particles 4 may be formed into fine particles by heating after forming a catalyst metal film, or metal fine particles prepared by controlling the size in advance using a differential electrostatic classifier (DMA) or the like. It may be used. As a material of the catalyst fine particles 4, Fe, Co, Ni, Au, Ag, Pt, or an alloy containing at least one of these materials may be used.
カーボンナノチューブ５は、ホットフィラメントＣＶＤ法、熱ＣＶＤ法或いはリモートプラズマＣＶＤ法などにより形成しても良い。また、成長するカーボンナノチューブは、単層カーボンナノチューブでも良い。また、炭素原料としては、アセチレンのほか、メタン、エチレン等の炭化水素類や、エタノール、メタノール等のアルコール類などを用いても良い。 The carbon nanotube 5 may be formed by a hot filament CVD method, a thermal CVD method, a remote plasma CVD method, or the like. The growing carbon nanotube may be a single-walled carbon nanotube. Moreover, as a carbon raw material, you may use hydrocarbons, such as methane and ethylene, alcohols, such as ethanol and methanol other than acetylene.
カーボンナノチューブの密度は、放熱性の観点から、１×１０１０本／ｃｍ２以上であることが望ましい。カーボンナノチューブ５の長さ、即ち、カーボンナノチューブシート１の厚さは、熱拡散装置の用途によって決まり、特に限定されるものではないが、好ましくは５μｍ〜５００μm程度の値に設定する。 The density of the carbon nanotubes is desirably 1 × 10 10 pieces / cm 2 or more from the viewpoint of heat dissipation. The length of the carbon nanotube 5, that is, the thickness of the carbon nanotube sheet 1 is determined by the application of the thermal diffusion device and is not particularly limited, but is preferably set to a value of about 5 μm to 500 μm.
充填層６としては、加熱により可塑化してカーボンナノチューブ５の間隙に充填が可能な熱可塑性樹脂が好適であり、熱可塑性樹脂としては、例えば、Ｍｉｃｒｏｍｅｌｔ６２３９ホットメルト充填材（ヘンケルジャパン社製品名）を用いることができる。この熱可塑性樹脂が冷却固化する際に収縮により発生する圧縮歪によりカーボンナノチューブシート１が基板７から自然に剥離する。 The filling layer 6 is preferably a thermoplastic resin that can be plasticized by heating and can be filled in the gaps of the carbon nanotubes 5. As the thermoplastic resin, for example, Micromelt 6239 hot melt filler (product name of Henkel Japan) is used. Can be used. The carbon nanotube sheet 1 is naturally peeled from the substrate 7 by the compressive strain generated by the shrinkage when the thermoplastic resin is cooled and solidified.
また、カーボンナノチューブ５の成長側の先端部を金属膜で被覆しても良い。この金属膜としては、熱伝導性に優れたＣｕ、Ｎｉ、Ａｕ、Ｉｎ、或いは、低融点はんだ等を用いることができる。また、金属膜は、単層構造である必要はなく、例えば、ＴｉとＡｕとの積層構造など、２層或いは３層以上の積層構造であっても良い。 Further, the tip of the carbon nanotube 5 on the growth side may be covered with a metal film. As this metal film, Cu, Ni, Au, In, or a low melting point solder excellent in thermal conductivity can be used. In addition, the metal film does not have to have a single layer structure, and may have a laminated structure of two layers or three or more layers such as a laminated structure of Ti and Au.
図１（ｂ）は、カーボンナノチューブシートを用いた実装構造を示す断面図であり、カーボンナノチューブシート１は、発熱部となる電子デバイス１１と放熱体１４との間に配置され、加熱、加圧する。この時、充填層６より、カーボンナノチューブ５の先端を露出させて、カーボンナノチューブ５と放熱体とを熱的に接続すると同時に、下地層を介して、カーボンナノチューブ５と電子デバイス１１とを熱的に接続する。なお、電子デバイス１１がバンプ１２を介して実装基板１３に接続・固定され、また、放熱体１４は接着層15によって実装基板１３に固着される。 FIG. 1B is a cross-sectional view showing a mounting structure using a carbon nanotube sheet. The carbon nanotube sheet 1 is disposed between an electronic device 11 serving as a heat generating portion and a radiator 14 and is heated and pressurized. . At this time, the tips of the carbon nanotubes 5 are exposed from the filling layer 6 to thermally connect the carbon nanotubes 5 and the radiator, and at the same time, the carbon nanotubes 5 and the electronic device 11 are thermally connected to each other through the underlayer. Connect to. The electronic device 11 is connected and fixed to the mounting substrate 13 via the bumps 12, and the heat radiator 14 is fixed to the mounting substrate 13 with the adhesive layer 15.
