JP2004026554A - Transparent conductive film-forming liquid and method for manufacturing substrate having transparent conductive film using the same - Google Patents
Transparent conductive film-forming liquid and method for manufacturing substrate having transparent conductive film using the same Download PDFInfo
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- JP2004026554A JP2004026554A JP2002184144A JP2002184144A JP2004026554A JP 2004026554 A JP2004026554 A JP 2004026554A JP 2002184144 A JP2002184144 A JP 2002184144A JP 2002184144 A JP2002184144 A JP 2002184144A JP 2004026554 A JP2004026554 A JP 2004026554A
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- Prior art keywords
- transparent conductive
- conductive film
- substrate
- compound
- indium
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- 239000000758 substrate Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000007788 liquid Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 150000002472 indium compounds Chemical class 0.000 claims abstract description 61
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 58
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 30
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 30
- 229910052738 indium Inorganic materials 0.000 claims abstract description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 14
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 description 26
- 239000004973 liquid crystal related substance Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 for example Chemical compound 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- 229910052700 potassium Inorganic materials 0.000 description 3
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- 238000002834 transmittance Methods 0.000 description 3
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052798 chalcogen Inorganic materials 0.000 description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 2
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- OVZUSPADPSOQQN-UHFFFAOYSA-N tri(propan-2-yloxy)indigane Chemical compound [In+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] OVZUSPADPSOQQN-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- IEDKVDCIEARIIU-UHFFFAOYSA-N 2-Nonadecanone Chemical compound CCCCCCCCCCCCCCCCCC(C)=O IEDKVDCIEARIIU-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- QZUFYZAIYPHVTL-UHFFFAOYSA-L diacetyloxy(butyl)tin Chemical compound CCCC[Sn](OC(C)=O)OC(C)=O QZUFYZAIYPHVTL-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
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- 229910052745 lead Inorganic materials 0.000 description 1
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- 239000004571 lime Substances 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 125000005474 octanoate group Chemical group 0.000 description 1
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- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052696 pnictogen Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、透明導電膜形成液、及び前記透明導電膜形成液を用いた透明導電膜付基体の製法に関する。
【０００２】
【従来の技術】
透明導電膜（ＩＴＯ膜）は、その優れた透明性と導電性を利用して、液晶ディスプレイ、有機ＥＬディスプレイ、面発熱体、タッチパネル電極、太陽電池等に広く利用されている。
上記液晶ディスプレイや有機ＥＬディスプレイ等においては、液晶や有機ＥＬといったデバイス素子を構成する有機化合物中にアルカリ金属が含まれるとデバイス素子の信頼性に悪影響をおよぼすことから、デバイス素子の作製においては、できる限りアルカリ金属を排除することが望まれている。
デバイス素子の作製において、例えば、透明導電膜の基体（ガラス基板）として安価なソーダライム基板（略称：ＳＬＧ基板）を用いた場合、基体自身からのアルカリ金属がデバイス素子を構成する有機化合物中に拡散して素子の信頼性を著しく低下することを防止するため、酸化珪素膜（ＳｉＯ２膜）をアンダーコート膜として用いてアルカリ金属の拡散を阻止しているが、ＳｉＯ２膜の上に成膜する透明電極膜自身にアルカリ金属が含有される場合、これがデバイス素子に拡散することになり、結果として、ＳｉＯ２膜は機能しないことになってしまう。
【０００３】
【発明が解決しようとする課題】
本発明は、かかる実状に鑑みてなされたものであり、本発明の課題は、デバイス素子の信頼性を向上させることのできる透明導電膜を形成可能な透明導電膜形成液、及びデバイス素子の信頼性を向上させることのできる透明導電膜付基体を容易に製造可能な透明導電膜付基体の製法を提供することにある。
【０００４】
【課題を解決するための手段】
本発明者らは、液晶ディスプレイや有機ＥＬディスプレイ等におけるデバイス素子の信頼性を高めるべく鋭意研究を重ねた結果、透明導電膜を形成するための透明導電膜形成液に含有されるアルカリ金属量を特定量（２質量ｐｐｍ）以下に設定することにより、デバイス阻止の信頼性を大幅に向上させることができることを見い出し、本発明を完成するに至った。
【０００５】
すなわち本発明は、インジウム化合物及びスズ化合物を含有し、かつ、アルカリ金属の含有量が２質量ｐｐｍ以下であることを特徴とする透明導電膜形成液（請求項１）や、インジウム化合物が、式〔１〕
Ｉｎ（Ｒ１ＣＯＣＨＣＯＲ２）３ 〔１〕
（式中、Ｒ１及びＲ２は、それぞれ独立して炭素数１〜１０のアルキル基又はフェニル基を表す。）で表されるインジウム化合物であって、スズ化合物が、式〔２〕
（Ｒ３）２Ｓｎ（ＯＲ４）２ 〔２〕
