JP2006307084A - 金属微粒子と無機微粒子とを含む組成物およびその製造方法 - Google Patents
金属微粒子と無機微粒子とを含む組成物およびその製造方法 Download PDFInfo
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- JP2006307084A JP2006307084A JP2005133483A JP2005133483A JP2006307084A JP 2006307084 A JP2006307084 A JP 2006307084A JP 2005133483 A JP2005133483 A JP 2005133483A JP 2005133483 A JP2005133483 A JP 2005133483A JP 2006307084 A JP2006307084 A JP 2006307084A
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- fine particles
- metal
- polysilane
- compound
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- 239000010419 fine particle Substances 0.000 title claims abstract description 253
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 221
- 239000002184 metal Substances 0.000 title claims abstract description 221
- 239000000203 mixture Substances 0.000 title claims abstract description 158
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229920000548 poly(silane) polymer Polymers 0.000 claims abstract description 205
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 121
- 150000001875 compounds Chemical class 0.000 claims abstract description 115
- 239000000178 monomer Substances 0.000 claims abstract description 95
- 239000000758 substrate Substances 0.000 claims abstract description 93
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 79
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- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 44
- 238000007772 electroless plating Methods 0.000 claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 41
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 28
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 238000007747 plating Methods 0.000 claims description 62
- 125000001165 hydrophobic group Chemical group 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
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- 125000003277 amino group Chemical group 0.000 claims description 18
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- 125000001033 ether group Chemical group 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 6
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- 239000002904 solvent Substances 0.000 description 52
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- 239000000243 solution Substances 0.000 description 47
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 34
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- 125000000217 alkyl group Chemical group 0.000 description 33
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- 229910052763 palladium Inorganic materials 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 14
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- 238000006722 reduction reaction Methods 0.000 description 14