このように、本発明の実施の形態においては、充填層の冷却・固化時に発生する圧縮歪を利用しているので、充填層の充填工程における温度や時間による制御も必要なく、カーボンナノチューブシート１を基板７から容易に剥離することができる。 As described above, in the embodiment of the present invention, since the compressive strain generated when the packed bed is cooled and solidified is used, it is not necessary to control the temperature and time in the filling process of the packed bed, and the carbon nanotube sheet 1 Can be easily peeled off from the substrate 7.
また、カーボンナノチューブシート１を剥離した後の基板７には、充填層となる樹脂やカーボンナノチューブ５が残らないので、基板７を再利用することができ、コスト面でのメリットもある。 Moreover, since the resin and carbon nanotube 5 which become a filling layer do not remain in the board | substrate 7 after peeling the carbon nanotube sheet | seat 1, the board | substrate 7 can be reused and there exists a merit in terms of cost.
次に、図２乃至図４を参照して、本発明の実施例１のカーボンナノチューブシートの製造工程を説明する。まず、図２（ａ）に示すように、表面に３００ｎｍのＳｉＯ２膜２２を形成したシリコン基板２１を用意する。 Next, with reference to FIG. 2 thru | or FIG. 4, the manufacturing process of the carbon nanotube sheet | seat of Example 1 of this invention is demonstrated. First, as shown in FIG. 2A, a silicon substrate 21 having a 300 nm SiO 2 film 22 formed on the surface is prepared.
次いで、図２（ｂ）に示すように、蒸着法を用いてＳｉＯ２膜２２上に、第１下地層となる厚さが１００ｎｍのＡｕ膜２３を堆積させる。次いで、図３（ｃ）に示すように、スパッタ法を用いて厚さが１０ｎｍの第２下地層となるＡｌ２Ｏ３膜２４を堆積させる。 Next, as shown in FIG. 2B, an Au film 23 having a thickness of 100 nm serving as a first underlayer is deposited on the SiO 2 film 22 by vapor deposition. Next, as shown in FIG. 3C, an Al 2 O 3 film 24 serving as a second underlayer having a thickness of 10 nm is deposited by sputtering.
次いで、図２（ｄ）に示すように、スパッタ法を用いてＡｌ２Ｏ３膜２４上にカーボンナノチューブ成長工程において触媒となる厚さが２．５ｎｍのＦｅ膜２５を成膜する。次いで、図２（ｅ）に示すように、ホットフィラメントＣＶＤ法の初期過程でＦｅ膜２５を微粒子化してＦｅ微粒子２６を形成する。 Next, as shown in FIG. 2D, an Fe film 25 having a thickness of 2.5 nm serving as a catalyst in the carbon nanotube growth step is formed on the Al 2 O 3 film 24 by sputtering. Next, as shown in FIG. 2E, the Fe film 25 is made fine particles in the initial process of the hot filament CVD method to form Fe fine particles 26.
引き続いて、図３（ｆ）に示すようにＦｅ微粒子２６を成長核としてカーボンナノチューブ２７を成長させる。カーボンナノチューブ２７の成長条件は、例えば、原料ガスとしてアセチレン・アルゴンの混合ガス（分圧比１：９）を用い、成膜室内の総ガス圧を１ｋＰａ、ホットフィラメント温度を１０００℃、成長時間を２０分とする。これにより、層数が３〜６層（平均４層程度）、直径が４〜８ｎｍ（平均６ｎｍ）、長さが８０μｍ（成長レート：４μｍ／ｍｉｎ）の多層カーボンナノチューブが成長する。 Subsequently, as shown in FIG. 3F, carbon nanotubes 27 are grown using Fe fine particles 26 as growth nuclei. The growth conditions of the carbon nanotube 27 include, for example, a mixed gas of acetylene and argon (partial pressure ratio 1: 9) as a source gas, a total gas pressure in the film formation chamber of 1 kPa, a hot filament temperature of 1000 ° C., and a growth time of 20 Minutes. As a result, multi-walled carbon nanotubes having 3 to 6 layers (average of about 4 layers), a diameter of 4 to 8 nm (average of 6 nm), and a length of 80 μm (growth rate: 4 μm / min) are grown.