（式中、Ｒ３は炭素数１〜１０のアルキル基を表し、Ｒ４は炭素数１〜１０のアルキル基又は炭素数１〜１０のアシル基を表す。）で表されるスズ化合物であることを特徴とする請求項１に記載の透明導電膜形成液（請求項２）や、式〔１〕で表されるインジウム化合物が、インジウムトリスアセチルアセトナートであることを特徴とする請求項２に記載の透明導電膜形成液（請求項３）や、式〔２〕で表されるスズ化合物が、ジ−ｎ−ブチルスズジアセテートであることを特徴とする請求項２又は３に記載の透明導電膜形成液（請求項４）や、インジウム化合物及びスズ化合物を溶解する溶媒が、β−ジケトン類化合物であることを特徴とする請求項１〜４のいずれかに記載の透明導電膜形成液（請求項５）や、β−ジケトン類化合物が、アセチルアセトンであることを特徴とする請求項５に記載の透明導電膜形成液（請求項６）に関する。
【０００６】
また本発明は、基体上に、直接又は中間膜を介して透明導電膜を形成して透明導電膜付基体を製造する方法であって、前記基体又は中間膜上に、インジウム化合物とスズ化合物を含有し、かつ、アルカリ金属の含有量が２質量ｐｐｍ以下である透明導電膜形成液を用いて、化学的熱分解法により透明導電膜を形成することを特徴とする透明導電膜付基体の製法（請求項７）や、インジウム化合物が、式〔１〕
Ｉｎ（Ｒ１ＣＯＣＨＣＯＲ２）３ 〔１〕
（式中、Ｒ１及びＲ２は、それぞれ独立して炭素数１〜１０のアルキル基又はフェニル基を表す。）で表されるインジウム化合物であって、スズ化合物が、式〔２〕
（Ｒ３）２Ｓｎ（ＯＲ４）２ 〔２〕
（式中、Ｒ３は炭素数１〜１０のアルキル基を表し、Ｒ４は炭素数１〜１０のアルキル基又は炭素数１〜１０のアシル基を表す。）で表されるスズ化合物であることを特徴とする請求項７に記載の透明導電膜付基体の製法（請求項８）や、式〔１〕で表されるインジウム化合物が、インジウムトリスアセチルアセトナートであることを特徴とする請求項８に記載の透明導電膜形成液（請求項９）や、式〔２〕で表されるスズ化合物が、ジ−ｎ−ブチルスズジアセテートであることを特徴とする請求項８又は９に記載の透明導電膜付基体の製法（請求項１０）や、インジウム化合物及びスズ化合物を溶解する溶媒が、β−ジケトン類化合物であることを特徴とする請求項７〜１０のいずれかに記載の透明導電膜付基体の製法（請求項１１）や、β−ジケトン類化合物が、アセチルアセトンであることを特徴とする請求項１１に記載の透明導電膜付基体の製法（請求項１２）や、化学的熱分解法が、インジウム化合物及びスズ化合物を熱により分解させて基体又は中間膜上に堆積させる方法であることを特徴とする請求項７〜１２のいずれかに記載の透明導電膜付基体の製法（請求項１３）や、インジウム化合物及びスズ化合物を熱により分解させて基体又は中間膜上に堆積させる方法が、パイロゾルプロセス法であることを特徴とする請求項１３記載の透明導電膜付基体の製法（請求項１４）に関する。
【０００７】
【発明の実施の形態】
本発明の透明導電膜形成液は、インジウム化合物及びスズ化合物を含有し、かつ、透明導電膜形成液中のアルカリ金属の含有量が２質量ｐｐｍ以下であることを特徴とする。
アルカリ金属の含有量が２質量ｐｐｍ以下である透明導電膜形成液を用いて形成した透明導電膜は、液晶ディスプレイ等におけるデバイス素子に悪影響を与えることなく、デバイス素子の信頼性を大幅に向上させることができる。
【０００８】
本発明の透明導電膜形成液においては、アルカリ金属の含有量は、上記のように２質量ｐｐｍ以下であることが必要であるが、１．５質量ｐｐｍ以下であることが好ましく、１質量ｐｐｍ以下であることがより好ましく、０．１質量ｐｐｍ以下であることがさらに好ましい。
ここで、前記アルカリ金属は、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、フランシウムをいうが、実際に透明導電膜形成液に混入する可能性を考慮して、実際には、ナトリウム及びカリウムの合計の含有量を管理すればよいと考える。
【０００９】
本発明の透明導電膜形成液におけるインジウム化合物としては、熱分解して酸化インジウムとなるものが好ましく、例えば、インジウムトリスアセチルアセトナート（Ｉｎ（ＣＨ３ＣＯＣＨＣＯＣＨ３）３）、インジウムトリスベンゾイルメタネート（Ｉｎ（Ｃ６Ｈ５ＣＯＣＨＣＯＣ６Ｈ５）３）、三塩化インジウム（ＩｎＣｌ３）、硝酸インジウム（Ｉｎ（ＮＯ３）３）、インジウムトリイソプロポキシド（Ｉｎ（Ｏ−ｉ−Ｐｒ）３）等を例示することができる。
【００１０】
本発明の透明導電膜形成液におけるスズ化合物としては、熱分解して酸化第２スズとなるものが好ましく、例えば、塩化第２スズ、ジメチルスズジクロライド、ジブチルスズジクロライド、テトラブチルスズ、スタニアスオクトエート（Ｓｎ（ＯＣＯＣ７Ｈ１５）２）、ジブチルスズマレエート、ジブチルスズビスアセチルアセトナート、ジブチルスズジアセテート等を例示することができる。
【００１１】
また、本発明の透明導電膜形成液は、インジウム化合物及びスズ化合物を含有すればその種類において特に制限されるものではないが、インジウム化合物が、式〔１〕
Ｉｎ（Ｒ１ＣＯＣＨＣＯＲ２）３ 〔１〕
で表されるインジウム化合物であり、スズ化合物が、式〔２〕
（Ｒ３）２Ｓｎ（ＯＲ４）２ 〔２〕
で表されるスズ化合物であることが好ましい。
式〔１〕中、Ｒ１及びＲ２は、それぞれ独立して炭素数１〜１０のアルキル基又はフェニル基を表し、具体的には、例えば、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ターシャリブチル基等を例示することができる。これらの中でも、式〔１〕で表されるインジウム化合物としては、インジウムトリスアセチルアセトナート（Ｉｎ（ＣＨ３ＣＯＣＨＣＯＣＨ３）３）であることが特に好ましい。
【００１２】
式〔２〕中、Ｒ３は炭素数１〜１０のアルキル基を表し、Ｒ４は炭素数１〜１０のアルキル基又は炭素数１〜１０のアシル基を表す。具体的に、Ｒ３としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ターシャリブチル基を例示することができ、Ｒ４としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ターシャリブチル基等のアルキル基、アセチル基、プロピオニル基等のアシル基を例示することができる。これらの中でも、式〔２〕で表されるスズ化合物としては、ジ−ｎ−ブチルスズジアセテート（（ｎ−Ｂｕ）２Ｓｎ（ＯＣＯＣＨ３）２）であることが特に好ましい。
【００１３】
上記式〔１〕で表わされるインジウム化合物と式〔２〕で表わされるスズ化合物は、熱分解温度が近いので、化学的熱分解法を用いて透明導電膜を形成する場合に、両者が均一に拡散して特に均一な膜質の透明導電膜を形成することができると考えられる。なお、式〔１〕で表されるインジウム化合物の一例であるインジウムトリスアセチルアセトナートの熱分解温度は３２０℃近辺であり、式〔２〕で表されるスズ化合物の一例であるジ−ｎ−ブチルスズジアセテートの熱分解温度は３６０℃近辺である。
ここで、前記化学的熱分解法とは、透明導電膜形成液に含有されるインジウム化合物及びスズ化合物を熱により分解させて基体又は中間膜上に堆積させる方法、並びに透明導電膜形成液をコーティングした後、インジウム化合物及びスズ化合物を熱により分解させて基体又は中間膜上に固定する方法をいう。
【００１４】
即ち、本発明において、透明導電膜形成液中の式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を熱により分解させて基体又は中間膜上に堆積させる場合には、熱分解温度の近い式〔１〕で表されるインジウム化合物と式〔２〕で表されるスズ化合物とが、所定温度のもとでほぼ同時に熱分解を起こすことで、両者が均一に拡散して基体又は中間膜上に堆積（蒸着）すると考えられ、膜質の極めて均一な膜を形成して、極めて均一な導電性及び透明性を保有する透明導電膜を形成することができる。また、透明導電膜形成液をコーティングした後、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を熱により分解させて基体又は中間膜上に固定する場合には、また、コーティング後の乾燥及び／又は焼成において、熱分解温度の近い式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物が、所定温度のもとでほぼ同時に熱分解を起こすことで、両者が均一に拡散して基体又は中間膜上に固定されると考えられ、膜質の極めて均一な膜を形成して、極めて均一な導電性及び透明性を保有する透明導電膜を形成することができる。
【００１５】
本発明の透明導電膜形成液は、式〔１〕で表されるインジウム化合物を含有することが好ましいが、他のインジウム化合物を併用することもできる。併用するインジウム化合物としては、熱分解して酸化インジウムとなるものが好ましく、例えば、三塩化インジウム（ＩｎＣｌ３）、硝酸インジウム（Ｉｎ（ＮＯ３）３）、インジウムトリイソプロポキシド（Ｉｎ（Ｏ−ｉ−Ｐｒ）３）等を例示することができる。インジウム化合物を併用する場合、式〔１〕で表されるインジウム化合物は、全インジウム化合物中、８０質量％以上含有されていることが好ましく、９０質量％以上含有されていることがより好ましく、９５質量％以上含有されていることがさらに好ましく、式〔１〕で表されるインジウム化合物がより多く含有されているほど好ましい。
【００１６】
また、本発明の透明導電膜形成液は、式〔２〕で表されるスズ化合物を含有することが好ましいが、他のスズ化合物を併用することもできる。併用するスズ化合物としては、熱分解して酸化第２スズとなるものが好ましく、例えば、塩化第２スズ、ジメチルスズジクロライド、ジブチルスズジクロライド、テトラブチルスズ、スタニアスオクトエート（Ｓｎ（ＯＣＯＣ７Ｈ１５）２）、ジブチルスズマレエート、ジブチルスズビスアセチルアセトナート等を例示することができる。スズ化合物を併用する場合、式〔２〕で表されるスズ化合物は、全スズ化合物中、８０質量％以上含有されていることが好ましく、９０質量％以上含有されていることがより好ましく、９５質量％以上含有されていることがさらに好ましく、式〔２〕で表されるスズ化合物がより多く含有されているほど好ましい。
