JP6536819B2 - Method of forming copper film - Google Patents
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- JP6536819B2 JP6536819B2 JP2015236503A JP2015236503A JP6536819B2 JP 6536819 B2 JP6536819 B2 JP 6536819B2 JP 2015236503 A JP2015236503 A JP 2015236503A JP 2015236503 A JP2015236503 A JP 2015236503A JP 6536819 B2 JP6536819 B2 JP 6536819B2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 54
- 229910052802 copper Inorganic materials 0.000 title claims description 54
- 239000010949 copper Substances 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 68
- 239000002041 carbon nanotube Substances 0.000 claims description 65
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 65
- 239000000758 substrate Substances 0.000 claims description 28
- 125000003277 amino group Chemical group 0.000 claims description 24
- 238000009713 electroplating Methods 0.000 claims description 19
- 238000007747 plating Methods 0.000 claims description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 13
- 229910001431 copper ion Inorganic materials 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000009832 plasma treatment Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 238000001237 Raman spectrum Methods 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- -1 polyoxypropylene Polymers 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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Description
本発明は、電解メッキ処理により、基材の表面に、カーボンナノチューブを含有した銅皮膜を成膜する銅皮膜の成膜方法に関する。 The present invention relates to a film forming method of a copper film in which a copper film containing carbon nanotubes is formed on the surface of a substrate by electrolytic plating.
従来から、硫酸銅などの銅イオンを含むメッキ液を用いて、電解メッキ処理により、基材の表面に銅皮膜を成膜する技術が利用されている。銅皮膜の熱伝導性および電気伝導性を高めるべく、成膜時に銅皮膜にカーボンナノチューブを含有させることがある。 BACKGROUND ART Conventionally, a technology of forming a copper film on the surface of a substrate by electrolytic plating using a plating solution containing copper ions such as copper sulfate has been used. In order to enhance the thermal conductivity and electrical conductivity of the copper film, carbon nanotubes may be included in the copper film during film formation.
このような技術として、例えば、特許文献１には、カーボンナノチューブと銅イオンを含有したメッキ液を用いて、電解メッキ処理により、基材の表面に銅皮膜を成膜する技術が提案されている。電解メッキ処理に用いられるメッキ液には、カーボンナノチューブの凝集を抑えるべく、ポリアクリル酸などの分散剤が添加されている。 As such a technique, for example, Patent Document 1 proposes a technique of forming a copper film on the surface of a substrate by electrolytic plating using a plating solution containing carbon nanotubes and copper ions. . A dispersing agent such as polyacrylic acid is added to the plating solution used for the electrolytic plating process in order to suppress the aggregation of carbon nanotubes.
しかしながら、成膜される銅皮膜の熱伝導性および電気伝導性をより高めるべく、結晶性の高いカーボンナノチューブを用いた場合、このようなカーボンチューブの分子間力は高いため、溶液中で凝集し易い。このため、ポリアクリル酸などの分散剤をメッキ液に添加したとしても、メッキ液にカーボンナノチューブを均一に分散させることができない。 However, when carbon nanotubes with high crystallinity are used to further improve the thermal conductivity and electrical conductivity of the deposited copper film, the intermolecular force of such a carbon tube is high, and therefore, aggregation occurs in the solution. easy. Therefore, even if a dispersant such as polyacrylic acid is added to the plating solution, carbon nanotubes can not be uniformly dispersed in the plating solution.
これにより、凝集したカーボンナノチューブが、電解メッキ処理の際に、基材の表面への均一な電場形成を阻害するため、カーボンナノチューブを含有した銅皮膜を、効率良く成膜することが難い。 As a result, the aggregated carbon nanotubes inhibit the formation of a uniform electric field on the surface of the substrate during the electrolytic plating process, so it is difficult to efficiently form a copper film containing carbon nanotubes.
本発明は、このような点を鑑みてなされたものであり、その目的とするところは、電解メッキ処理により、高結晶性を有したカーボンナノチューブが均一に分散された銅皮膜を、効率良く成膜することができる銅皮膜の成膜方法を提供することにある。 The present invention has been made in view of these points, and the object of the present invention is to efficiently form a copper film in which carbon nanotubes having high crystallinity are uniformly dispersed by electrolytic plating. An object of the present invention is to provide a method of forming a copper film which can be formed into a film.
