JPH07182939A - Transparent conducting film forming composition and transparent conducting film forming method - Google Patents
Transparent conducting film forming composition and transparent conducting film forming methodInfo
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- JPH07182939A JPH07182939A JP32384193A JP32384193A JPH07182939A JP H07182939 A JPH07182939 A JP H07182939A JP 32384193 A JP32384193 A JP 32384193A JP 32384193 A JP32384193 A JP 32384193A JP H07182939 A JPH07182939 A JP H07182939A
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- transparent conductive
- conductive film
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- conducting film
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は圧電半導体材料、透明導
電膜等として使用される、透明導電膜形成用組成物、及
び透明導電膜形成方法に関する。さらに詳しくは、酸化
亜鉛系薄膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for forming a transparent conductive film and a method for forming a transparent conductive film, which are used as a piezoelectric semiconductor material, a transparent conductive film and the like. More specifically, it relates to a zinc oxide thin film.
【０００２】[0002]
【従来の技術】近年、デバイス構成の上で透明電極が不
可欠な各種フラットパネル・ディスプレイや薄膜太陽電
池の開発が活発化してきており、それに伴い、透明導電
膜の使用が多くなってきている。圧電半導体の材料とし
て広く使用されてきた酸化亜鉛系薄膜は、透明導電膜の
一種であり、高い可視光透過率を有し、低温成膜が可能
であり、還元されにくい、という長所を有している。2. Description of the Related Art In recent years, development of various flat panel displays and thin film solar cells in which transparent electrodes are indispensable for device construction has been activated, and along with this, the use of transparent conductive films has increased. The zinc oxide thin film, which has been widely used as a material for piezoelectric semiconductors, is a type of transparent conductive film, has the advantages of high visible light transmittance, low temperature film formation, and difficulty in reduction. ing.
【０００３】従来、酸化亜鉛系薄膜の形成は、アルキル
亜鉛、有機酸亜鉛または亜鉛アルコキシドを有機溶媒に
溶解した液を用いて基板上に塗布し、焼成することによ
って得ていた。Conventionally, the formation of a zinc oxide type thin film has been obtained by coating a substrate with a solution prepared by dissolving an alkyl zinc, an organic zinc salt or a zinc alkoxide in an organic solvent and baking it.
【０００４】[0004]
【発明が解決しようとする課題】しかし、アルキル亜鉛
は発火性があるため、塗布液の調製・保管時および焼成
時に非常な注意を払わなければならず、取扱いが困難で
あった。However, since alkyl zinc is ignitable, great care must be taken when preparing and storing the coating solution and at the time of baking, and it is difficult to handle.
【０００５】一方、有機酸亜鉛や亜鉛アルコキシドは、
基板との濡れ性および溶媒への溶解性が悪いために作業
性が悪く、薄膜の作製が容易でないという問題を有して
いた。また、溶解性が悪いことから、塗布液の貯蔵安定
性も低かった。On the other hand, organic acid zinc and zinc alkoxide are
Since the wettability with the substrate and the solubility in the solvent are poor, the workability is poor, and there is a problem that it is not easy to form a thin film. Further, since the solubility was poor, the storage stability of the coating solution was low.
【０００６】本発明の目的は、上記の問題点を解消した
透明導電膜形成用組成物、及び透明導電膜形成方法の提
供である。An object of the present invention is to provide a composition for forming a transparent conductive film and a method for forming a transparent conductive film, which solve the above problems.
【０００７】[0007]
【課題を解決するための手段】本発明者は、アルキル亜
鉛をアルコールまたはキレート化剤と反応させて得た有
機亜鉛化合物が、発火性がなく、かつ溶解性が大きく、
取扱い容易で成膜性に優れており、これを用いて上記目
的が達成できることを見出した。The present inventors have found that an organozinc compound obtained by reacting an alkylzinc with an alcohol or a chelating agent is non-ignitable and highly soluble.
It has been found that the above-mentioned object can be achieved by using it because it is easy to handle and has excellent film-forming property.
【０００８】本発明の要旨とするところは、下記一般式
(1) または(2) [R1−Zn−(OR2)]4 (1) [R1−Zn←R3]4 (2) （式中、R1およびR2はそれぞれアルキル、アリール、ま
たはアラルキル基であり、R3は多座配位子である）で表
される有機亜鉛化合物の有機溶媒溶液からなる、透明導
電膜形成用組成物である。The gist of the present invention lies in the following general formula
(1) or (2) [R 1 −Zn− (OR 2 )] 4 (1) [R 1 −Zn ← R 3 ] 4 (2) (In the formula, R 1 and R 2 are each alkyl, aryl, Or a aralkyl group, and R 3 is a polydentate ligand), which is a composition for forming a transparent conductive film, comprising a solution of an organic zinc compound represented by the formula ( 3 ).