【００１７】
また、本発明の透明導電膜形成液は、インジウム化合物とスズ化合物を含有すればその含有比に特に制限はないが、インジウム化合物中のＩｎが、質量で、スズ化合物中のＳｎより多く含有されていること（形成される透明導電膜がＩＴＯ膜であること）が好ましく、スズ化合物中のＳｎが、質量比で、インジウム化合物中のＩｎ１に対して０．００１〜０．５含有されていることがより好ましく、０．０５〜０．３５含有されていることがさらに好ましい。
上記質量比の範囲でインジウム化合物とスズ化合物を含有することにより、透明度及び抵抗値の均一性に優れた透明導電膜の形成され、かかる抵抗値を有する透明導電膜は、例えば、タッチパネル用の透明電極として特に有用である。
【００１８】
また、上記インジウム化合物及びスズ化合物を溶解する溶媒としては、アセトン、アセチルアセトン、メチルイソブチルケトン、ジエチルケトン等のケトン系溶媒、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等のアルコール系溶媒、アセト酢酸メチル、アセト酢酸エチル、マロン酸ジメチル、マロン酸ジエチル、酢酸エチル、酢酸ブチル等のエステル系溶媒、メチルセルソルブ、テトラヒドロフラン等のエーテル系溶媒、ベンゼン、トルエン、キシレン等の芳香族炭化水素類、ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素類等を例示することができ、β−ジケトン類化合物が特に好ましく、該β−ジケトン類化合物は、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物との組み合わせにおいて用いることがさらに好ましい。
【００１９】
ここで、前記β−ジケトン類化合物としては、アセチルアセトン等のβ−ジケトン、アセト酢酸メチル、アセト酢酸エチル等のβ−ケトン酸エステル、マロン酸ジメチル、マロン酸ジエチル等のβ−カルボン酸エステル等を例示することができ、これらの中でも、アセチルアセトンが好ましい。なお、β−ジケトン類化合物を用いる場合、他の溶媒と併用することもでき、他の溶媒を併用する場合、β−ケトン類は、全溶媒中、８０質量％以上含有されていることが好ましく、９０質量％以上含有されていることがより好ましく、９５質量％以上含有されていることがさらに好ましく、β−ジケトン類化合物がより多く含有されているほど好ましい。
上記β−ジケトン類化合物を用いることにより、インジウム化合物及びスズ化合物を十分に溶解し、透明導電膜形成液中の組成比が変動することがないので、これを用いて透明導電膜を形成することにより、均一な膜質の透明導電膜を形成することができると考えられる。
【００２０】
また、上記β−ジケトン類化合物は、インジウム化合物及びスズ化合物を溶解することができればその量に特に制限はないが、インジウム化合物及びスズ化合物の合計金属分（Ｉｎ＋Ｓｎ）が、質量比で、β−ジケトン類化合物１に対して０．０７以下含有するようになるようにβ−ジケトン類化合物を添加することが好ましく、０．００００１〜０．０７の範囲となるように添加することがより好ましく、０．００１〜０．０４の範囲となるように添加することがさらに好ましい。β−ジケトン類化合物を上記範囲で使用することにより、インジウム化合物及びスズ化合物を適当な濃度の下に溶解させることができ、より均一な膜質の透明導電膜を形成することが可能となる。
【００２１】
また、本発明の透明導電膜形成液は、前記式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物に加えて、第３成分として、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ等の周期律表第２族元素、Ｓｃ、Ｙ等の第３族元素、Ｌａ、Ｃｅ、Ｎｄ、Ｓｍ、Ｇｄ等のランタノイド、Ｔｉ、Ｚｒ、Ｈｆ等の第４族元素、Ｖ、Ｎｂ、Ｔａ等の第５族元素、Ｃｒ、Ｍｏ、Ｗ等の第６族元素、Ｍｎ等の第７族元素、Ｃｏ等の第９族元素、Ｎｉ、Ｐｄ、Ｐｔ等の第１０族元素、Ｃｕ、Ａｇ等の第１１族元素、Ｚｎ、Ｃｄ等の第１２族元素、Ｂ、Ａｌ、Ｇａ等の第１３族元素、Ｓｉ、Ｇｅ、Ｐｂ等の第１４族元素、Ｐ、Ａｓ、Ｓｂ等の第１５族元素、Ｓｅ、Ｔｅ等の第１６族元素等からなる単体若しくはこれらの化合物を含有することも好ましい。
これらの元素の添加割合は、インジウムに対して、０．０５〜２０原子％程度が好ましく、添加元素によって添加割合は異なり、目的とする抵抗値にあった元素及び添加量を適宜選定することができる。
【００２２】
以下、本発明の透明導電膜付基体の製造方法について説明する。
本発明の透明導電膜付基体の製法は、基体上に、直接又は中間膜を介して透明導電膜を形成して透明導電膜付基体を製造する方法であって、前記基体又は中間膜上に、インジウム化合物とスズ化合物を含有し、かつ、アルカリ金属の含有量が２質量ｐｐｍ以下である透明導電膜形成液を用いて、化学的熱分解法により透明導電膜を形成することを特徴とする。即ち、上記透明導電膜形成液を用いて化学的熱分解法により透明導電膜を形成することを特徴とする。
本発明の透明導電膜付基体の製法によれば、アルカリ金属の含有量が２質量ｐｐｍ以下である透明導電膜形成液を用いるので、液晶ディスプレイ等のにおけるデバイス素子に悪影響を与えることなく、デバイス素子の信頼性を大幅に向上させることができる透明導電膜付基体を容易に製造することができる。また、本発明の透明導電膜付基体の製法により製造された透明導電膜は導電性及び透明性に優れているので、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、面発熱体、タッチパネル電極、太陽電池等に広く利用することができる。さらに、本発明の透明導電膜付基体の製法においては、成膜の一般的手法である化学的熱分解法を用いることによって簡便に均質な膜を形成することができる。
【００２３】
ここで、前記化学的熱分解法とは、透明導電膜形成液に含有されるインジウム化合物及びスズ化合物を熱により分解させて基体又は中間膜上に堆積させる方法、並びに透明導電膜形成液をコーティングした後、インジウム化合物及びスズ化合物を熱により分解させて基体又は中間膜上に固定する方法をいい、例えば、スプレー法、ディップコーティング法、スピンコート法、ＬＢ法、ゾル−ゲル法、液相エピタキシー法、熱ＣＶＤ法、プラズマＣＶＤ法、ＭＯＣＶＤ法、パイロゾルプロセス法、（超音波霧化による常圧ＣＶＤ法）、ＳＰＤ法、Ｃａｔ−ＣＶＤ法等のＣＶＤ法（ｃｈｅｍｉｃａｌ ｖａｐｏｒ ｄｅｐｏｓｉｔｉｏｎ）等が挙げられ、これらの中でもパイロゾルプロセス法を用いることが特に好ましい。パイロゾルプロセス法を用いることにより、より均一な膜質を有する透明導電膜を製造することができる。また、パイロゾルプロセス法においては、透明導電膜形成液がコンベア炉（膜形成装置）に導入されてから透明導電膜が形成されるまでアルカリ金属と接触する機会が全くないので、アルカリ金属の含有量の少ない透明導電膜を極めて容易に形成することができる。
【００２４】
前記中間膜は、一層の膜であってもよく、二層以上の膜であってもよい。かかる中間膜としては、例えば、酸化シリコン膜、有機ポリシラン化合物から形成されるポリシラン膜、ＭｇＦ２膜、ＣａＦ２膜、ＳｉＯ２とＴｉＯ２の複合酸化物膜等を挙げることができる。これらの中間膜は、例えば、基板としてソーダーガラスを用いる場合のＮａイオンの拡散防止の為に形成される。また、透明導電膜と異なる屈折率、好ましくは低屈折率の下地膜を形成することによって、反射防止或いは透明性を向上させることもできる。これらの膜は、一般に知られている成膜方法、例えば、スパッタ法、ＣＶＤ法、スプレー法、ディップ法等により形成することができ、膜厚としては、特に制限されるものではないが、通常２０〜２００ｎｍ程度である。
【００２５】
前記基体としては、シート状（基板）、ハニカム状、ファイバー状、ビーズ状、発泡状やそれらが集積したもの等であってもよく、透明導電膜形成液の成分が熱分解を起こす温度で耐熱性を有するものであれば特に制限されるものではないが、例えば、ガラス基板、セラミックス基板、金属基板等を挙げることができる。これらのうち、本発明の透明導電膜付基体の製法においてはガラス基板を用いるのが好ましい。ガラス基板としては、例えば、ケイ酸ガラス（石英ガラス）、ケイ酸アルカリガラス、ソーダ石灰ガラス、カリ石灰ガラス、鉛ガラス、バリウムガラス、ホウケイ酸ガラス等を挙げることができるが、デバイス素子への悪影響を防止するための中間膜を形成する必要がないという点から、アルカリ金属を含まないガラス基板が好ましく、特にケイ酸ガラスが好ましい。
【００２６】
なお、本発明の透明導電膜付基体の製法によって形成する透明導電膜の膜厚としては、特に制限されるものではなく、その用途等によって適宜選定すればよいが、シート抵抗値が３０Ω／□以下のＩＴＯ膜を形成する場合には、一般に８０ｎｍ以上であり、シート抵抗値が６０〜２００Ω／□のＩＴＯ膜を形成する場合には、一般に３０ｎｍ程度であり、シート抵抗値が２００〜３０００Ω／□のＩＴＯ膜を形成する場合には、一般に１０〜２５ｎｍである。
【００２７】
また、本発明の透明導電膜付基体の製法において、上記パイロゾルプロセス法を用いる場合には、インジウム化合物及びスズ化合物をβ−ジケトン類化合物に溶解させた透明導電膜形成液を超音波によるアトマイジング法を利用して、粒状の比較的そろった微小な小液滴からなるエアロゾルにし、インジウム化合物及びスズ化合物が熱分解を起こして酸化インジウム及び酸化第２スズを形成し得る温度、例えば、３００〜８００℃の均一な温度に管理した加熱炉内の基体上に供給して、インジウム化合物及びスズ化合物を加熱炉内で気化させ気相状態から基体上で反応させて透明導電膜を形成する。