次いで、図３（ｇ）に示すように、熱可塑性樹脂からなる樹脂シート２８をカーボンナノチューブ２７上に載置する。熱可塑性樹脂としては、Ｍｉｃｒｏｍｅｌｔ６２３９ホットメルト充填材（ヘンケルジャパン社製商品名、融解温度：１３５〜１４５℃、融解時粘度：５．５〜８．５Ｐａ・ｓ＠２２５℃）を用いる。 Next, as shown in FIG. 3G, a resin sheet 28 made of a thermoplastic resin is placed on the carbon nanotubes 27. As the thermoplastic resin, Micromelt 6239 hot melt filler (trade name, manufactured by Henkel Japan, melting temperature: 135 to 145 ° C., viscosity at melting: 5.5 to 8.5 Pa · s @ 225 ° C.) is used.
次いで、図３（ｈ）に示すように、２２５℃で溶融させて、Ａｌ２Ｏ３膜２４に達するまで完全に樹脂層２９で充填する。 Next, as shown in FIG. 3 (h), it is melted at 225 ° C. and completely filled with the resin layer 29 until it reaches the Al 2 O 3 film 24.
次いで、図４（ｉ）に示すように、樹脂層２９を冷却固化させる工程において圧縮歪が発生して、端部において剥離が発生する。次いで、図４（ｊ）に示すように、剥離が発生した部分から機械的に引き剥がす。図４（ｋ）は、このようにして基板から引き離したカーボンナノチューブシートの概念的側面を示している。 Next, as shown in FIG. 4I, compressive strain is generated in the step of cooling and solidifying the resin layer 29, and peeling occurs at the end. Next, as shown in FIG. 4 (j), it is mechanically peeled off from the portion where peeling has occurred. FIG. 4 (k) shows a conceptual aspect of the carbon nanotube sheet thus separated from the substrate.
このカーボンナノチューブシートをヒートスプレッダとして用いる場合には、上記の図１（ｂ）に示したように、カーボンナノチューブシートを発熱体である半導体チップと放熱体との間に配置し、加熱しながら加圧する。このような加熱・加圧により、樹脂層２９よりカーボンナノチューブ２７の先端を露出させ、放熱体と熱的に接続させる。 When this carbon nanotube sheet is used as a heat spreader, as shown in FIG. 1B, the carbon nanotube sheet is disposed between a semiconductor chip that is a heating element and a radiator, and is pressurized while being heated. . By such heating and pressurization, the tips of the carbon nanotubes 27 are exposed from the resin layer 29 and are thermally connected to the radiator.
一方、発熱体とは下地層であるＡｌ２Ｏ３膜２４及びＡｕ膜２３を介して熱的に接続される。この場合、Ａｌ２Ｏ３膜２４は熱伝導性に優れているので、発熱体からの発熱をカーボンナノチューブ２７を介して効率的に放熱体に伝達することができる。 On the other hand, the heating element is thermally connected through the Al 2 O 3 film 24 and the Au film 23 which are the underlying layers. In this case, since the Al 2 O 3 film 24 is excellent in thermal conductivity, the heat generated from the heat generator can be efficiently transmitted to the heat radiator via the carbon nanotubes 27.
また、Ａｌ２Ｏ３膜２４は優れた絶縁体であるので、放熱体との間を完全に電気的に絶縁することができ、発熱体が半導体ベアチップである場合、薄層化により非常に薄くなっても、欠陥等を介してリーク電流が放熱体に流れることはない。 Further, since the Al 2 O 3 film 24 is an excellent insulator, it can be completely electrically insulated from the heat radiating body, and when the heating element is a semiconductor bare chip, it is very thin by thinning. Even in this case, the leakage current does not flow to the heat radiating body through the defect or the like.