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- 239000010931 gold Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
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- 230000018109 developmental process Effects 0.000 description 12
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- 125000000753 cycloalkyl group Chemical group 0.000 description 11
- 229910052737 gold Inorganic materials 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 239000011859 microparticle Substances 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 125000001424 substituent group Chemical group 0.000 description 11
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 10
- 239000003446 ligand Substances 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 125000005372 silanol group Chemical group 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
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- 150000002576 ketones Chemical class 0.000 description 9
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 9
- 230000000737 periodic effect Effects 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 238000004220 aggregation Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
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- 229920005989 resin Polymers 0.000 description 8
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- 229910052703 rhodium Inorganic materials 0.000 description 8
- 229910000077 silane Inorganic materials 0.000 description 8
- 150000003377 silicon compounds Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 7
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- 150000002170 ethers Chemical class 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000002985 plastic film Substances 0.000 description 7
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 125000004434 sulfur atom Chemical group 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
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- 206010034972 Photosensitivity reaction Diseases 0.000 description 6
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- 238000010521 absorption reaction Methods 0.000 description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 150000004292 cyclic ethers Chemical group 0.000 description 6
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 6
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Abstract
【解決手段】 ポリシラン化合物と、還元により前記金属微粒子を生成可能な金属化合物(例えば、貴金属化合物)と、無機微粒子(シリカなど)とで前記組成物を構成する。前記ポリシラン化合物は、ポリシランと、金属化合物及び/又は金属微粒子に対する親和性を有するユニットを含むビニル単量体との共重合体であってもよい。このような組成物を基板に塗布し、活性エネルギー線を作用させてポリシラン化合物を分解させることにより、金属微粒子を生成できる。このような方法は種々の方法に応用でき、例えば、基板に、前記組成物を塗布し、露光して金属微粒子を生成させたのち現像して金属微粒子を含むパターンを形成し、無電解めっき処理することにより無電解めっきパターンを形成することもできる。
【選択図】 なし
Description
ポリシラン化合物は、少なくともポリシラン(又はポリシランユニット、ポリシラン単位)で構成されていればよく、例えば、(a)ポリシランユニットのみで構成された化合物(すなわち、ポリシラン)であってもよく、(b)ポリシランと、このポリシランに結合し、金属化合物及び/又は金属微粒子に対する親和性を有するユニットとで構成されたポリシラン化合物であってもよい。