【００２８】
【実施例】
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。
［実施例１］
アルカリ金属の含有量が０．０３質量ｐｐｍのインジウムトリスアセチルアセトナート（Ｉｎ（ＡｃＡｃ）３）をアルカリ金属の含有量が０．０５質量ｐｐｍのアセチルアセトン（β−ジケトン類化合物）にモル濃度で０．２ｍｏｌ／Ｌになるように溶解して黄色透明溶液を得た。この溶液にＳｎ／Ｉｎ＝５質量％となるようにアルカリ金属の含有量が０．０３質量ｐｐｍのジ−ｎ−ブチルスズジアセテートを加えてＩＴＯ膜形成液（透明導電膜形成液）を調製した。
このＩＴＯ膜形成液を用いてパイロゾルプロセス法により、ＩＴＯ膜形成液の霧化による化学的熱分解量を調整しながら、ディッピング法によりＳｉＯ２膜をアンダーコートしたガラス基板上（ＳＬＧ基板）に、厚さ２０ｎｍのＩＴＯ膜を形成し、無色透明のＩＴＯ膜を有するＩＴＯ膜付ガラス基板（透明導電膜付基体）を得た。
【００２９】
［実施例２］
上記実施例１と同様にして、ガラス基板上に厚さ４０ｎｍのＩＴＯ膜を形成し、透明のＩＴＯ膜を有するＩＴＯ膜付ガラス基板を得た。
［実施例３］
上記実施例１と同様にして、ガラス基板上に厚さ２００ｎｍのＩＴＯ膜を形成し、透明のＩＴＯ膜を有するＩＴＯ膜付ガラス基板を得た。
【００３０】
［比較例１］
アルカリ金属の含有量が０．０３質量ｐｐｍのインジウムトリスアセチルアセトナート（Ｉｎ（ＡｃＡｃ）３）をアルカリ金属の含有量が０．０５質量ｐｐｍのアセチルアセトンにモル濃度で０．２ｍｏｌ／Ｌになるように溶解して黄色透明溶液を得た。この溶液にＳｎ／Ｉｎ＝５質量％となるように、アルカリ金属の含有量が０．０３質量ｐｐｍのジ−ｎ−ブチルスズジアセテートを加え、さらに、Ｎａ／Ｉｎ＝１０質量ｐｐｍとなるようにステアリン酸ナトリウムを加えてＩＴＯ膜形成液を調製した。
このＩＴＯ膜形成液を用いてパイロゾルプロセス法により、ＩＴＯ膜形成液の霧化による化学的熱分解量を調整しながら、ディッピング法によりＳｉＯ２膜をアンダーコートしたガラス基板上（ＳＬＧ基板）に、厚さ４０ｎｍのＩＴＯ膜を形成し、ＩＴＯ膜付ガラス基板を製造した。
【００３１】
（評価）
上記実施例１〜３及び比較例１に係るＩＴＯ膜付ガラス基板のＩＴＯ膜を酸でエッチングして溶解し、ＩＣＰ発光分光分析装置でアルカリ金属の含有量を測定した。また、上記実施例１〜３及び比較例１に係るＩＴＯ膜付ガラス基板の比抵抗値をロレスタ（三菱化学社製）を用いて測定し、シート抵抗値を算出した。なお、シート抵抗値は、比抵抗／導電膜の膜厚で求められる値である。また、実施例１〜３及び比較例１に係るＩＴＯ膜付ガラス基板の任意に選ばれた部分ａ〜ｃ（３箇所）について５５０ｎｍの波長における光透過率を磁気分光光度計（日立製作所製）を用いて測定した。さらに、実施例１〜３に係るＩＴＯ膜付ガラス基板のＩＴＯ膜の深さ方向でのインジウムとスズの含有量をＥＳＣＡで測定した。アルカリ金属量の測定結果を下記表１に示し、シート抵抗値の測定結果を下記表２に示し、光透過率の測定結果を下記表３に示す。また、実施例１〜３に係るＩＴＯ膜付ガラス基板についてのＥＳＣＡによる測定結果を図１に示す。
【００３２】
【表１】
【表２】
【表３】
（結果）
表１から明らかなように、本発明に係る実施例１〜３のＩＴＯ膜付ガラス基板におけるＩＴＯ膜は、アルカリ金属の含有量が０．１質量ｐｐｍであり、これを用いて液晶ディスプレイ等のデバイス素子を作製することにより、より信頼性の向上したデバイス素子を製造することができる。一方、比較例に係るＩＴＯ膜付ガラス基板におけるＩＴＯ膜は、アルカリ金属の含有量が１２質量ｐｐｍであって、これを用いて液晶ディスプレイ等のデバイス素子を作製すると、信頼性の低いデバイス素子が製造される。
表２から明らかなように、本発明の透明導電膜付基体の製法により、膜厚を変化させることによって、シート抵抗値が１０〜５００Ω／□のＩＴＯ膜付基体を製造することができ、種々の用途に対応した所望のシート抵抗値のＩＴＯ膜を有するＩＴＯ膜付基体を得ることができる。
また、表３から明らかなように、本発明に係る実施例１〜３のＩＴＯ膜付ガラス基板は、それぞれ、任意の部分において光透過率がほぼ等しく、膜の透明度が均一であった。
また、図１から明らかなように、本発明に係る実施例１〜３のＩＴＯ膜付ガラス基板においては、スズの含有率がほぼ一定しており、膜の表面及び内部でインジウムとスズが均一に分散した膜が形成された。
【００３６】
【発明の効果】
本発明の透明導電膜形成液によれば、デバイス素子の信頼性を向上させることのできる透明導電膜を形成することができる。また、本発明の透明導電膜付基体の製法によれば、デバイス素子の信頼性を向上させることのできる透明導電膜付基体を容易に製造することができる。
【図面の簡単な説明】
【図１】本発明の透明導電膜付基体の製法により製造した透明導電膜付基体（実施例のＩＴＯ膜付ガラス基板）についてのＥＳＣＡによる測定結果を示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a liquid for forming a transparent conductive film and a method for producing a substrate with a transparent conductive film using the liquid for forming a transparent conductive film.
[0002]
[Prior art]
BACKGROUND ART Transparent conductive films (ITO films) are widely used in liquid crystal displays, organic EL displays, surface heating elements, touch panel electrodes, solar cells, and the like, utilizing their excellent transparency and conductivity.
In the above-mentioned liquid crystal display, organic EL display, and the like, when an alkali metal is contained in an organic compound constituting a device element such as a liquid crystal or an organic EL, the reliability of the device element is adversely affected. It is desired to eliminate alkali metals as much as possible.
In the case of manufacturing a device element, for example, when an inexpensive soda lime substrate (abbreviation: SLG substrate) is used as a base (glass substrate) of a transparent conductive film, alkali metal from the base itself is contained in an organic compound constituting the device element. to prevent that significantly reduce the reliability of the device by diffusion, but by preventing diffusion of alkali metal with a silicon oxide film (SiO 2 film) as an undercoat layer, formed on the SiO 2 film If the transparent electrode film itself contains an alkali metal, it diffuses into the device element, and as a result, the SiO 2 film does not function.
[0003]
[Problems to be solved by the invention]
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a transparent conductive film forming liquid capable of forming a transparent conductive film capable of improving the reliability of a device element, and a method for forming a transparent conductive film. It is an object of the present invention to provide a method for producing a substrate with a transparent conductive film, which can easily produce a substrate with a transparent conductive film capable of improving the performance.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to improve the reliability of device elements in a liquid crystal display, an organic EL display, and the like. As a result, the amount of alkali metal contained in the transparent conductive film forming solution for forming the transparent conductive film was reduced. It has been found that by setting the content to a specific amount (2 ppm by mass) or less, the reliability of device blocking can be greatly improved, and the present invention has been completed.