前記課題を鑑みて、本発明に係る銅皮膜の成膜方法は、電解メッキ処理により、基材の表面に、カーボンナノチューブを含有した銅皮膜を成膜する銅皮膜の成膜方法であって、前記カーボンナノチューブとして、ラマンスペクトルにおいて、１３５０ｃｍ−１付近に現れるＤバンドの面積に対する１５９０ｃｍ−１付近に現れるＧバンドの面積の比（Ｇ／Ｄ比）が０．１以上であるカーボンナノチューブを、アミノ基を含む官能基付与剤を含有した溶液に混合する工程と、前記カーボンナノチューブを混合した溶液をプラズマ処理することにより、前記カーボンナノチューブの表面に、前記官能基付与剤のアミノ基を付与する工程と、前記アミノ基が付与されたカーボンナノチューブを含む溶液に、銅イオンを添加する工程と、前記電解メッキ処理により、前記銅イオンが添加された溶液をメッキ液として、前記基材の表面に前記銅皮膜を成膜する工程と、を含むことを特徴とする。 In view of the above problems, the method for forming a copper film according to the present invention is a method for forming a copper film in which a copper film containing carbon nanotubes is formed on the surface of a substrate by electrolytic plating. as the carbon nanotube, in the Raman spectrum, the carbon nanotube ratio of the area of the G band appearing near 1590 cm -1 (G / D ratio) is 0.1 or more to the area of D band appearing in the vicinity of 1350 cm -1, amino Adding an amino group of the functional group imparting agent to the surface of the carbon nanotube by subjecting the solution containing the functional group imparting agent containing the group to a solution containing the functional group imparting agent and plasma treating the solution containing the carbon nanotube mixed And adding a copper ion to a solution containing the carbon nanotube to which the amino group is attached, and The key process, a solution in which the copper ions are added as a plating solution, characterized in that it comprises a, a step of forming the copper film on the surface of the substrate.
本発明によれば、アミノ基を含む官能基付与剤を含有した溶液に、プラズマ処理を行うことにより、官能基を付与し難い高結晶性を有した（Ｇ／Ｄ比が０．１以上の）カーボンナノチューブであっても、その表面にアミノ基を付与（修飾）することができる。 According to the present invention, by performing plasma treatment on a solution containing a functional group imparting agent containing an amino group, it has high crystallinity which hardly imparts a functional group (G / D ratio is 0.1 or more Even in the case of carbon nanotubes, amino groups can be provided (modified) on the surface thereof.
これにより、アミノ基は、水やアルコールなどを溶媒とした溶液に対して親和性が高い基であるので、カーボンナノチューブを溶液中に均一に分散させることができる。このような結果、溶液中に均一に分散されたカーボンナノチューブにより、電解メッキ処理の際に、基材の表面への均一な電場形成が阻害され難い。 Thereby, since the amino group is a group having high affinity to a solution using water, alcohol or the like as a solvent, carbon nanotubes can be uniformly dispersed in the solution. As a result, due to the carbon nanotubes uniformly dispersed in the solution, the formation of a uniform electric field on the surface of the substrate is less likely to be inhibited during the electrolytic plating process.
さらに、メッキ液中のアミノ基がプラス（＋）に帯電するため、アミノ基が付与されたカーボンナノチューブは、メッキ液中に分散した状態で、電解メッキ処理の際にメッキ液中の銅イオンとともに、陰極である基材の表面に移動する。これにより、基材の表面で銅イオンが銅に還元されて、銅皮膜が成膜されるとともに、銅皮膜にカーボンナノチューブを均一に分散させることができる。 Furthermore, since the amino group in the plating solution is positively charged (+), the carbon nanotube to which the amino group is added is dispersed in the plating solution, and together with the copper ion in the plating solution in the electrolytic plating treatment. Move to the surface of the substrate which is the cathode. As a result, copper ions are reduced to copper on the surface of the substrate to form a copper film, and carbon nanotubes can be uniformly dispersed in the copper film.