このように、本発明の実施例１においては、自発的な剥離が発生する下地構造を採用しているので、温度や時間による制御も必要なく、カーボンナノチューブが抜け落ちすることなくカーボンナノチューブシートを基板から容易に剥離することができる。 As described above, in Example 1 of the present invention, since the base structure in which the spontaneous peeling occurs is adopted, it is not necessary to control by temperature and time, and the carbon nanotube sheet is used as a substrate without dropping the carbon nanotube. Can be easily peeled off.
また、剥離した後の基板には、樹脂やＣＮＴが残らないので、基板を再利用することができ、カーボンナノチューブシートの製造コストを低減することができるとともに、廃棄物の発生量を大幅に低減することができる。 In addition, since the resin and CNT do not remain on the substrate after peeling, the substrate can be reused, the manufacturing cost of the carbon nanotube sheet can be reduced, and the amount of waste generated is greatly reduced. can do.
次に、図５乃至図７を参照して、本発明の実施例２のカーボンナノチューブシートの製造工程を説明する。まず、実施例１と同様に、図５（ａ）に示すように、表面に３００ｎｍのＳｉＯ２膜２２を形成したシリコン基板２１を用意する。 Next, with reference to FIG. 5 thru | or FIG. 7, the manufacturing process of the carbon nanotube sheet | seat of Example 2 of this invention is demonstrated. First, as in Example 1, as shown in FIG. 5A, a silicon substrate 21 having a 300 nm SiO 2 film 22 formed on the surface is prepared.
次いで、図５（ｂ）に示すように、スパッタ法、蒸着法或いは、ＡＬＤ法を用いてＳｉＯ２膜２２上に、第１下地層となる厚さが１００ｎｍのＡｕ膜２３を堆積させる。次いで、図５（ｃ）に示すように、スパッタ法を用いて厚さが１０ｎｍの第２下地層となるＡｌ２Ｏ３膜２４を堆積させる。 Next, as shown in FIG. 5B, an Au film 23 having a thickness of 100 nm serving as a first underlayer is deposited on the SiO 2 film 22 by using a sputtering method, a vapor deposition method, or an ALD method. Next, as shown in FIG. 5C, an Al 2 O 3 film 24 serving as a second underlayer having a thickness of 10 nm is deposited by sputtering.
次いで、図５（ｄ）に示すように、スパッタ法を用いてＡｌ２Ｏ３膜２４上にカーボンナノチューブ成長工程において触媒となる厚さが２．５ｎｍのＦｅ膜２５を成膜する。次いで、図５（ｅ）に示すように、ホットフィラメントＣＶＤ法の初期過程でＦｅ膜２５を微粒子化してＦｅ微粒子２６を形成する。 Next, as shown in FIG. 5D, an Fe film 25 having a thickness of 2.5 nm serving as a catalyst in the carbon nanotube growth step is formed on the Al 2 O 3 film 24 by sputtering. Next, as shown in FIG. 5E, the Fe film 25 is atomized in the initial process of the hot filament CVD method to form Fe particles 26.
引き続いて、図６（ｆ）に示すようにＦｅ微粒子２６を成長核としてカーボンナノチューブ２７を成長させる。カーボンナノチューブ２７の成長条件は、例えば、原料ガスとしてアセチレン・アルゴンの混合ガス（分圧比１：９）を用い、成膜室内の総ガス圧を１ｋＰａ、ホットフィラメント温度を１０００℃、成長時間を２０分とする。これにより、層数が３〜６層（平均４層程度）、直径が４〜８ｎｍ（平均６ｎｍ）、長さが８０μｍ（成長レート：４μｍ／ｍｉｎ）の多層カーボンナノチューブが成長する。 Subsequently, as shown in FIG. 6F, carbon nanotubes 27 are grown using Fe fine particles 26 as growth nuclei. The growth conditions of the carbon nanotube 27 include, for example, a mixed gas of acetylene and argon (partial pressure ratio 1: 9) as a source gas, a total gas pressure in the film formation chamber of 1 kPa, a hot filament temperature of 1000 ° C., and a growth time of 20 Minutes. As a result, multi-walled carbon nanotubes having 3 to 6 layers (average of about 4 layers), a diameter of 4 to 8 nm (average of 6 nm), and a length of 80 μm (growth rate: 4 μm / min) are grown.
