JPH0530001B2 - - Google Patents
Info
- Publication number
- JPH0530001B2 JPH0530001B2 JP27265187A JP27265187A JPH0530001B2 JP H0530001 B2 JPH0530001 B2 JP H0530001B2 JP 27265187 A JP27265187 A JP 27265187A JP 27265187 A JP27265187 A JP 27265187A JP H0530001 B2 JPH0530001 B2 JP H0530001B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- composition
- chlorine
- transparent conductive
- alkoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 16
- -1 indium alkoxide Chemical class 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 8
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 239000010408 film Substances 0.000 description 49
- 239000000243 solution Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010063836 Atrioventricular septal defect Diseases 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001211 electron capture detection Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical group [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Surface Treatment Of Glass (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Manufacturing Of Electric Cables (AREA)
Description
［産業上の利用分野］
本発明は、基板上に透明導電性膜を形成せしめ
る際に用いられる組成物、および透明性導電性膜
の形成方法に関し、さらに詳しくは帯電防止膜
（液晶用）、太陽電池、ECD等の電極としての用
途に有用な透明導電性膜用の溶液組成物、および
その膜の形成方法に関するものである。
［従来の技術］
近年、種々の基板表面上を薄膜で被覆し、基板
上に所望の導電特性を付与させる試みがなされて
いる。その中で酸化インジウムと酸化スズの混合
組成の膜はITO膜（以下ITO膜と称す）といわ
れ、透明性が良好でかつ導電性を有する皮膜であ
り、通常はPVD、真空蒸着、スパツター、CVD
（プラズマCVD、熱CVD）等により成膜される。
現状では、PVDやCVDが主流であり、PVDスパ
ツタリングが盛んに行われている。しかし、上記
方法においては、成膜速度が遅い、成膜装置が大
がかりで高価、大面積化や大量生産が難しい等の
問題があつた。
そこで生産性、均質性、作業性、経済性等のか
かる欠点の解消を考慮し、分解熱処理によりITO
膜とし、しかも優れた電気的特性を与える方法と
して、インジウム化合物およびスズ化合物を含む
有機溶剤を使用してのスプレー法、ロールコート
法、スピンコート法、浸漬法によるITO膜の形成
法が提案されている。例えば、特開昭59−198606
号公報では塩素を含有したインジウムアルコキシ
ドとスズ化合物と、適当な有機溶剤と、水とから
なる組成物が開示されており、これを使つた成膜
方法としては、浸漬法が用いられている。
［発明が解決しようとする問題点］
しかし、前記発明においては、スズ化合物とし
て、実質的には完全置換型のテトラエトキシスズ
使つており、しかもアルコキシドの系に水を添加
しているため、保存寿命（ポツトライフ）の長い
組成を製造するのは非常に難しく、また再現性の
あるデータを得るのがきわめて困難である。ま
た、成膜した際も膜厚も不均一になり、白濁など
を生じる場合が多いことがわかつた。従つて、本
発明においては広い組成範囲にわたつてポツトラ
イフが長く、導電特性のよい薄膜が再現性よく得
られる組成物および導電性膜の形成方法を提供す
ることを目的とする。
［問題点を解決するための手段］
上記目的を達成するため、本発明者らは鋭意検