【０００９】得られる酸化亜鉛系薄膜の導電性を増大さ
せるために、この溶液にさらにドーパントとして、Ｂ、
Al、Ga、またはInの化合物を溶解状態で含有させてもよ
い。In order to increase the conductivity of the obtained zinc oxide thin film, B was added to this solution as a dopant.
A compound of Al, Ga, or In may be contained in a dissolved state.
【００１０】前記透明導電膜形成用組成物は、これを
基板に塗布し焼成するか、あるいはこれをミスト化し
て加熱した基板と接触させると、亜鉛化合物（およびド
ーパント）が基板上で熱分解し、基板上に透明導電膜す
なわち酸化亜鉛系薄膜を形成することができる。When the transparent conductive film-forming composition is applied to a substrate and baked, or when the composition is made into a mist and brought into contact with a heated substrate, the zinc compound (and the dopant) is thermally decomposed on the substrate. A transparent conductive film, that is, a zinc oxide-based thin film can be formed on the substrate.
【００１１】本発明の透明導電膜形成用組成物は、前記
一般式(1) または(2) で表される有機亜鉛化合物を適当
な有機溶媒に溶解した溶液からなる。The composition for forming a transparent conductive film of the present invention comprises a solution prepared by dissolving the organozinc compound represented by the general formula (1) or (2) in a suitable organic solvent.
【００１２】一般式(1) ならびに(2) におけるR1基およ
びR2基の具体例としては、メチル基、エチル基、ｎ−プ
ロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル
基、ｔ−ブチル基などのアルキル基；フェニル基、ビフ
ェニル基、ナフチル基などのアリール基；ベンジル基、
フェネチル基などのアラルキル基が挙げられる。アリー
ル基の芳香環は置換基を有していてもよい。Specific examples of the R 1 group and the R 2 group in the general formulas (1) and (2) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an i-butyl group. Group, alkyl group such as t-butyl group; aryl group such as phenyl group, biphenyl group and naphthyl group; benzyl group
An aralkyl group such as a phenethyl group may be mentioned. The aromatic ring of the aryl group may have a substituent.
【００１３】一般式(2) の多座配位子R3の例には、β−
ジケトン、β−イミノケトン、ジアミン、アミノアルコ
ール、アルコキシアルコール、オキシエステル、グリコ
ールなどがある。具体例としては、アセチルアセトン、
エチレンジアミン、モノエタノールアミン、ジエタノー
ルアミン、メトキシエチルアルコール、オキソブタン酸
エチル、エチレングリコールなどが挙げられる。Examples of the polydentate ligand R 3 of the general formula (2) include β-
Examples include diketone, β-imino ketone, diamine, amino alcohol, alkoxy alcohol, oxyester, glycol and the like. As a specific example, acetylacetone,
Examples thereof include ethylenediamine, monoethanolamine, diethanolamine, methoxyethyl alcohol, ethyl oxobutanoate, and ethylene glycol.
【００１４】一般式(1) の有機亜鉛化合物は、Zn(R1)2
で示されるジアルキル、ジアリールまたはジアラルキル
亜鉛化合物を、アルコールまたはフェノールなどのモノ
ヒドロキシ化合物R2OHと反応させることにより合成でき
る。例えばR2OHが、メタノール、エタノール、ｎ−プロ
ピルアルコール、ｉ−プロピルアルコール、ｎ−ブチル
アルコール、ｉ−ブチルアルコールのように液状アルコ
ールである場合、亜鉛化合物Zn(R1)2 をペンタン、ｎ−
ヘキサン、ヘプタン、石油エーテル、ベンゼンなどの適
当な有機溶媒に溶解する。次にこの溶液をアルコールR2
OH中に滴下し、得られた混合物を攪拌または加熱攪拌し
て反応を行う。R2OHが固体の場合は、加熱溶融するか、
或いは適当な溶媒で溶液化して同様に反応させることが
できる。アルコールR2OHとZn(R1)2 とはほぼ等モルで反
応させるのがよい。反応温度は一般に０〜80℃の範囲内
である。The organozinc compound of the general formula (1) is Zn (R 1 ) 2
It can be synthesized by reacting a dialkyl, diaryl or diaralkylzinc compound represented by with an monohydric compound R 2 OH such as alcohol or phenol. For example, when R 2 OH is a liquid alcohol such as methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, zinc compound Zn (R 1 ) 2 is replaced with pentane, n −
It is soluble in a suitable organic solvent such as hexane, heptane, petroleum ether, benzene. This solution is then alcohol R 2
The mixture is added dropwise to OH, and the resulting mixture is stirred or heated and stirred to carry out the reaction. If R 2 OH is solid, melt by heating or
Alternatively, it can be made into a solution with an appropriate solvent and similarly reacted. The alcohol R 2 OH and Zn (R 1 ) 2 are preferably reacted in approximately equimolar amounts. The reaction temperature is generally within the range of 0 to 80 ° C.