ポリシラン化合物を構成するポリシラン(ユニット)は、Si−Si結合を有する直鎖状、分岐鎖状、環状、網目状などの種々のポリシラン(以下、単にポリシランということがある)であれば特に制限されない。通常、ポリシランは、下記式(1)〜(3)で表された構造単位のうち少なくとも1つの単位で構成されている場合が多い。
前記式(1)〜(3)において、アルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、t−ブチル、ペンチル基などのC1-14アルキル基(好ましくはC1-10アルキル基、さらに好ましくはC1-6アルキル基)が挙げられる。アルコキシ基としては、メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ、t−ブトキシ、ペンチルオキシ基などのC1-14アルコキシ基(好ましくはC1-10アルコキシ基、さらに好ましくはC1-6アルコキシ基)が挙げられる。アルケニル基としては、ビニル、アリル基などのC2-14アルケニル基(好ましくはC2-10アルケニル基、さらに好ましくはC2-6アルケニル基)が挙げられる。シクロアルキル基としては、シクロペンチル、シクロヘキシル基などのC5-14シクロアルキル基(好ましくはC5-10シクロアルキル基、さらに好ましくはC5-8シクロアルキル基)が挙げられる。シクロアルキルオキシ基としては、シクロヘキシルオキシ基などのC5-14シクロアルキルオキシ基(好ましくはC5-10シクロアルキルオキシ基、さらに好ましくはC5-8シクロアルキルオキシ基)が挙げられる。シクロアルケニル基としては、シクロペンテニル基、シクロヘキセニル基などのC5-14シクロアルケニル基(好ましくはC5-10シクロアルケニル基、さらに好ましくはC5-8シクロアルケニル基)が挙げられる。アリール基としては、フェニル、ナフチル基などのC6-20アリール基(好ましくはC6-15アリール基、さらに好ましくはC6-12アリール基)が挙げられる。アリールオキシ基としては、フェノキシ基、ナフチルオキシ基などのC6-20アリールオキシ基(好ましくはC6-15アリールオキシ基、さらに好ましくはC6-12アリールオキシ基)が挙げられる。アラルキル基としては、ベンジル基、フェネチル基などのC6-20アリール−C1-4アルキル基(好ましくはC6-10アリール−C1-2アルキル基)が挙げられる。アラルキルオキシ基としては、ベンジルオキシ基、フェネチルオキシ基などのC6-20アリール−C1-4アルキルオキシ基(好ましくはC6-10アリール−C1-2アルキルオキシ基)が挙げられる。シリル基としては、シリル基、ジシラニル基、トリシラニル基などのSi1-10シリル基(好ましくはSi1-6シリル基)が例示できる。
親和性を有するユニットを含むポリシラン化合物(b)は、前記のように、ポリシラン(ポリシランユニット)と、このポリシランに結合し、前記金属化合物(又は金属化合物を構成する金属原子)及び/又は金属微粒子(詳細には前記金属化合物が還元されて生成した金属微粒子)に対する親和性を有するユニット(以下、親和性ユニットということがある)とで構成されている。
金属化合物は、還元により前記金属微粒子(又は金属微粒子を構成する金属)を生成可能な化合物(すなわち、金属原子の酸化数が正である金属化合物)であれば特に限定されず、通常、金属塩である場合が多い。
前記組成物は、金属微粒子を効率よく生成するため無機微粒子を含んでいる。また、無機微粒子を含むことにより、基板と還元により生成した金属微粒子との密着性を著しく向上できる。そのため、後述するように金属微粒子を含むパターンに、高い密着性で無電解めっき層(めっきパターン)を形成できる。
[式中、Xは、疎水性基又は疎水性基を含む基を示し、R4は、ヒドロキシル基又はシラノール基に対する反応性基又はこの反応性基を含む基を示す。aは1〜3の整数を示す。]
上記式(2)のXにおいて、疎水性基としては、前記例示の疎水性基(アルキル基、アリール基などの炭化水素基など)などが挙げられる。また、R4で表される反応性基としては、置換されていてもよいヒドロキシル基[ヒドロキシル基、アルコキシ基(例えば、メトキシ基、エトキシ基、プロポキシ基などのC1-6アルコキシ基、好ましくはC1-4アルコキシ基、さらに好ましくはC1-2アルコキシ基)など]、アミノ基、イミノ基、カルボキシル基、エポキシ基、ハロゲン原子(塩素原子など)などが挙げられる。好ましい反応性基には、加水分解縮合性基(アルコキシ基、ハロゲン原子など)が含まれ、特にアルコキシ基が好ましい。
本発明の組成物は、前記のように、金属微粒子(又は金属コロイド)および無機微粒子を含む組成物(以下、金属微粒子を含有する無機微粒子組成物、金属微粒子含有組成物、無機微粒子組成物、組成物などということがある)を得るための組成物として好適に用いることができる。すなわち、本発明では、前記金属微粒子生成用組成物において、前記ポリシラン化合物を分解させて[詳細には、分解によりラジカル(シリルラジカル)を発生させて]、金属微粒子(前記金属化合物に対応する金属微粒子)を生成することができる。なお、生成した金属微粒子は、溶媒との混合物であってもよく、この混合物の形態は、例えば、溶媒(前記例示の溶媒など)に溶解した溶液、又は溶媒(前記例示の溶媒など)に分散した分散液などであってもよい。
なお、基板をめっき液に浸漬する場合、浸漬時間は、例えば、10秒〜10分、好ましくは20秒〜5分、さらに好ましくは40秒〜3分程度であってもよい。また、めっき処理後の基板は、通常、洗浄(および乾燥)してもよい。
ウルツ(Wurtz)カップリング反応(R.D.Miller and J.Michi, Chem.Rev., 89,1359(1989)に記載の方法)により合成したポリ(メチルフェニルシラン)(PMPS)1.0gと、2−(アセトアセトキシ)エチルメタクリレート(AAEM)1.0gとを無水トルエン7mlに溶解し、アンプル管に入れて凍結真空脱気を十分に行った後に、高圧水銀ランプ(ウシオ電機(株)製、「UM−4536−A1」)を用いて、紫外線を照射エネルギー10mW/cm2で20分間照射した。そして、ヘキサンにて再沈殿、ろ過・減圧乾燥を行い、下記式で表されるPMPSとAAEMのブロック共重合体[以下、P(MPS−co−AAEM)という。数平均分子量Mn=1.7x104、分子量分布Mw/Mn=1.8、メチルフェニルシランのブロック数(又はユニット数)=121、AAEMのブロック数(又はユニット数)=151、紫外領域の最大吸収波長λmax=338.4nm]1.65gを得た。