次いで、図６（ｇ）に示すように、蒸着法を用いて、カーボンナノチューブ２７の先端部をＡｕ被覆膜３０で被覆する。次いで、図６（ｈ）に示すように、熱可塑性樹脂からなる樹脂シート２８をカーボンナノチューブ２７上に載置する。熱可塑性樹脂としては、Ｍｉｃｒｏｍｅｌｔ６２３９ホットメルト充填材（ヘンケルジャパン社製商品名、融解温度：１３５〜１４５℃、融解時粘度：５．５〜８．５Ｐａ・ｓ＠２２５℃）を用いる。 Next, as shown in FIG. 6G, the tip of the carbon nanotube 27 is covered with an Au coating film 30 by vapor deposition. Next, as shown in FIG. 6 (h), a resin sheet 28 made of a thermoplastic resin is placed on the carbon nanotubes 27. As the thermoplastic resin, Micromelt 6239 hot melt filler (trade name, manufactured by Henkel Japan, melting temperature: 135 to 145 ° C., viscosity at melting: 5.5 to 8.5 Pa · s @ 225 ° C.) is used.
次いで、図７（ｉ）に示すように、２２５℃で溶融させて、Ａｌ２Ｏ３膜２４に達するまで完全に樹脂層２９で充填する。この時、カーボンナノチューブ２７の先端部はＡｕ被覆膜３０で被覆されているが、図６（ｇ）の拡大図に示すように間隙があるので熱可塑性樹脂はカーボンナノチューブ２７の間隙に入り込んでＡｌ２Ｏ３膜２４に達する。 Next, as shown in FIG. 7 (i), it is melted at 225 ° C. and completely filled with the resin layer 29 until it reaches the Al 2 O 3 film 24. At this time, the tip of the carbon nanotube 27 is covered with the Au coating film 30, but there is a gap as shown in the enlarged view of FIG. 6G, so that the thermoplastic resin enters the gap of the carbon nanotube 27. The Al 2 O 3 film 24 is reached.
次いで、図７（ｊ）に示すように、樹脂層２９を冷却固化させる工程において圧縮歪が発生して、端部において剥離が発生する。次いで、剥離が発生した部分から機械的に引き剥がすことによって、図７（ｋ）に示した基板から引き離したカーボンナノチューブシートが得られる。 Next, as shown in FIG. 7J, compressive strain is generated in the step of cooling and solidifying the resin layer 29, and peeling occurs at the end. Next, the carbon nanotube sheet separated from the substrate shown in FIG. 7 (k) is obtained by mechanically peeling from the part where the peeling occurred.
このように、本発明の実施例２においては、カーボンナノチューブの先端部をＡｕ被覆膜で被覆しているので、放熱体との接触部における熱の広がりを良好にすることができる。その他の作用効果は上記の実施例１と全く同様である。 Thus, in Example 2 of this invention, since the front-end | tip part of a carbon nanotube is coat | covered with Au coating film, the spread of the heat | fever in a contact part with a heat radiator can be made favorable. Other functions and effects are the same as those of the first embodiment.