討を行つた結果、特定組成の塩素含有アルコキシ
ドを組合せることにより、ポツトライフが非常に
長く、かつ再現性よく導電特性の優れた透明導電
性膜が形成したことを見いだし、本発明に到達し
たものである。すなわち、本発明は一般式In
（OR1）xCl3-x（ただし、R1は炭素数１〜10のアル
キル基またはアルコキシアルキル基を示し、1.0
≦ｘ≦2.5）で示される塩素含有インジウムアル
コキシドと、一般式Sn（OR2）yClo-y（ただし、R2
は炭素数１〜10のアルキル基またはアルコキシア
ルキル基を示し、ｎは２または４であり、ｎ＝２
の場合1.0≦ｙ≦1.8、ｎ＝４の場合 2.5≦ｙ≦
3.5）で示される塩素含有スズアルコキシドを、
In／Snのモル比で98／２≧In／Sn≧70／30の割
合で混合することを特徴とする透明導電性膜用組
成物および上記組成物を用い、基板に塗布し、室
温〜200℃で乾燥し、400〜600℃で焼成すること
を特徴とする透明導電性膜の形成方法である。
本発明で用いられるアルキル基は炭素数１〜10
であるが、特に炭素数２〜５が好ましく、さらに
はアルコキシアルキル基がこのましい。
また、Snについてはｎが２と４のばあいがあ
り、２通りの組合せが考えられるが、いずれの場
合でもよい。本発明組成物の濃度は、塩素含有ス
ズアルコキシドと塩素含有インジウムアルコキシ
ドの合計が0.1〜1.0mol／が好ましい。
両者の濃度合計が0.1mol／未満の場合、１
回で塗布する膜の厚さが薄すぎるため、重ね塗り
する回数が多くなりすぎ、膜自体の透明性や導電
特性が劣る。一方、濃度が1.0mol／を越える
場合、一回で形成される塗膜の厚さが厚すぎるた
め、塗膜がひび割れを起こしやすく、導電特性の
優れた膜を得ることが難しい。
このような組成、濃度の導電膜用組成物は非常
にポツトライフが長く、普通の保存状態では６カ
月以上、加水分解を起こさず、沈殿等を生じな
い。
これらの溶液は溶媒によつて希釈してもよく、
希釈溶媒としては、ヘキサン、ヘプタン等の炭化
水素、ベンゼン、トルエン、キシレン等の芳香族
炭化水素、ｎ−プロパノール、ｉ−プロパノー
ル、ｎ−ブタノール、ｉ−ブタノール等のアルコ
ール、酢酸エチル、酢酸ブチル等の酢酸エステ
ル、ジエチルケトン、アセトン等のケトン類、エ
チレングリコールモノエチルエーテル等のエーテ
ル、THF、クロロホルム等が挙げられ、これら
の溶剤で希釈した後種々の条件で成膜することが
できる。
塗布する方法としては、スプレー法、ロールコ
ート法、スクリーン印刷、スピンコート法、浸漬
法を用いて成膜することができるが、浸漬法、ス
ピンコート法が好ましい。
また、塗布時の温度、湿度などの条件は、加水
分解速度に大きく影響されるので厳重な管理が必
要である。
上記方法で成膜した後、約５分〜１時間室温放
置し、空気中の水分で充分アルコキシドをゲル化
させる。その後、室温〜200℃で10分〜１時間乾
燥することによりフリーの有機物、残りの溶媒、
および水分を飛散せしめる。その際、急激に200
℃以上の温度で乾燥すると、表面と内部の乾燥速
度の差により膜の白濁、収縮が生じやすい。
最後に、400〜600℃で焼成することにより、有
機物が酸化分解により飛散し、金属も酸化物とな
る。
この乾燥、焼成工程において、昇温速度は非常
に重要であり、10℃／min以内にゆつくり加熱す
れば緻密で透明な膜が得られるが、昇温速度が早
すぎる場合、微細クラツクの原因となり易い。ま
た、焼成温度によつても膜の導電特性が大きく変
り、470〜520℃が最も低い抵抗値を示し、より好
ましい。
さらに、焼成する時の雰囲気も導電特性に大き
く影響を及ぼす。通常は、酸化雰囲気で焼成する
が、400〜600℃で焼成する際に、外部より水素、
窒素等のガスを流入させることにより、系内が還
元性雰囲気になり、酸素欠陥の多い膜が得られ、
さらに抵抗値を下げることが可能となる。
また膜厚を調整するためには、２回以上塗布す
る必要があるが、一旦乾燥、焼成して膜を基板上
に固定した後、必要な回数塗布、乾燥、焼成を繰
り返す。この場合、最終焼成処理の後、約300℃
付近で１〜６時間ゆつくりアニールする工程が必
要となる。この際、同様に還元性雰囲気で行うと
より抵抗値の減少が可能になる。
以上複数回の工程において、塗布する溶液の濃
度、塗布回数をうまく設定することにより、膜厚
をコントロールできる。
本発明で使用される基板としては、各種のガラ
スの他、アルミナ等のセラミツクスでもよい。
なお、本発明においてソーダライムガラスを使
用する場合は、ネサ膜を形成させる前、アルカリ
の膜への拡散を防止するため、シリカのアンダー
コートが必要である。
［実施例］
以下、実施例により本発明を具体的に説明する
が、本発明は係る実施例に限定されるものではな