このようにして、凝集したカーボンナノチューブに起因して、銅皮膜の成長が妨げられることを回避することができる。また、成膜された銅皮膜には、高結晶性を有したカーボンナノチューブが均一に分散しているので、電気伝導性および熱伝導性の高い均質な銅皮膜を得ることができる。 In this way, it is possible to avoid that the growth of the copper film is prevented due to the aggregated carbon nanotubes. Further, since carbon nanotubes having high crystallinity are uniformly dispersed in the deposited copper film, it is possible to obtain a homogeneous copper film having high electrical conductivity and thermal conductivity.
以下に本発明の実施形態に係る銅皮膜の成膜方法を、図１を参照しながら説明する。
図１は、本発明の実施形態に係る銅皮膜の成膜方法を説明するためのフロー図である。本実施形態では、金属製の基材の表面に、カーボンナノチューブを含有した銅皮膜を成膜する。
Hereinafter, a method for forming a copper film according to an embodiment of the present invention will be described with reference to FIG.
FIG. 1 is a flow chart for explaining a film forming method of a copper film according to an embodiment of the present invention. In the present embodiment, a copper film containing carbon nanotubes is formed on the surface of a metal base.
まず、図１のステップＳ１１に示すように、イオン交換水などの水、またはアルコール等の溶媒を準備し、これに、アミノ基を含む官能基付与剤を添加した溶液を作製する。官能基付与剤とは、後述するカーボンナノチューブの表面にアミノ基を付与する添加剤である。 First, as shown in step S11 of FIG. 1, a solvent such as water such as ion-exchanged water or an alcohol is prepared, and a solution to which a functional group imparting agent containing an amino group is added is prepared. The functional group imparting agent is an additive which imparts an amino group to the surface of a carbon nanotube described later.
例えば、アミノ基を含む官能基付与剤として、トリエチレンテトラミン、メタキシリレンジアミン、ジエチレントリアミン、イソホロンジアミン、ノルボルナンジアミン、ポリオキシプロピレンジアミン、またはポリオキシエチレンジアミンなどのポリアミンを挙げることができる。プラズマ処理により、カーボンナノチューブの表面にアミノ基を付与することができるのであれば、特に、その種類は限定されるものではない。 For example, as a functional group imparting agent containing an amino group, polyamines such as triethylenetetramine, metaxylylenediamine, diethylenetriamine, isophorone diamine, norbornane diamine, polyoxypropylene diamine, or polyoxyethylene diamine can be mentioned. The type is not particularly limited as long as an amino group can be provided to the surface of the carbon nanotube by plasma treatment.
次に、ステップＳ１２に進み、作製した溶液にカーボンナノチューブを混合する。ここで、カーボンナノチューブは、ラマンスペクトルにおいて、１３５０ｃｍ−１付近に現れるＤバンドの面積に対する１５９０ｃｍ−１付近に現れるＧバンドの面積の比（Ｇ／Ｄ比）が０．１以上の条件を満たすカーボンナノチューブである。また、カーボンナノチューブの直径は、２０ｎｍ未満であることが好ましい。 Next, in step S12, carbon nanotubes are mixed with the prepared solution. Here, carbon nanotubes, in the Raman spectrum, the ratio of the area of the G band appearing near 1590 cm -1 to the area of D band appearing in the vicinity of 1350 cm -1 (G / D ratio) is 0.1 or more conditions are satisfied carbon It is a nanotube. In addition, the diameter of the carbon nanotube is preferably less than 20 nm.
ここで、ラマン分光法によって得られるカーボンナノチューブのラマンスペクトル８００〜２０００ｃｍ−１の領域において、このスペクトルの両端を直線で結んだ線をベースラインとし、１３５０ｃｍ−１付近に現れる吸収ピークをＤバンドとし、１５９０ｃｍ−１付近に現れる吸収ピークをＧバンドとする。ここで、カーボンナノチューブのＧバンド及びＤバンドの吸収ピークの面積は、これら２つの吸収ピークをローレンツ関数を用いてカーブフィッティングすることで波形分離を行った後、各バンドの分離した波形とベースラインとで囲まれた面積を算出することにより、求めることができる。Ｄバンドの面積に対するＧバンドの面積の比（Ｇ／Ｄ比）は、求めたＧバンドの吸収ピークの面積を、Ｄバンドの吸収ピークの面積で除することにより、得ることができる。 Here, in a region of a Raman spectrum 800 to 2000 cm −1 of a carbon nanotube obtained by Raman spectroscopy, a line connecting both ends of this spectrum by a straight line is used as a base line, and an absorption peak appearing in the vicinity of 1350 cm −1 is used as a D band. The absorption peak appearing in the vicinity of 1590 cm −1 is taken as a G band. Here, the areas of the absorption peaks of the G and D bands of carbon nanotubes are subjected to waveform separation by curve fitting these two absorption peaks using the Lorentz function, and then the separated waveform and baseline of each band It can be determined by calculating the area enclosed by and. The ratio of the G band area to the D band area (G / D ratio) can be obtained by dividing the area of the determined G band absorption peak by the area of the D band absorption peak.