ここで、実施例１及び実施例２を含む本発明の実施の形態に関して、以下の付記を付す。
（付記１）導電性の第１下地層と、前記第１下地層上に設けた酸化物からなる第２下地層と、前記第２下地層の表面に設けた触媒微粒子と、前記触媒微粒子を成長核として成長したカーボンナノチューブと、前記カーボンナノチューブの間隙を充填する充填層とを備えたことを特徴とするカーボンナノチューブシート。
（付記２）前記カーボンナノチューブの成長側の先端部が金属膜により被覆されていることを特徴とする付記１に記載のカーボンナノチューブシート。
（付記３）基板上に下地層を介して触媒微粒子を形成し、前記触媒微粒子を触媒として前記下地層上に複数のカーボンナノチューブを成長させる工程と、前記複数のカーボンナノチューブの間隙を充填層で充填する工程と、前記充填層を冷却固化する際に、冷却固化時に生じる圧縮歪みを利用して前記第１下地層と前記基板とを剥離する剥離工程とを有することを特徴とするカーボンナノチューブシートの製造方法。
（付記４）前記基板上に下地層を介して触媒微粒子を形成し、前記触媒微粒子を触媒として前記下地層上に複数のカーボンナノチューブを成長させる工程が、前記下地層上に触媒金属膜を形成したのち、ホットフィラメント化学気相成長法により、前記触媒金属膜を微粒子化して触媒微粒子を形成するとともに、前記触媒微粒子を触媒として前記下地層上に複数のカーボンナノチューブを成長させる工程であることを特徴とする付記３に記載のカーボンナノチューブの製造方法。
（付記５）前記複数のカーボンナノチューブの間隙を充填層で充填する工程の前に、前記複数のカーボンナノチューブの成長側の先端部を金属膜で被覆する工程を備えていることを特徴とする付記３または付記４に記載のカーボンナノチューブシートの製造方法。
（付記６）前記下地層が、前記基板に接する導電性の第１下地層と、前記第１下地層に接する酸化物からなる第２下地層の２層構造からなることを特徴とする付記３乃至付記５のいずれか１に記載のカーボンナノチューブシートの製造方法。
（付記７）前記基板が、表面にＳｉＯ２膜を備えたシリコン基板、Ａｌ２Ｏ３基板、ＭｇＯ基板或いはガラス基板のいずれかからなり、前記第１下地層がＡｕ、Ａｇ或いはＰｔのいずれかからなり、前記第２下地層がＡｌ２Ｏ３からなり、前記充填層が熱可塑性樹脂からなることを特徴とする付記３乃至付記６のいずれか１に記載のカーボンナノチューブシートの製造方法。
（付記８）付記１または付記２に記載のカーボンナノチューブシートを発熱部と放熱部との間に配置し、加熱及び加圧することにより、前記熱可塑性樹脂の表面から前記カーボンナノチューブの先端を露出させ、前記カーボンナノチューブを前記発熱部または前記放熱部の一方とを熱的に接続させるとともに、前記下地層と前記発熱部または前記放熱部の他方とを熱的に接続させることを特徴とする熱拡散装置の製造方法。
Here, the following supplementary notes are attached to the embodiments of the present invention including Example 1 and Example 2.
(Supplementary Note 1) A conductive first underlayer, a second underlayer made of an oxide provided on the first underlayer, catalyst fine particles provided on the surface of the second underlayer, and the catalyst fine particles. A carbon nanotube sheet comprising carbon nanotubes grown as growth nuclei and a filling layer filling a gap between the carbon nanotubes.
(Additional remark 2) The carbon nanotube sheet of Additional remark 1 characterized by the front-end | tip part by the side of the growth of the said carbon nanotube being covered with the metal film.
(Supplementary Note 3) Forming catalyst fine particles on a substrate through an underlayer, growing a plurality of carbon nanotubes on the underlayer using the catalyst fine particles as a catalyst, and filling the gaps between the plurality of carbon nanotubes with a filling layer A carbon nanotube sheet comprising: a filling step; and a peeling step of peeling the first base layer and the substrate using a compressive strain generated during cooling and solidification when the filling layer is cooled and solidified. Manufacturing method.
(Appendix 4) The step of forming catalyst fine particles on the substrate through an underlayer, and growing a plurality of carbon nanotubes on the underlayer using the catalyst fine particles as a catalyst forms a catalyst metal film on the underlayer Then, the catalyst metal film is formed into fine particles by hot filament chemical vapor deposition, and a plurality of carbon nanotubes are grown on the underlayer using the catalyst fine particles as a catalyst. The method for producing a carbon nanotube according to Supplementary Note 3, wherein the carbon nanotube is produced.
(Additional remark 5) Before the process of filling the gap | interval of these multiple carbon nanotubes with a filling layer, it has the process of coat | covering the front-end | tip part of the growth side of these multiple carbon nanotubes with a metal film. 3. The method for producing a carbon nanotube sheet according to 3 or appendix 4.