い。
実施例 １
２の三ツ口フラスコに、In（Ｏ−ｉ−Pr）2Cl
を0.3molとSn（Ｏ−ｎ−Bu）3をClを0.033molをと
り、これにエチレングリコールモノエチルエーテ
ルを加えて、１溶液として成膜工程にもちい
た。
この溶液は、通常の保存状態では、６カ月以上
安定でゲル化等を起こさなかつた。
さらにこの溶液を使用し、基板としてソーダラ
イムガラス（100×100）を用い、表面を充分に洗
浄した後、予めシリカコート（約1000Å）した
後、浸漬法により引き上げ速度0.3cm／secで塗布
した。その後10分間内放置し、10℃／minの昇温
速度で昇温させた後、200゜で10分間乾燥させ、同
様に10℃／minで昇温した後560℃で30分間焼成
を行つた。
使用した溶液の液組成、および得られた膜の物
性を表−１に示す。
膜の特性については、透光性、強度、密着性に
ついての試験を行い、特性の良好なものについて
は○、ひび割れ、白濁、剥がれ等がみられたもの
については、具体的に記述した。これは比較例
（表−２）についても同様である。
実施例 ２
塗膜用組成物の調整は実施例１と全く同様に行
つた。使用した溶液については、表１に示す。
この溶液５mlをとり、基板としてソーダライム
ガラス（100×100）を用い、実施例１と同様に前
処理した後、スピンコート法により膜の塗布を行
つた。塗布条件としては、最初回転数が
1000rpm／minで滴下した後、さらに2000rpm／
minに回転数を上げ、塗膜を形成せしめた。成膜
後、室温で30分放置して加水分解を行わせた後、
10℃／minの昇温速度で200℃に昇温、15分間保
持した。その後、同様に10℃／minで520℃に昇
温し、１時間焼成した。膜の物性を実施例と同様
に表−１に示す。
実施例 ３〜８
インジウムアルコキシド、スズアルコキシド組
成、モル比（In／Sn）、希釈溶媒の種類、濃度を
変化させ、その他の条件は同様にして、膜用組成
物を調整を行つた。
用いた希釈溶媒が２種類の場合、１対１の混合
溶液であり、これは比較例についても同様であ
る。
この溶液を用い、浸漬法またはスピンコート法
により、成膜を行つた。その条件は実施例１また
は２と同様である。
本実験の条件および結果を、表−１に示す。本
実施例で用いた溶液においても、ポツトライフは
６カ月以上であつた。
比較例 １〜６
変化させた条件、および表の表わし方は実施例
と全く同様である。前記条件、結果を表−２に示
す。
比較例１、２、６のポツトライフは非常にみじ
かく、１カ月以内に溶液は白濁、または沈殿を生
成した。一方、比較例３、４、５については、溶
液のポツトライフは６カ月以上と充分であつた
が、膜の特性は不良であつた。
[Industrial Application Field] The present invention relates to a composition used for forming a transparent conductive film on a substrate, and a method for forming a transparent conductive film, and more specifically to antistatic films (for liquid crystals), The present invention relates to a solution composition for a transparent conductive film useful as an electrode for solar cells, ECDs, etc., and a method for forming the film. [Prior Art] In recent years, attempts have been made to coat the surfaces of various substrates with thin films to impart desired conductive properties to the substrates. Among them, a film with a mixed composition of indium oxide and tin oxide is called an ITO film (hereinafter referred to as ITO film), and it is a film that has good transparency and conductivity, and is usually produced by PVD, vacuum evaporation, sputtering, or CVD.
(plasma CVD, thermal CVD), etc.