本実施形態では、上述したカーボンナノチューブは、そのＧ／Ｄ比が０．１以上であるため、カーボンナノチューブのなかでも、結晶性の高いカーボンナノチューブである。例えば、このようなＧ／Ｄ比の範囲を満たすカーボンナノチューブは、アセチレン等の炭化水素ガスを用いた化学気相成長法で製造する際に、たとえば、炭化水素ガスの濃度、種類等を変更することにより、得ることができる。 In the present embodiment, since the G / D ratio of the above-described carbon nanotube is 0.1 or more, the carbon nanotube is a carbon nanotube having high crystallinity among carbon nanotubes. For example, a carbon nanotube satisfying such a range of G / D ratio changes, for example, the concentration, type, etc. of hydrocarbon gas when it is produced by a chemical vapor deposition method using a hydrocarbon gas such as acetylene. Can be obtained by
次に、ステップＳ１３に進み、液中プラズマ発生装置を用いて、溶液をプラズマ処理（ソリューションプラズマ処理）し、カーボンナノチューブにアミノ基を付与する。液中プラズマ発生装置を用いれば、溶液中で形成された気泡内にプラズマを発生させ、液中に活性種を浸透拡散させることができる。これにより、カーボンナノチューブの表面にアミノ基を付与することができる。例えば、液中プラズマ発生装置に、特開２００７−２０７５４０号公報に開示されるような装置を用いてもよい。 Next, proceeding to step S13, the solution is subjected to plasma treatment (solution plasma treatment) using an in-liquid plasma generator to impart amino groups to the carbon nanotubes. With the in-liquid plasma generator, plasma can be generated in bubbles formed in the solution, and active species can be permeated and diffused in the liquid. Thereby, an amino group can be provided to the surface of the carbon nanotube. For example, an apparatus as disclosed in JP-A-2007-207540 may be used as the in-liquid plasma generation apparatus.
本実施形態では、このプラズマ処理において、溶液中に一対の電極を浸漬し、溶液を冷却しながら、一対の電極間にパルス電圧を印加し、溶液中でプラズマを発生させる。これにより、溶液の蒸発を抑制しつつ、カーボンナノチューブの表面に、官能基付与剤のアミノ基を付与することができる。 In this embodiment, in this plasma treatment, a pair of electrodes is immersed in a solution, and while the solution is cooled, a pulse voltage is applied between the pair of electrodes to generate plasma in the solution. Thereby, the amino group of a functional group imparting agent can be provided to the surface of a carbon nanotube, controlling evaporation of a solution.
このようにプラズマ処理を行うことにより、官能基を付与し難い高結晶性を有した（Ｇ／Ｄ比が０．１以上の）カーボンナノチューブであっても、その表面にアミノ基を付与（修飾）することができる。これにより、アミノ基は、水やアルコールなど溶媒に対して親和性が高い（水の場合は親水性が高い）基であるので、カーボンナノチューブを溶液中に均一に分散させることができる。特に、直径が２０ｎｍ未満のカーボンナノチューブは、凝集し易いところ、このようなカーボンナノチューブであっても、これを溶液中に均一に分散させることができる。 By performing plasma treatment in this way, even if the carbon nanotube (G / D ratio is 0.1 or more) having high crystallinity to which a functional group is hard to be imparted is imparted with an amino group on its surface (modification )can do. As a result, since the amino group is a group having high affinity to a solvent such as water or alcohol (high hydrophilicity in the case of water), carbon nanotubes can be uniformly dispersed in a solution. In particular, carbon nanotubes having a diameter of less than 20 nm are easily aggregated, and even such carbon nanotubes can be uniformly dispersed in a solution.