(Supplementary Note 6) The supplementary note 3 is characterized in that the base layer has a two-layer structure of a conductive first base layer in contact with the substrate and a second base layer made of an oxide in contact with the first base layer. The manufacturing method of the carbon nanotube sheet | seat of any one of thru | or appendix 5.
(Supplementary Note 7) The substrate is a silicon substrate with a SiO 2 film on the surface, Al 2 O 3 substrate, made from either MgO substrate or a glass substrate, either the first base layer is Au, the Ag or Pt The method for producing a carbon nanotube sheet according to any one of appendices 3 to 6, wherein the second underlayer is made of Al 2 O 3 and the filling layer is made of a thermoplastic resin.
(Appendix 8) The carbon nanotube sheet according to appendix 1 or appendix 2 is disposed between the heat generating portion and the heat radiating portion, and heated and pressurized to expose the tip of the carbon nanotube from the surface of the thermoplastic resin. The thermal diffusion is characterized in that the carbon nanotube is thermally connected to one of the heat generating part or the heat radiating part and the base layer is thermally connected to the other of the heat generating part or the heat radiating part. Device manufacturing method.
１ カーボンナノチューブシート
２ 第１下地層
３ 第２下地層
４ 触媒微粒子
５ カーボンナノチューブ
６ 充填層
７ 基板
８ 絶縁膜
１１ 電子デバイス
１２ バンプ
１３ 実装基板
１４ 放熱体
１５ 接着層
２１ シリコン基板
２２ ＳｉＯ２膜
２３ Ａｕ膜
２４ Ａｌ２Ｏ３膜
２５ Ｆｅ膜
２６ Ｆｅ微粒子
２７ カーボンナノチューブ
２８ 樹脂シート
２９ 樹脂層
３０ Ａｕ被覆膜
DESCRIPTION OF SYMBOLS 1 Carbon nanotube sheet 2 1st foundation layer 3 2nd foundation layer 4 Catalyst fine particle 5 Carbon nanotube 6 Filling layer 7 Substrate 8 Insulating film 11 Electronic device 12 Bump 13 Mounting substrate 14 Radiator 15 Adhesion layer 21 Silicon substrate 22 SiO 2 film 23 Au film 24 Al 2 O 3 film 25 Fe film 26 Fe fine particle 27 Carbon nanotube 28 Resin sheet 29 Resin layer 30 Au coating film
Claims (6)
前記第１下地層上に設けた酸化物からなる第２下地層と、
前記第２下地層の表面に設けた触媒微粒子と、
前記触媒微粒子を成長核として成長したカーボンナノチューブと、
前記カーボンナノチューブの間隙を充填する充填層と
を備えたことを特徴とするカーボンナノチューブシート。 A conductive first underlayer;
A second underlayer made of an oxide provided on the first underlayer;
Fine catalyst particles provided on the surface of the second underlayer;
Carbon nanotubes grown using the catalyst fine particles as growth nuclei,
A carbon nanotube sheet comprising: a filling layer filling a gap between the carbon nanotubes.
前記複数のカーボンナノチューブの間隙を充填層で充填する工程と、
前記充填層を冷却固化する際に、冷却固化時に生じる圧縮歪みを利用して前記第１下地層と前記基板とを剥離する剥離工程と
を有することを特徴とするカーボンナノチューブシートの製造方法。 Catalyst fine particles are formed on the substrate through a two-layer underlayer of a conductive first underlayer in contact with the substrate and a second underlayer made of an oxide in contact with the first underlayer , and the catalyst fine particles Using a catalyst as a catalyst to grow a plurality of carbon nanotubes on the underlayer,
Filling a gap between the plurality of carbon nanotubes with a filling layer;
A method for producing a carbon nanotube sheet, comprising: a peeling step of peeling the first base layer and the substrate using compressive strain generated during cooling and solidification when the filling layer is cooled and solidified.
前記複数のカーボンナノチューブの成長側の先端部を金属膜で被覆する工程を備えていることを特徴とする請求項４に記載のカーボンナノチューブシートの製造方法。 Before the step of filling the gap between the plurality of carbon nanotubes with a packed bed,
The method for producing a carbon nanotube sheet according to claim 4 , further comprising a step of coating a growth side tip portion of the plurality of carbon nanotubes with a metal film.
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