Currently, PVD and CVD are the mainstream, and PVD sputtering is widely used. However, the above method has problems such as slow film formation speed, large and expensive film forming equipment, and difficulty in increasing area and mass production. Therefore, considering the elimination of such drawbacks such as productivity, homogeneity, workability, economic efficiency, etc., ITO
As methods for forming ITO films and providing excellent electrical properties, methods for forming ITO films using organic solvents containing indium compounds and tin compounds by spraying, roll coating, spin coating, and dipping methods have been proposed. ing. For example, JP-A-59-198606
The publication discloses a composition consisting of a chlorine-containing indium alkoxide, a tin compound, an appropriate organic solvent, and water, and a dipping method is used to form a film using this composition. [Problems to be Solved by the Invention] However, in the above invention, substantially fully substituted tetraethoxytin is used as the tin compound, and water is added to the alkoxide system, so storage is difficult. It is very difficult to produce compositions with long pot lives, and it is very difficult to obtain reproducible data. It was also found that when a film is formed, the film thickness becomes non-uniform and cloudiness often occurs. Therefore, it is an object of the present invention to provide a composition and a method for forming a conductive film, which can provide a thin film with good conductivity over a wide composition range and a long pot life with good reproducibility. [Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have conducted intensive studies and found that by combining chlorine-containing alkoxides of a specific composition, the pot life is extremely long and reproducibility is achieved. It was discovered that a transparent conductive film with excellent conductive properties was formed, and the present invention was achieved. That is, the present invention is based on the general formula In
(OR 1 ) x Cl 3-x (However, R 1 represents an alkyl group or alkoxyalkyl group having 1 to 10 carbon atoms, and 1.0
≦x≦2.5) and a chlorine-containing indium alkoxide with the general formula Sn(OR 2 ) y Cl oy (where R 2
represents an alkyl group or an alkoxyalkyl group having 1 to 10 carbon atoms, n is 2 or 4, and n=2
If 1.0≦y≦1.8, if n=4, 2.5≦y≦
The chlorine-containing tin alkoxide shown in 3.5) is
A composition for a transparent conductive film characterized by mixing In/Sn at a molar ratio of 98/2≧In/Sn≧70/30, and the above composition, is applied to a substrate, and This method of forming a transparent conductive film is characterized by drying at ℃ and baking at 400 to 600 ℃. The alkyl group used in the present invention has 1 to 10 carbon atoms.
However, a carbon number of 2 to 5 is particularly preferable, and an alkoxyalkyl group is more preferable. Regarding Sn, there are cases where n is 2 and 4, and two possible combinations are possible, but either case may be used. The concentration of the composition of the present invention is preferably 0.1 to 1.0 mol/in total of chlorine-containing tin alkoxide and chlorine-containing indium alkoxide. 1 if the total concentration of both is less than 0.1 mol/
Because the thickness of the film that is applied once is too thin, the number of times of overcoating is too large, and the transparency and conductive properties of the film itself are poor. On the other hand, if the concentration exceeds 1.0 mol/l, the coating film formed at one time is too thick, and the coating film is likely to crack, making it difficult to obtain a film with excellent conductive properties. A conductive film composition having such a composition and concentration has a very long pot life, and does not undergo hydrolysis or precipitation for more than 6 months under normal storage conditions. These solutions may be diluted with a solvent,
Examples of diluent solvents include hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, alcohols such as n-propanol, i-propanol, n-butanol, and i-butanol, ethyl acetate, butyl acetate, etc. Examples include acetic acid ester, ketones such as diethyl ketone and acetone, ethers such as ethylene glycol monoethyl ether, THF, chloroform, etc. After diluting with these solvents, films can be formed under various conditions. As a coating method, a spray method, a roll coating method, a screen printing method, a spin coating method, and a dipping method can be used to form a film, and the dipping method and the spin coating method are preferable. Furthermore, conditions such as temperature and humidity during coating must be strictly controlled because they are greatly affected by the rate of hydrolysis. After forming a film by the above method, it is left at room temperature for about 5 minutes to 1 hour, and the alkoxide is sufficiently gelled by moisture in the air. After that, drying at room temperature to 200℃ for 10 minutes to 1 hour frees organic matter, remaining solvent,
and allow moisture to evaporate. At that time, suddenly 200
When dried at temperatures above ℃, the film tends to become cloudy and shrink due to the difference in drying speed between the surface and the inside. Finally, by firing at a temperature of 400 to 600°C, organic substances are scattered by oxidative decomposition, and metals also become oxides. In this drying and firing process, the rate of temperature rise is very important.If the temperature is heated slowly within 10℃/min, a dense and transparent film can be obtained.However, if the rate of temperature rise is too fast, it may cause fine cracks. It's easy to become. Furthermore, the conductive properties of the film vary greatly depending on the firing temperature, and 470 to 520°C exhibits the lowest resistance value and is more preferable. Furthermore, the atmosphere during firing also has a large effect on the conductive properties. Normally, firing is performed in an oxidizing atmosphere, but when firing at 400 to 600°C, hydrogen is added externally.
By introducing a gas such as nitrogen, the system becomes a reducing atmosphere and a film with many oxygen defects is obtained.