[0005]
That is, the present invention provides a transparent conductive film forming solution (invention 1), which contains an indium compound and a tin compound, and has an alkali metal content of 2 mass ppm or less, [1]
In (R 1 COCHCOR 2 ) 3 [1]
(In the formula, R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group.) The indium compound represented by the formula [2]
(R 3 ) 2 Sn (OR 4 ) 2 [2]
(Wherein, R 3 represents an alkyl group having 1 to 10 carbon atoms, and R 4 represents an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms). The liquid for forming a transparent conductive film according to claim 1, wherein the indium compound represented by the formula [1] is indium trisacetylacetonate. The transparent conductive film forming liquid according to claim 2 or 3, wherein the tin compound represented by the formula (2) or the tin compound represented by the formula [2] is di-n-butyltin diacetate. The liquid for forming a transparent conductive film according to any one of claims 1 to 4, wherein the solvent for dissolving the indium compound and the tin compound is a β-diketone compound. (Claim 5) or the β-diketone compound is A transparent conductive film forming solution according to claim 5, characterized in that cetyl acetone relates (claim 6).
[0006]
Further, the present invention is a method for producing a substrate with a transparent conductive film by forming a transparent conductive film directly or via an intermediate film on a substrate, wherein an indium compound and a tin compound are formed on the substrate or the intermediate film. A method for producing a substrate with a transparent conductive film, characterized in that a transparent conductive film is formed by a chemical pyrolysis method using a transparent conductive film forming solution containing 2 mass ppm or less of an alkali metal. (Claim 7) The compound of the formula [1]
In (R 1 COCHCOR 2 ) 3 [1]
(In the formula, R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group.) The indium compound represented by the formula [2]
(R 3 ) 2 Sn (OR 4 ) 2 [2]
(Wherein, R 3 represents an alkyl group having 1 to 10 carbon atoms, and R 4 represents an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms). The method for producing a substrate with a transparent conductive film according to claim 7, wherein the indium compound represented by the formula (1) is indium trisacetylacetonate. The transparent conductive film forming liquid according to claim 8 (claim 9) or the tin compound represented by the formula [2] is di-n-butyltin diacetate. The method according to any one of claims 7 to 10, wherein the solvent for dissolving the indium compound and the tin compound is a β-diketone compound. A method for producing a substrate with a conductive film (claim 11), The method for producing a substrate with a transparent conductive film according to claim 11, wherein the β-diketone compound is acetylacetone (claim 12), and the method for thermally decomposing an indium compound and a tin compound by heat. The method for producing a substrate with a transparent conductive film according to any one of claims 7 to 12, wherein the indium compound and the tin compound are decomposed and deposited on a substrate or an intermediate film. The method for producing a substrate with a transparent conductive film according to claim 13, wherein the method of decomposing by heat and depositing on a substrate or an intermediate film is a pyrosol process method.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
The transparent conductive film forming solution of the present invention contains an indium compound and a tin compound, and the content of the alkali metal in the transparent conductive film forming solution is 2 ppm by mass or less.