次に、ステップＳ１４に進み、アミノ基が付与されたカーボンナノチューブを含む溶液に銅イオンを添加する。具体的には、この溶液に銅イオンとして電離するたとえば硫酸銅等を添加する。次に、ステップＳ１５に進む。 Next, proceeding to step S14, copper ions are added to the solution containing carbon nanotubes to which amino groups have been attached. Specifically, for example, copper sulfate or the like which is ionized as copper ions is added to this solution. Next, the process proceeds to step S15.
次に、ステップＳ１５では、電解メッキ処理を行い、基材の表面に金属皮膜を成膜する。具体的には、基材を陰極として、陽極と基材との間に、上述した銅イオンが添加された溶液をメッキ液として介在させ、陽極と基材との間に電圧を印加することにより、基材の表面に銅皮膜を成膜する。基材として、例えば、銅、鉄、アルミニウム等の金属材料などを挙げることができる。 Next, in step S15, electrolytic plating is performed to form a metal film on the surface of the substrate. Specifically, the substrate is used as a cathode, and the above-described solution to which copper ions are added is interposed as a plating solution between the anode and the substrate, and a voltage is applied between the anode and the substrate. , Forming a copper film on the surface of the substrate. As a base material, metal materials, such as copper, iron, aluminum, etc. can be mentioned, for example.
このようにして、ステップＳ１３で、溶液中にカーボンナノチューブが均一に分散されたので、ステップＳ１５の電解メッキ処理の際に、基材の表面への均一な電場形成が阻害され難い。また、メッキ液中のアミノ基がプラス（＋）に帯電するため、アミノ基が付与されたカーボンナノチューブは、メッキ液中に分散した状態で、電解メッキ処理の際にメッキ液中の銅イオンとともに、陰極である基材の表面に移動する。 Thus, in step S13, the carbon nanotubes are uniformly dispersed in the solution, so that the formation of a uniform electric field on the surface of the substrate is unlikely to be inhibited during the electrolytic plating process of step S15. In addition, since the amino group in the plating solution is positively charged (+), the carbon nanotube to which the amino group is added is dispersed with the plating solution, and along with the copper ions in the plating solution, in the electrolytic plating process. Move to the surface of the substrate which is the cathode.
これにより、基材の表面で銅イオンが銅に還元され、銅皮膜が形成されるとともに、銅皮膜にカーボンナノチューブを均一に分散させることができる。このようにして、銅皮膜の成膜時に、凝集したカーボンナノチューブに起因して、銅皮膜の成長が妨げられることを回避することができる。 As a result, copper ions are reduced to copper on the surface of the substrate to form a copper film, and carbon nanotubes can be uniformly dispersed in the copper film. In this way, it is possible to avoid that the growth of the copper film is hindered due to the aggregated carbon nanotubes during the film formation of the copper film.
最後に、ステップＳ１６で、銅皮膜を形成した基材を超音波で洗浄する。基材の表面に成膜された銅皮膜には、高結晶性を有したカーボンナノチューブが均一に分散しているので、電気伝導性および熱伝導性の高い均質な銅皮膜を得ることができる。このような点から、銅皮膜の成膜は、例えば放熱部材の表面に行うことが好ましい。 Finally, in step S16, the substrate on which the copper film has been formed is ultrasonically cleaned. Since a carbon nanotube having high crystallinity is uniformly dispersed in the copper film formed on the surface of the substrate, a homogeneous copper film having high electric conductivity and thermal conductivity can be obtained. From such a point, it is preferable to form the copper film on, for example, the surface of the heat radiation member.
以下に本発明に係る実施例を説明する。 Examples according to the present invention will be described below.
（実施例）
まず、溶媒としてイオン交換水を準備し、アミノ基を含む官能基付与剤としてトリエチレンテトラミン（関東化学（株）社製）を、０．２５Ｍになるように添加した。次に、直径１０ｎｍ、Ｇ／Ｄ比１．２のカーボンナノチューブ（宇部興産（株）社製ＡＭＣ）を準備し、これを、トリエチレンテトラミンを添加した溶液に、混合した。
(Example)
First, ion-exchanged water was prepared as a solvent, and triethylenetetramine (manufactured by Kanto Chemical Co., Ltd.) as an amino group-containing functional group imparting agent was added to a concentration of 0.25M. Next, a carbon nanotube with a diameter of 10 nm and a G / D ratio of 1.2 (AMC manufactured by Ube Industries, Ltd.) was prepared, and this was mixed with a solution to which triethylenetetramine was added.