【００１５】一般式(2) の有機亜鉛化合物も、一般式
(1) の有機亜鉛化合物の場合とほぼ同様に、有機亜鉛化
合物Zn(R1)2 をキレート化剤と反応させることにより合
成できる。多座配位子として、アミノアルコール（例：
ジエタノールアミン）、β−ジケトン（例：アセチルア
セトン）のような求核性の強い物質を使用する場合に
は、１段階で反応させると反応が不安定で生成物の収率
が悪いため、まず原料のZn(R1)2 を求核性の弱い配位子
（例：アルコキシアルコール）と反応させ、次にその反
応物とジエタノールアミンを反応させて配位子を交換す
るという２段階の反応によって目的化合物を得ることが
できる。The organozinc compound of the general formula (2) is also represented by the general formula
It can be synthesized by reacting the organozinc compound Zn (R 1 ) 2 with a chelating agent in almost the same manner as in the case of the organozinc compound ( 1 ). Amino alcohols (eg:
When using a highly nucleophilic substance such as diethanolamine) or β-diketone (eg acetylacetone), the reaction is unstable and the product yield is poor if the reaction is carried out in one step. Zn (R 1 ) 2 is reacted with a weakly nucleophilic ligand (eg, alkoxy alcohol), and then the reaction product is reacted with diethanolamine to exchange the ligand to exchange the target compound. Can be obtained.
【００１６】こうして得た一般式(1) または(2) の有機
亜鉛化合物の溶液を必要に応じて適当な粘度になるま
で、上記のような有機溶媒で希釈すると本発明の透明導
電膜形成用組成物が得られる。The solution of the organozinc compound of the general formula (1) or (2) thus obtained is diluted with the above-mentioned organic solvent until a suitable viscosity is obtained, if necessary, to form the transparent conductive film of the present invention. A composition is obtained.
【００１７】本発明の組成物は、導電性を増大させるた
めに、さらにドーパントとして、Ｂ、Al、Ga、またはIn
の化合物を溶解状態で含有していてもよい。ドーパント
としては、次のような化合物が使用できる。The composition of the present invention further comprises B, Al, Ga, or In as a dopant to increase conductivity.
The compound may be contained in a dissolved state. The following compounds can be used as the dopant.
【００１８】 H3BO3, B(OR)m(OH)3-m, NH4BF4, Al(OR)m(R3)3-m, Ga(OR)m(R3)3-m, In(OR)m(R3)3-m 式中のＲはアルキル基であり、メチル基、エチル基、ｎ
−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブ
チル基などが好ましく；R3は前述したような多座配位子
である。また、ｍは０〜３である。[0018] H 3 BO 3, B (OR ) m (OH) 3-m, NH 4 BF 4, Al (OR) m (R 3) 3-m, Ga (OR) m (R 3) 3-m , In (OR) m (R 3 ) 3-m In the formula, R is an alkyl group, methyl group, ethyl group, n
- propyl, i- propyl, n- butyl group, etc. i- butyl group are preferable; R 3 is a polydentate ligand as described above. Further, m is 0 to 3.
【００１９】上記のドーパントの添加量は、有機亜鉛化
合物中の亜鉛に対するドーパント中の金属の原子％とし
て0.１〜４％の範囲内が好ましい。ドーパントを添加す
ると、形成された膜の導電性は増大するが、その透明性
はやや低下する傾向があるので、目的とする用途に必要
な特性を考慮して、ドーパントの添加の有無や添加量を
決定すれば良い。The amount of the above-mentioned dopant added is preferably in the range of 0.1 to 4% as the atomic% of the metal in the dopant with respect to the zinc in the organozinc compound. When a dopant is added, the conductivity of the formed film increases, but its transparency tends to decrease slightly.Therefore, in consideration of the properties required for the intended use, the presence or absence of addition of a dopant and the amount added Should be decided.