A transparent conductive film formed using a transparent conductive film forming solution having an alkali metal content of 2 mass ppm or less greatly improves the reliability of device elements without adversely affecting device elements in a liquid crystal display or the like. be able to.
[0008]
In the transparent conductive film forming liquid of the present invention, the content of the alkali metal is required to be 2 mass ppm or less as described above, but is preferably 1.5 mass ppm or less, and preferably 1 mass ppm. Or less, more preferably 0.1 mass ppm or less.
Here, the alkali metal refers to lithium, sodium, potassium, rubidium, cesium, and francium, but in consideration of the possibility of actually mixing into the transparent conductive film forming liquid, the alkali metal is actually the sum of sodium and potassium. We think that the content should be controlled.
[0009]
As the indium compound in the transparent conductive film forming solution of the present invention, a compound which is thermally decomposed into indium oxide is preferable. For example, indium trisacetylacetonate (In (CH 3 COCHCOCH 3 ) 3 ), indium trisbenzoyl methanate ( In (C 6 H 5 COCHCOC 6 H 5) 3), indium trichloride (InCl 3), indium nitrate (In (NO 3) 3) , indium triisopropoxide (In (O-i-Pr ) 3) , etc. Can be exemplified.
[0010]
The tin compound in the transparent conductive film forming solution of the present invention is preferably a compound which is thermally decomposed to form stannic oxide, for example, stannic chloride, dimethyltin dichloride, dibutyltin dichloride, tetrabutyltin, stanias octoate ( Sn (OCOC 7 H 15 ) 2 ), dibutyltin maleate, dibutyltin bisacetylacetonate, dibutyltin diacetate and the like can be exemplified.
[0011]
The type of the transparent conductive film forming solution of the present invention is not particularly limited as long as it contains an indium compound and a tin compound.
In (R 1 COCHCOR 2 ) 3 [1]
Wherein the tin compound is represented by the formula [2]
(R 3 ) 2 Sn (OR 4 ) 2 [2]
Is preferably a tin compound represented by
In Formula [1], R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and specifically, for example, a methyl group, an ethyl group, an n-propyl group, -Butyl group, tertiary butyl group and the like. Among these, the indium compound represented by the formula [1] is particularly preferably indium trisacetylacetonate (In (CH 3 COCHCOCH 3 ) 3 ).
[0012]
In the formula [2], R 3 represents an alkyl group having 1 to 10 carbon atoms, and R 4 represents an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms. Specifically, examples of R 3 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group and a tertiary butyl group, and examples of R 4 include a methyl group and an ethyl group. , An n-propyl group, an n-butyl group, an alkyl group such as a tertiary butyl group, and an acyl group such as an acetyl group and a propionyl group. Among these, the tin compounds represented by the formula (2), particularly preferably di -n- butyl tin diacetate ((n-Bu) 2 Sn (OCOCH 3) 2).
[0013]
Since the indium compound represented by the formula [1] and the tin compound represented by the formula [2] have similar thermal decomposition temperatures, when forming a transparent conductive film using a chemical pyrolysis method, both are uniformly formed. It is considered that a transparent conductive film having particularly uniform film quality can be formed by diffusion. The thermal decomposition temperature of indium trisacetylacetonate which is an example of the indium compound represented by the formula [1] is around 320 ° C., and di-n- which is an example of the tin compound represented by the formula [2] The thermal decomposition temperature of butyltin diacetate is around 360 ° C.
Here, the chemical pyrolysis method is a method in which an indium compound and a tin compound contained in a transparent conductive film forming liquid are decomposed by heat and deposited on a substrate or an intermediate film, and a method of coating the transparent conductive film forming liquid. After that, the indium compound and the tin compound are decomposed by heat and fixed on the substrate or the intermediate film.
[0014]
That is, in the present invention, when the indium compound represented by the formula [1] and the tin compound represented by the formula [2] in the transparent conductive film forming liquid are decomposed by heat and deposited on the substrate or the intermediate film, Is that the indium compound represented by the formula [1] and the tin compound represented by the formula [2], which are close to each other in thermal decomposition temperature, undergo thermal decomposition almost simultaneously at a predetermined temperature, so that both are uniformly formed. It is considered that the film is diffused and deposited (deposited) on the substrate or the intermediate film, so that a film having extremely uniform film quality can be formed, and a transparent conductive film having extremely uniform conductivity and transparency can be formed. In addition, after coating the transparent conductive film forming solution, the indium compound represented by the formula [1] and the tin compound represented by the formula [2] are decomposed by heat and fixed on a substrate or an intermediate film. In addition, in the drying and / or baking after coating, the indium compound represented by the formula [1] and the tin compound represented by the formula [2], which have similar thermal decomposition temperatures, are heated almost simultaneously at a predetermined temperature. By decomposing, it is thought that both diffuse uniformly and are fixed on the substrate or the intermediate film, forming a film with extremely uniform film quality, and a transparent conductive material having extremely uniform conductivity and transparency. A film can be formed.
[0015]
The liquid for forming a transparent conductive film of the present invention preferably contains an indium compound represented by the formula [1], but another indium compound may be used in combination. As the indium compound to be used in combination, a compound which is thermally decomposed into indium oxide is preferable. For example, indium trichloride (InCl 3 ), indium nitrate (In (NO 3 ) 3 ), indium triisopropoxide (In (O− i-Pr) 3 ). When an indium compound is used in combination, the indium compound represented by the formula [1] is preferably contained in an amount of 80% by mass or more, more preferably 90% by mass or more, and more preferably 95% by mass in all indium compounds. It is more preferable that the indium compound represented by the formula [1] be contained in an amount of at least 1% by mass.
[0016]
The liquid for forming a transparent conductive film of the present invention preferably contains a tin compound represented by the formula [2], but another tin compound may be used in combination. As the tin compound to be used in combination, a compound which is thermally decomposed into stannic oxide is preferable. For example, stannic chloride, dimethyltin dichloride, dibutyltin dichloride, tetrabutyltin, staniasoctoate (Sn (OCOC 7 H 15 )) 2 ), dibutyltin maleate, dibutyltin bisacetylacetonate and the like. When a tin compound is used in combination, the content of the tin compound represented by the formula [2] is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total tin compound. It is more preferable that the tin compound is contained in an amount of not less than mass%, and it is more preferable that the tin compound represented by the formula [2] is contained in a larger amount.
[0017]
The content ratio of the transparent conductive film forming liquid of the present invention is not particularly limited as long as it contains an indium compound and a tin compound, but In in the indium compound is contained in a larger amount than Sn in the tin compound by mass. (The transparent conductive film to be formed is an ITO film), and Sn in the tin compound is contained in a mass ratio of 0.001 to 0.5 with respect to In1 in the indium compound. More preferably, the content is more preferably 0.05 to 0.35.