次に、カーボンナノチューブを混合した溶液に、液中プラズマ発生装置として、バリア放電型ソリューションズプラズマ発生装置（アドバンテック東洋（株）社製：型式：ＳＰＡＤ３０３０）を用いて、ソリューションプラズマ処理を施した。具体的には、この溶液に、電流３Ａ（電圧７０Ｖ程度）、周波数２０ｋＨｚ、パルス幅２μ秒、２時間の条件で、プラズマ処理を行った。 Next, solution plasma processing was performed to the solution which mixed carbon nanotube, using a barrier discharge type solutions plasma generator (Advantec Toyo Co., Ltd. make: model: SPAD3030) as an in-liquid plasma generator. Specifically, this solution was subjected to plasma treatment under the conditions of current 3 A (about 70 V voltage), frequency 20 kHz, pulse width 2 μ seconds, and 2 hours.
プラズマ処理を行った溶液の一部を抽出し、カーボンナノチューブを抽出後、Ｘ線光電子分光分析装置（アルバック・ファイ（株）社製、型式：Ｑｕａｎｔｕｍ２０００）を用いて、カーボンナノチューブにアミノ基が装飾されているかを調べた。その結果、カーボンナノチューブは、１．４原子％の窒素が含有されていることがわかり、カーボンナノチューブにアミノ基が修飾されていることを確認できた。 After extracting a part of the solution subjected to plasma treatment and extracting carbon nanotubes, amino groups are decorated on the carbon nanotubes using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Inc., model: Quantum 2000) I checked if it was. As a result, it was found that the carbon nanotube contained nitrogen of 1.4 atomic%, and it was confirmed that the carbon nanotube was modified with an amino group.
次に、プラズマ処理を行った溶液に、硫酸銅５水和物（ナカライテスク（株）社製）を、１Ｍとなるように添加し、基材の表面に、電解メッキ処理を施した。基材には、無酸素銅板を用いた。電解メッキ処理は、定電流法で、電流密度を１２０Ａ／ｍ２で２０分の条件で行った。これにより、基材の表面に、カーボンナノチューブが分散した銅皮膜を成膜した。 Next, copper sulfate pentahydrate (manufactured by Nacalai Tesque, Inc.) was added to the solution subjected to plasma treatment so as to be 1 M, and the surface of the substrate was subjected to electrolytic plating treatment. An oxygen free copper plate was used as the substrate. The electrolytic plating treatment was performed by a constant current method under the conditions of a current density of 120 A / m 2 for 20 minutes. Thus, a copper film in which carbon nanotubes were dispersed was formed on the surface of the substrate.
その後、超音波洗浄機（アズワン（株）社製、型番：ＵＳ−１Ｒ）で、銅皮膜が形成された基材を超音波洗浄し、送風乾燥した。得られた銅皮膜の重量を測定した。この結果を表１に示す。さらに、高周波燃焼−赤外線吸収法（炭素・硫黄分析装置、ＬＥＣＯ社製、型番：ＣＳ８４４型）で調べた結果、銅皮膜全体に対するカーボンナノチューブの含有率は、０．５質量％であった。 Thereafter, the substrate on which the copper film was formed was subjected to ultrasonic cleaning using a ultrasonic cleaning machine (manufactured by As One Co., Ltd., model number: US-1R), and was air-dried. The weight of the obtained copper film was measured. The results are shown in Table 1. Furthermore, as a result of investigating with a high frequency combustion-infrared absorption method (a carbon and sulfur analyzer, LECO company make, model number: CS844 type), the content rate of the carbon nanotube with respect to the whole copper film was 0.5 mass%.
さらに、基材に形成された銅皮膜の断面を、クロスセクションポリッシャー（日本電子（株）社製）を用いて抽出し、走査型電子顕微鏡（日立ハイテクノロジーズ（株）社製、型番：Ｓ４８００）を用いて、ＳＥＭ観察を行った。この結果を、図２に示す。なお、図２に示す、黒色部分がカーボンナノチューブであり、それ以外が銅である。 Furthermore, the cross section of the copper film formed on the substrate is extracted using a cross section polisher (manufactured by Nippon Denshi Co., Ltd.), and a scanning electron microscope (manufactured by Hitachi High-Technologies Co., Ltd., model number: S4800) SEM observation was performed using The results are shown in FIG. In addition, the black part shown in FIG. 2 is a carbon nanotube, and others are copper.