It becomes possible to further lower the resistance value. Further, in order to adjust the film thickness, it is necessary to apply the film two or more times, but once the film is fixed on the substrate by drying and baking, the coating, drying, and baking are repeated as many times as necessary. In this case, after the final firing process, approximately 300℃
A slow annealing process for 1 to 6 hours is required nearby. At this time, the resistance value can be further reduced by similarly performing in a reducing atmosphere. In the multiple steps described above, the film thickness can be controlled by appropriately setting the concentration of the solution to be applied and the number of times of application. In addition to various glasses, the substrate used in the present invention may be made of ceramics such as alumina. Note that when soda lime glass is used in the present invention, a silica undercoat is required before forming the Nesa film in order to prevent alkali from diffusing into the film. [Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Example 1 In (O-i-Pr) 2 Cl into the 2-necked flask
0.3 mol of Sn(O-n-Bu) 3 and 0.033 mol of Cl were taken, and ethylene glycol monoethyl ether was added thereto to form a single solution which was used in the film forming process. This solution was stable for more than 6 months and did not undergo gelation under normal storage conditions. Furthermore, using this solution, using soda lime glass (100 x 100) as a substrate, after thoroughly cleaning the surface and coating it with silica (approximately 1000 Å) in advance, it was coated by dipping at a pulling speed of 0.3 cm/sec. . After that, it was left to stand for 10 minutes, heated at a rate of 10°C/min, dried at 200° for 10 minutes, and then heated at 10°C/min for 30 minutes at 560°C. . Table 1 shows the liquid composition of the solution used and the physical properties of the obtained membrane. Regarding the properties of the film, tests were conducted on translucency, strength, and adhesion, and those with good properties were marked as ○, and those with cracks, cloudiness, peeling, etc. were described in detail. This also applies to the comparative example (Table 2). Example 2 A coating composition was prepared in exactly the same manner as in Example 1. The solutions used are shown in Table 1. 5 ml of this solution was taken and pretreated in the same manner as in Example 1 using soda lime glass (100 x 100) as a substrate, and then a film was applied by spin coating. The coating conditions are as follows:
After dropping at 1000rpm/min, further 2000rpm/min.
The rotation speed was increased to min to form a coating film. After the film was formed, it was left at room temperature for 30 minutes to undergo hydrolysis.
The temperature was raised to 200°C at a heating rate of 10°C/min and held for 15 minutes. Thereafter, the temperature was raised to 520°C at a rate of 10°C/min and fired for 1 hour. The physical properties of the membrane are shown in Table 1 as in the Examples. Examples 3 to 8 Film compositions were prepared by changing the compositions of indium alkoxide and tin alkoxide, the molar ratio (In/Sn), the type and concentration of the diluting solvent, and keeping the other conditions the same. When two types of diluent solvents were used, it was a 1:1 mixed solution, and the same was true for the comparative example. Using this solution, film formation was performed by a dipping method or a spin coating method. The conditions are the same as in Example 1 or 2. The conditions and results of this experiment are shown in Table-1. The solution used in this example also had a pot life of 6 months or more. Comparative Examples 1 to 6 The changed conditions and the way the tables are presented are exactly the same as in the examples. The conditions and results are shown in Table 2. The pot lives of Comparative Examples 1, 2, and 6 were very short, and the solutions became cloudy or formed a precipitate within one month. On the other hand, in Comparative Examples 3, 4, and 5, the pot life of the solution was sufficient at 6 months or more, but the properties of the membrane were poor.
【表】【table】
【表】【table】
【表】【table】
【表】
［発明の効果］
本発明に組成物は、従来の薬液に比べポツトラ
イフが非常に長く、塗布液として使用し、成膜し
た場合、再現性よく導電特性、透光性、膜強度等
の優れた透明性導電性を得ることができる。ま
た、他の金属を含むアルコキシドと組合せること
により、さらに膜強度等の特性を改善することが
できる。[Table] [Effects of the Invention] The composition of the present invention has a very long pot life compared to conventional chemical solutions, and when used as a coating solution and formed into a film, it has excellent conductivity properties, translucency, film strength, etc. with good reproducibility. Excellent transparency and conductivity can be obtained. Further, by combining it with an alkoxide containing another metal, properties such as film strength can be further improved.