By containing the indium compound and the tin compound in the range of the mass ratio, a transparent conductive film having excellent transparency and uniformity of the resistance value is formed, and the transparent conductive film having such a resistance value is, for example, a transparent conductive film for a touch panel. It is particularly useful as an electrode.
[0018]
Further, as a solvent for dissolving the indium compound and the tin compound, acetone, acetylacetone, methyl isobutyl ketone, ketone solvents such as diethyl ketone, methanol, ethanol, propanol, isopropanol, alcohol solvents such as butanol, methyl acetoacetate, Ester solvents such as ethyl acetoacetate, dimethyl malonate, diethyl malonate, ethyl acetate and butyl acetate; ether solvents such as methylcellosolve and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; hexane and heptane And octane, cyclohexane and other aliphatic hydrocarbons, and β-diketone compounds are particularly preferred. The β-diketone compounds are an indium compound represented by the formula [1] and a formula [2] ] Represented by tin More preferably, they are used in combination with a compound.
[0019]
Here, examples of the β-diketone compound include β-diketones such as acetylacetone, β-ketone esters such as methyl acetoacetate and ethyl acetoacetate, and β-carboxylates such as dimethyl malonate and diethyl malonate. Among them, acetylacetone is preferable. When a β-diketone compound is used, it can be used in combination with another solvent. When another solvent is used in combination, the β-ketone is preferably contained in an amount of 80% by mass or more in all the solvents. , 90% by mass or more, more preferably 95% by mass or more, and more preferably a β-diketone compound.
By using the β-diketone compound, the indium compound and the tin compound are sufficiently dissolved, and the composition ratio in the transparent conductive film forming liquid does not fluctuate. Therefore, a transparent conductive film is formed using the compound. Thus, it is considered that a transparent conductive film having uniform film quality can be formed.
[0020]
The amount of the β-diketone compound is not particularly limited as long as the indium compound and the tin compound can be dissolved, but the total metal component (In + Sn) of the indium compound and the tin compound is expressed by a mass ratio of β- It is preferable to add the β-diketone compound so as to contain 0.07 or less with respect to the diketone compound 1, and it is more preferable to add the β-diketone compound so as to be in the range of 0.00001 to 0.07. More preferably, it is added in a range of 0.001 to 0.04. By using the β-diketone compound in the above range, the indium compound and the tin compound can be dissolved under an appropriate concentration, and a more uniform transparent conductive film can be formed.
[0021]
Further, the liquid for forming a transparent conductive film of the present invention contains Mg, Ca, Sr, and Ba as a third component in addition to the indium compound represented by the formula [1] and the tin compound represented by the formula [2]. Group 3 elements such as Sc, Y, lanthanoids such as La, Ce, Nd, Sm, and Gd; Group 4 elements such as Ti, Zr, and Hf; V, Nb, and Ta Group 5 element such as Cr, Mo, W, etc., Group 7 element such as Mn, Group 9 element such as Co, Group 10 element such as Ni, Pd, Pt, Cu, Ag Group 11 elements such as Zn, Cd, etc., Group 13 elements such as B, Al, Ga, etc., Group 14 elements such as Si, Ge, Pb, etc., and Group 15 elements such as P, As, Sb, etc. It is also preferable to contain a simple substance composed of a
The addition ratio of these elements is preferably about 0.05 to 20 atomic% with respect to indium. The addition ratio differs depending on the added element, and the element and the addition amount suitable for the target resistance value can be appropriately selected. it can.
[0022]
Hereinafter, a method for producing the substrate with a transparent conductive film of the present invention will be described.
The method for producing a substrate with a transparent conductive film of the present invention is a method for producing a substrate with a transparent conductive film by forming a transparent conductive film directly or via an intermediate film on the substrate, wherein the method comprises the steps of: Forming a transparent conductive film by a chemical pyrolysis method using a transparent conductive film forming liquid containing an indium compound and a tin compound, and having an alkali metal content of 2 mass ppm or less. . That is, a transparent conductive film is formed by a chemical thermal decomposition method using the above-mentioned transparent conductive film forming liquid.
According to the method for producing a substrate with a transparent conductive film of the present invention, since a transparent conductive film forming liquid having an alkali metal content of 2 mass ppm or less is used, the device is not adversely affected by a device such as a liquid crystal display. A substrate with a transparent conductive film that can greatly improve the reliability of the element can be easily manufactured. Further, since the transparent conductive film produced by the method for producing a substrate with a transparent conductive film of the present invention has excellent conductivity and transparency, it is widely used in liquid crystal displays, electroluminescent displays, surface heating elements, touch panel electrodes, solar cells, and the like. Can be used. Further, in the method for producing a substrate with a transparent conductive film of the present invention, a uniform film can be easily formed by using a chemical pyrolysis method which is a general method of film formation.
[0023]
Here, the chemical pyrolysis method is a method in which an indium compound and a tin compound contained in a transparent conductive film forming liquid are decomposed by heat and deposited on a substrate or an intermediate film, and a method of coating the transparent conductive film forming liquid. After that, a method in which the indium compound and the tin compound are decomposed by heat and fixed on a substrate or an intermediate film, for example, a spray method, a dip coating method, a spin coating method, an LB method, a sol-gel method, a liquid phase epitaxy Method, thermal CVD method, plasma CVD method, MOCVD method, pyrosol process method, (atmospheric pressure CVD method by ultrasonic atomization), SPD method, CVD method such as Cat-CVD method (chemical vapor deposition), and the like. Of these, it is particularly preferable to use the pyrosol process method. By using the pyrosol process method, a transparent conductive film having more uniform film quality can be manufactured. In the pyrosol process method, there is no opportunity to come into contact with an alkali metal until a transparent conductive film is formed after the transparent conductive film forming liquid is introduced into a conveyor furnace (film forming apparatus). A small amount of transparent conductive film can be formed very easily.
[0024]
The intermediate film may be a one-layer film or a two-layer or more film. Examples of such an intermediate film include a silicon oxide film, a polysilane film formed from an organic polysilane compound, an MgF 2 film, a CaF 2 film, and a composite oxide film of SiO 2 and TiO 2 . These intermediate films are formed, for example, to prevent diffusion of Na ions when soda glass is used as the substrate. Further, by forming a base film having a refractive index different from that of the transparent conductive film, preferably a low refractive index, the antireflection or the transparency can be improved. These films can be formed by a generally known film forming method, for example, a sputtering method, a CVD method, a spray method, a dipping method, and the like. The thickness is not particularly limited, but is usually It is about 20 to 200 nm.
[0025]
The substrate may be a sheet (substrate), a honeycomb, a fiber, a bead, a foam, or a combination thereof, and is heat-resistant at a temperature at which a component of the transparent conductive film forming liquid thermally decomposes. The material is not particularly limited as long as it has properties, and examples thereof include a glass substrate, a ceramics substrate, and a metal substrate. Among them, a glass substrate is preferably used in the method for producing a substrate with a transparent conductive film of the present invention. Examples of the glass substrate include silicate glass (quartz glass), alkali silicate glass, soda lime glass, potassium lime glass, lead glass, barium glass, borosilicate glass, and the like. In view of the fact that there is no need to form an intermediate film for preventing the above, a glass substrate containing no alkali metal is preferable, and silicate glass is particularly preferable.