（比較例）
実施例と同じように、基材の表面に銅皮膜を成膜した。実施例１と相違する点は、イオン交換水に、トリエチレンテトラミン（官能基付与剤）の代わりに、ポリアクリル酸ナトリウム（分散剤）を添加し、（ソリューション）プラズマ処理を行っていない点である。実施例と同じ電解メッキ処理の条件で成膜した銅皮膜の重量を測定した。この結果を表１に示す。
(Comparative example)
A copper film was formed on the surface of the substrate as in the example. The difference from Example 1 is that sodium polyacrylate (dispersant) is added to ion-exchanged water instead of triethylenetetramine (functional group imparting agent) and (solution) plasma treatment is not performed. is there. The weight of the copper film formed under the same conditions of electrolytic plating as in the example was measured. The results are shown in Table 1.
＜結果および考察＞
実施例の銅皮膜の重量は、比較例のものに比べて大きく、実施例では、電解メッキ処理の電流効率は、９５％に相当し、効率良く銅皮膜が成膜されたといえる。また、図２に示すように、銅皮膜には、カーボンナノチューブが均一に分散していることが確認できた。
<Results and Discussion>
The weight of the copper film of the example is larger than that of the comparative example. In the example, the current efficiency of the electrolytic plating process corresponds to 95%, and it can be said that the copper film was formed efficiently. Moreover, as shown in FIG. 2, it has confirmed that the carbon nanotube was disperse | distributed uniformly in the copper film.
実施例では、溶液中にカーボンナノチューブが均一分散されているので、電解メッキ処理の際に、基材の表面への均一な電場形成が阻害されず、銅皮膜の成長が妨げられなかったことにより、銅皮膜の重量が比較例のものに比べて大きかったと考えられる。 In the example, since the carbon nanotubes are uniformly dispersed in the solution, the formation of the uniform electric field on the surface of the substrate is not inhibited during the electrolytic plating process, and the growth of the copper film is not impeded. The weight of the copper film is considered to be larger than that of the comparative example.
以上、本発明の実施の形態を詳述してきたが、具体的な構成はこの実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲における設計変更があっても、それらは本発明に含まれるものである。 As mentioned above, although the embodiment of the present invention has been described in detail, the specific configuration is not limited to this embodiment, and even if there is a design change without departing from the scope of the present invention, they are It is included in the invention.
Claims (1)
前記カーボンナノチューブとして、ラマンスペクトルにおいて、１３５０ｃｍ−１付近に現れるＤバンドの面積に対する１５９０ｃｍ−１付近に現れるＧバンドの面積の比（Ｇ／Ｄ比）が０．１以上であるカーボンナノチューブを、アミノ基を含む官能基付与剤を含有した溶液に混合する工程と、
前記カーボンナノチューブを混合した溶液をプラズマ処理することにより、前記カーボンナノチューブの表面に、前記官能基付与剤のアミノ基を付与する工程と、
前記アミノ基が付与されたカーボンナノチューブを含む溶液に、銅イオンを添加する工程と、
前記電解メッキ処理により、前記銅イオンが添加された溶液をメッキ液として、前記基材の表面に前記銅皮膜を成膜する工程と、を含むことを特徴とする銅皮膜の成膜方法。 A method of forming a copper film, wherein a copper film containing carbon nanotubes is formed on the surface of a substrate by electrolytic plating,
As the carbon nanotube, in the Raman spectrum, the carbon nanotube ratio of the area of the G band appearing near 1590 cm -1 (G / D ratio) is 0.1 or more to the area of D band appearing in the vicinity of 1350 cm -1, amino Mixing into a solution containing a functionalizing agent comprising a group;
Applying the amino group of the functional group-imparting agent to the surface of the carbon nanotube by subjecting the solution in which the carbon nanotube is mixed to plasma treatment;
Adding a copper ion to the solution containing the carbon nanotube to which the amino group is attached;
Forming a film of the copper film on the surface of the substrate by using a solution to which the copper ions are added by the electrolytic plating process as a plating solution.
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