Claims (1)
１〜10のアルキル基またはアルコキシアルキル基
を示し、1.0≦ｘ≦2.5）で示される塩素含有イン
ジウムアルコキシドと、一般式Sn（OR2）yClo-y
（ただし、R2は炭素数１〜10のアルキル基または
アルコキシアルキル基を示し、ｎは２または４で
あり、ｎ＝２の場合、1.0≦ｙ≦1.8、ｎ＝４の場
合 2.5≦ｙ≦3.5）で示される塩素含有スズアル
コキシドを、In／Snのモル比で98／２≧In／Sn
≧70／30の割合で混合することを特徴とする透明
導電性膜用組成物。 ２ 一般式In（OR1）xCl3-x（ただし、R1は炭素数
１〜10のアルキル基またはアルコキシアルキル基
を示し、1.0≦ｘ≦2.5）で示される塩素含有イン
ジウムアルコキシドと、一般式Sn（OR2）yClo-y
（ただし、R2は炭素数１〜10のアルキル基または
アルコキシアルキル基を示し、ｎは２または４で
あり、ｎ＝２の場合、1.0≦ｙ≦1.8、ｎ＝４の場
合 2.5≦ｙ≦3.5）で示される塩素含有スズアル
コキシドを、In／Snのモル比で98／２≧In／Sn
≧70／30の割合で混合した透明導電性膜用組成物
を、基板に塗布し、室温〜200℃で乾燥し、400〜
600℃で焼成することを特徴とする透明導電性膜
の形成方法。[Claims] 1 Chlorine represented by the general formula In(OR 1 ) x Cl 3-x (wherein R 1 represents an alkyl group or an alkoxyalkyl group having 1 to 10 carbon atoms, and 1.0≦x≦2.5) Containing indium alkoxide and general formula Sn(OR 2 ) y Cl oy
(However, R2 represents an alkyl group or an alkoxyalkyl group having 1 to 10 carbon atoms, n is 2 or 4, and when n=2, 1.0≦y≦1.8, and when n=4, 2.5≦y≦ The chlorine-containing tin alkoxide shown in 3.5) has an In/Sn molar ratio of 98/2≧In/Sn.
A composition for a transparent conductive film, characterized in that it is mixed at a ratio of ≧70/30. 2 Chlorine- containing indium alkoxide represented by the general formula In ( OR 1 ) Formula Sn (OR 2 ) y Cl oy
(However, R2 represents an alkyl group or an alkoxyalkyl group having 1 to 10 carbon atoms, n is 2 or 4, and when n=2, 1.0≦y≦1.8, and when n=4, 2.5≦y≦ The chlorine-containing tin alkoxide shown in 3.5) has an In/Sn molar ratio of 98/2≧In/Sn.
A transparent conductive film composition mixed at a ratio of 70/30 is applied to a substrate, dried at room temperature to 200°C, and heated to a temperature of 400°C to
A method for forming a transparent conductive film characterized by firing at 600°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62272651A JPH01115010A (en) | 1987-10-28 | 1987-10-28 | Composition for transparent conductive film and forming method for film thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62272651A JPH01115010A (en) | 1987-10-28 | 1987-10-28 | Composition for transparent conductive film and forming method for film thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01115010A JPH01115010A (en) | 1989-05-08 |
| JPH0530001B2 true JPH0530001B2 (en) | 1993-05-07 |
Family
ID=17516890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62272651A Granted JPH01115010A (en) | 1987-10-28 | 1987-10-28 | Composition for transparent conductive film and forming method for film thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01115010A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4893377B2 (en) * | 2007-03-06 | 2012-03-07 | パナソニック電工株式会社 | Electric bed |
| DE102009054997B3 (en) * | 2009-12-18 | 2011-06-01 | Evonik Degussa Gmbh | Process for producing indium oxide-containing layers, indium oxide-containing layers produced by the process and their use |
| DE102009054998A1 (en) * | 2009-12-18 | 2011-06-22 | Evonik Degussa GmbH, 45128 | Process for the preparation of indium chlorodialkoxides |
| DE102010043668B4 (en) | 2010-11-10 | 2012-06-21 | Evonik Degussa Gmbh | Process for producing indium oxide-containing layers, indium oxide-containing layers produced by the process and their use |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59198608A (en) * | 1983-04-27 | 1984-11-10 | 三菱マテリアル株式会社 | Composition for forming transparent conductive film |
| JPS59198606A (en) * | 1983-04-27 | 1984-11-10 | 三菱マテリアル株式会社 | Composition for forming transparent conductive film |
-
1987
- 1987-10-28 JP JP62272651A patent/JPH01115010A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59198608A (en) * | 1983-04-27 | 1984-11-10 | 三菱マテリアル株式会社 | Composition for forming transparent conductive film |
| JPS59198606A (en) * | 1983-04-27 | 1984-11-10 | 三菱マテリアル株式会社 | Composition for forming transparent conductive film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01115010A (en) | 1989-05-08 |
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