[0026]
The thickness of the transparent conductive film formed by the method for producing a substrate with a transparent conductive film of the present invention is not particularly limited, and may be appropriately selected depending on the application and the like, but the sheet resistance value is 30Ω / □. When the following ITO film is formed, it is generally 80 nm or more. When an ITO film having a sheet resistance value of 60 to 200 Ω / □ is formed, it is generally about 30 nm, and the sheet resistance value is 200 to 3000 Ω /. When an ITO film of □ is formed, the thickness is generally 10 to 25 nm.
[0027]
In the method for producing a substrate with a transparent conductive film according to the present invention, when the above-mentioned pyrosol process method is used, a transparent conductive film forming solution obtained by dissolving an indium compound and a tin compound in a β-diketone compound is subjected to atomization by ultrasonic waves. By using the Ising method, an aerosol composed of fine and relatively small particles in the form of particles is formed, and a temperature at which the indium compound and the tin compound can be thermally decomposed to form indium oxide and stannic oxide, for example, 300 The transparent conductive film is formed by supplying the indium compound and the tin compound in the heating furnace by evaporating the indium compound and the tin compound in the heating furnace and reacting the indium compound and the tin compound on the substrate in a gaseous state.
[0028]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the technical scope of the present invention is not limited to these examples.
[Example 1]
Indium trisacetylacetonate (In (AcAc) 3 ) having an alkali metal content of 0.03 mass ppm is converted to acetylacetone (β-diketone compound) having an alkali metal content of 0.05 mass ppm in a molar concentration of 0%. .2 mol / L to obtain a yellow transparent solution. Di-n-butyltin diacetate having an alkali metal content of 0.03 mass ppm was added to this solution so that Sn / In = 5 mass% to prepare an ITO film forming solution (transparent conductive film forming solution). .
Using this ITO film forming solution, a pyrosol process method is used to adjust the amount of chemical thermal decomposition caused by atomization of the ITO film forming solution, and onto a glass substrate (SLG substrate) with an SiO 2 film undercoated by a dipping method. Then, an ITO film having a thickness of 20 nm was formed, and a glass substrate with an ITO film having a colorless and transparent ITO film (substrate with a transparent conductive film) was obtained.
[0029]
[Example 2]
An ITO film having a thickness of 40 nm was formed on a glass substrate in the same manner as in Example 1 to obtain a glass substrate with an ITO film having a transparent ITO film.
[Example 3]
A 200-nm-thick ITO film was formed on a glass substrate in the same manner as in Example 1 to obtain a glass substrate with an ITO film having a transparent ITO film.
[0030]
[Comparative Example 1]
Indium trisacetylacetonate (In (AcAc) 3 ) having an alkali metal content of 0.03 mass ppm is converted to acetylacetone having an alkali metal content of 0.05 mass ppm in a molar concentration of 0.2 mol / L. To give a clear yellow solution. Di-n-butyltin diacetate having an alkali metal content of 0.03 mass ppm was added to the solution so that Sn / In = 5 mass%, and further Na / In = 10 mass ppm. Sodium stearate was added to prepare an ITO film forming solution.
Using this ITO film forming solution, a pyrosol process method is used to adjust the amount of chemical thermal decomposition caused by atomization of the ITO film forming solution, and onto a glass substrate (SLG substrate) with an SiO 2 film undercoated by a dipping method. Then, an ITO film having a thickness of 40 nm was formed, and a glass substrate with an ITO film was manufactured.
[0031]
(Evaluation)
The ITO film of the glass substrate with an ITO film according to Examples 1 to 3 and Comparative Example 1 was dissolved by etching with an acid using an acid, and the content of alkali metal was measured by an ICP emission spectrometer. Moreover, the specific resistance of the glass substrate with an ITO film according to Examples 1 to 3 and Comparative Example 1 was measured using Loresta (manufactured by Mitsubishi Chemical Corporation), and the sheet resistance was calculated. Note that the sheet resistance value is a value determined by the specific resistance / the thickness of the conductive film. In addition, the light transmittance at a wavelength of 550 nm of the arbitrarily selected portions a to c (three places) of the glass substrates with the ITO film according to Examples 1 to 3 and Comparative Example 1 was measured using a magnetic spectrophotometer (manufactured by Hitachi, Ltd.) It measured using. Furthermore, the content of indium and tin in the depth direction of the ITO film of the glass substrate with an ITO film according to Examples 1 to 3 was measured by ESCA. The measurement results of the amount of alkali metal are shown in Table 1 below, the measurement results of the sheet resistance value are shown in Table 2 below, and the measurement results of the light transmittance are shown in Table 3 below. FIG. 1 shows the results of ESCA measurement on the glass substrates with ITO films according to Examples 1 to 3.
[0032]
[Table 1]
[Table 2]
[Table 3]
(result)
As is clear from Table 1, the ITO film in the glass substrate with the ITO film of Examples 1 to 3 according to the present invention has an alkali metal content of 0.1 mass ppm, and is used for a liquid crystal display or the like. By manufacturing a device element, a device element with higher reliability can be manufactured. On the other hand, the ITO film in the glass substrate with the ITO film according to the comparative example has an alkali metal content of 12 ppm by mass, and when a device element such as a liquid crystal display is manufactured using the same, a device element having low reliability is obtained. Manufactured.
As is clear from Table 2, by changing the film thickness by the method for producing a substrate with a transparent conductive film of the present invention, a substrate with an ITO film having a sheet resistance of 10 to 500 Ω / □ can be produced. It is possible to obtain a substrate with an ITO film having an ITO film having a desired sheet resistance value corresponding to the use of (1).
Further, as is apparent from Table 3, the glass substrates with the ITO films of Examples 1 to 3 according to the present invention had substantially the same light transmittance in any part and uniform film transparency.
Also, as is clear from FIG. 1, in the glass substrates with the ITO film of Examples 1 to 3 according to the present invention, the tin content is almost constant, and indium and tin are uniform on the surface and inside of the film. A film dispersed in was formed.
[0036]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to the transparent conductive film forming liquid of this invention, the transparent conductive film which can improve the reliability of a device element can be formed. Further, according to the method for producing a substrate with a transparent conductive film of the present invention, a substrate with a transparent conductive film capable of improving the reliability of a device element can be easily produced.
[Brief description of the drawings]
FIG. 1 is a diagram showing the results of ESCA measurement on a substrate with a transparent conductive film (a glass substrate with an ITO film in Examples) manufactured by the method for producing a substrate with a transparent conductive film of the present invention.
Claims (14)
前記基体又は中間膜上に、インジウム化合物とスズ化合物を含有し、かつ、アルカリ金属の含有量が２質量ｐｐｍ以下である透明導電膜形成液を用いて、化学的熱分解法により透明導電膜を形成することを特徴とする透明導電膜付基体の製法。A method for producing a substrate with a transparent conductive film by forming a transparent conductive film directly or via an intermediate film on a substrate,
On the substrate or the intermediate film, a transparent conductive film is formed by a chemical pyrolysis method using a transparent conductive film forming solution containing an indium compound and a tin compound, and having an alkali metal content of 2 mass ppm or less. A method for producing a substrate with a transparent conductive film, characterized by being formed.
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