ウルツカップリング反応により合成したポリ(シクロヘキシルメチルシラン)(PCHMS)0.5gとAAEM0.5gとを無水トルエン7mlに溶解し、実施例1と同様の方法で光重合を行い、PCHMSとAAEMとのブロック共重合体[以下、P(CHMS−co−AAEM)という。数平均分子量Mn=1.6x104、分子量分布Mw/Mn=2.0、シクロヘキシルメチルシランのブロック数(又はユニット数)=119、AAEMのブロック数(又はユニット数)=63、紫外領域の最大吸収波長λmax=321.0nm]0.43gを得た。
ポリ(メチルフェニルシラン)(PMPS、大阪ガスケミカル(株)製、商品名「オグソールSI−1010」)をトルエンに溶解し、2−プロパノールにて再沈殿精製を行って精製PMPSを得た。この精製PMPS1.0gと、AAEM1.0gとを無水トルエン7mlに溶解し、実施例1と同様の方法で光重合を行い、P(MPS−co−AAEM)「数平均分子量Mn=1.1x104、分子量分布Mw/Mn=1.4、メチルフェニルシランのブロック数(又はユニット数)=71、AAEMのブロック数(又はユニット数)=29、紫外領域の最大吸収波長λmax=332.4nm]1.18gを得た。
実施例2で得られたP(CHMS−co−AAEM)50mgを含むTHF溶液3mlと、シリカ微粒子を含むTHF溶液[コロイダルシリカのトルエン溶液(扶桑化学工業(株)製、「PL−2L−Tol」、平均粒径20nm)0.1mlをTHF10mlにて希釈して作製した溶液]1mlと、ビスアセチルアセトナトパラジウム(II)(Pd(CH3COCHCOCH3)2)5mgを含むTHF溶液1mlと、酢酸およびTHFの混合溶液(酢酸/THF(重量比)=10/1)とを混合して10分間攪拌し、P(CHMS−co−AAEM)とジアセチルアセトナトパラジウム(II)とシリカ微粒子とを含む組成物を得た。なお、液の色は黄色から変色しなかった。
実施例2で得られた組成物を、2000回転および20秒の条件でポリエチレンテレフタレートフィルム(PETフィルム)にスピンコートして、P(CHMS−co−AAEM)とPd(CH3CO2)2とシリカ微粒子とを含む組成物の薄膜を形成した。そして、得られた薄膜の一部をアルミ箔で覆い、deepUVランプ(ウシオ(株)製、波長172nm)を用いて、光照射した。その後、2−プロパノールで現像し、乾燥および150℃で加熱することにより、光照射した部分のみが硬化したパラジウム微粒子とシリカ微粒子とを含む組成物がコーティングされたPETフィルムを得た。続いて、このPETフィルムに、ビルドカッパー(奥野製薬(株)製)を用いて、銅の無電解めっきを行ったところ、銅薄膜が形成された。なお、銅の無電解めっきでは、40℃のめっき液に薄膜を形成した基板を1.5分間浸漬した後に純水および2−プロパノールで洗浄して乾燥を行った。
実施例1において、シリカ微粒子を用いなかったこと以外は、実施例1と同様にしてネガ型パターンおよび銅配線パターンを形成した。しかし、無電解めっきで生じた銅配線パターンがガラス基板から剥がれた。
実施例2において、シリカ微粒子を用いなかったこと以外は、実施例2と同様にしてネガ型パターンおよび銅配線パターンを形成した。しかし、無電解めっきで生じた銅配線パターンがガラス基板から剥がれた。
実施例3において、シリカ微粒子を用いなかったこと以外は、実施例3と同様にしてネガ型パターンおよび銅配線パターンを形成した。しかし、無電解めっきで生じた銅配線パターンがガラス基板から剥がれた。
実施例4において、シリカ微粒子を用いなかったこと以外は、実施例4と同様にしてネガ型パターンおよび銅配線パターンを形成した。しかし、無電解めっきで生じた銅配線パターンがガラス基板から剥がれた。
実施例5において、シリカ微粒子を用いなかったこと以外は、実施例5と同様にして薄膜および銅薄膜を形成した。しかし、無電解めっきで生じた銅薄膜がPETフィルムから剥がれた。
Claims (14)
- ポリシラン化合物と、還元により金属微粒子を生成可能な金属化合物と、無機微粒子とで構成された組成物。
- ポリシラン化合物が、ポリシランと、金属化合物及び/又は金属微粒子に対する親和性を有するユニットを含むビニル単量体との共重合体であって、前記ビニル単量体が、アミド基、アミノ基、窒素環基、アシル基、アルコキシ基、エーテル基、カルボキシル基、チオ基及びスルホン酸基から選択された少なくとも1種の基を有するビニル単量体である請求項1記載の組成物。
- ビニル単量体が、金属化合物を構成する金属に配位可能な基を有するビニル単量体である請求項1記載の組成物。
- 金属化合物が、貴金属化合物である請求項1記載の組成物。
- 無機微粒子が、平均粒子径0.5nm〜10μmを有する無機酸化物微粒子である請求項1記載の組成物。
- 無機微粒子が、疎水性基を有するシリカである請求項1記載の組成物。
- ポリシラン化合物がポリシランとアシルアセチル基を有するビニル単量体との共重合体であり、金属化合物がパラジウム化合物であり、無機微粒子が疎水性基を有する平均粒子径5〜100nmのシリカである請求項1記載の組成物。
- 金属化合物の割合が、ポリシラン化合物100重量部に対して、2〜200重量部である請求項1記載の組成物。
- 無機微粒子の割合が、金属化合物100重量部に対して、5〜150重量部である請求項1記載の組成物。
- 請求項1記載の組成物に、活性エネルギー線を作用させることによりポリシラン化合物を分解させて、金属微粒子および無機微粒子を含む組成物を製造する方法。
- 基板に、請求項1記載の組成物を塗布し、露光して金属微粒子を生成させたのち、現像し、金属微粒子および無機微粒子を含むパターンを形成する請求項10記載の方法。
- 現像したのち、無電解めっき処理することによりめっきパターンを形成する請求項11記載の方法。
- 金属微粒子が金属ナノ粒子である請求項10記載の方法。
- 請求項11又は12記載の方法により得られるパターン。
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