【００２０】本発明の透明導電膜形成用組成物を基板に
塗布し、焼成すると、有機亜鉛化合物とドーパント (存
在する場合) が熱分解し、所望によりドープされた酸化
亜鉛の薄膜が形成される。基板への塗布は、スプレー
法、スピンコート法などの慣用手段により実施でき、焼
成は大気雰囲気で 400〜700 ℃の温度範囲内に0.５〜３
時間加熱することにより実施できる。必要であれば、所
望の膜厚（例、0.05〜１μｍ）になるまで、塗布と焼成
を繰り返してもよい。When the composition for forming a transparent conductive film of the present invention is applied to a substrate and baked, the organozinc compound and the dopant (if present) are thermally decomposed to form a thin film of zinc oxide doped as desired. . The coating on the substrate can be carried out by a conventional method such as a spray method or a spin coating method, and the baking is carried out in the temperature range of 400 to 700 ° C. in the atmosphere of 0.5 to 3 times.
It can be carried out by heating for a time. If necessary, coating and baking may be repeated until a desired film thickness (eg, 0.05 to 1 μm) is obtained.
【００２１】また、本発明の透明導電膜形成用組成物を
超音波式ミスト発生器等によりミスト化し、このミスト
を酸素、窒素、アルゴン等をキャリアーガスとして用い
て加熱した基板上に導き、基板上で亜鉛化合物およびド
ーパントを熱分解させて、酸化亜鉛系の透明導電膜を形
成することもできる。基板の温度は50〜700 ℃、好適に
は 400〜700 ℃で行う。この方法によると塗布後焼成し
て透明導電膜を得る場合に比べて体積抵抗率は若干劣る
が、ミスト化することにより凹凸のある基板上でも均一
に成膜できる。つまり、スピンコート法、ディップ法等
の他の成膜法に比べて、基板の形状を選ばず、成膜速度
が速いという点で優れている。この場合も基板の温度は
400〜700 ℃の範囲内とすることが望ましい。Further, the composition for forming a transparent conductive film of the present invention is made into a mist by an ultrasonic mist generator or the like, and this mist is introduced onto a heated substrate using oxygen, nitrogen, argon or the like as a carrier gas to form a substrate. A zinc oxide-based transparent conductive film can be formed by thermally decomposing the zinc compound and the dopant. The temperature of the substrate is 50 to 700 ° C, preferably 400 to 700 ° C. According to this method, the volume resistivity is slightly inferior to the case where a transparent conductive film is obtained by baking after coating, but by forming a mist, a uniform film can be formed even on a substrate having irregularities. That is, it is superior to other film forming methods such as the spin coating method and the dipping method in that the shape of the substrate is not selected and the film forming rate is high. Also in this case, the substrate temperature is
It is desirable to set the temperature within the range of 400 to 700 ° C.
【００２２】場合により、得られた透明導電膜の導電性
の向上のために、この薄膜の水素処理を行ってもよい。
水素処理の温度は 300〜600 ℃、処理時間は0.５〜３時
間が適当である。In some cases, the thin film may be subjected to hydrogen treatment in order to improve the conductivity of the obtained transparent conductive film.
The hydrogen treatment temperature is 300 to 600 ° C., and the treatment time is 0.5 to 3 hours.
【００２３】本発明の透明導電膜形成用組成物を用いて
透明導電膜を形成する場合、使用した一般式(1) または
(2) の有機亜鉛化合物が、金属やセラミックなどの基板
との濡れ性がよく、有機溶媒への溶解性が良好であるこ
とから、平滑で均一な透明導電膜を形成することができ
る。また、この有機亜鉛化合物の有機溶媒への溶解性が
良好であることから、溶液の貯蔵安定性が高く、ゲル化
を生ずることなく長期間保存できる。When a transparent conductive film is formed using the composition for forming a transparent conductive film of the present invention, the general formula (1) or
Since the organozinc compound (2) has good wettability with a substrate such as metal or ceramic and has good solubility in an organic solvent, a smooth and uniform transparent conductive film can be formed. Moreover, since the organozinc compound has good solubility in an organic solvent, the solution has high storage stability and can be stored for a long period of time without gelation.
【００２４】[0024]
【実施例１】ジエチル亜鉛（関東化学社製）12.4 g (0.
10 mol) をｎ−ヘキサン300 mLに溶解した溶液に、ｉ−
プロピルアルコール（関東化学社製）6.0 g (0.097 mo
l) を滴下し、得られた溶液を30℃で４時間攪拌した。
この溶液を減圧濃縮した後、ｎ−ブチルアルコールにて
３重量％濃度の溶液に調整し、透明導電膜形成用組成物
を得た。[Example 1] Diethyl zinc (manufactured by Kanto Chemical Co., Inc.) 12.4 g (0.
10 mol) in a solution of 300 mL of n-hexane, i-
Propyl alcohol (Kanto Chemical Co., Inc.) 6.0 g (0.097 mo
l) was added dropwise, and the resulting solution was stirred at 30 ° C. for 4 hours.
After concentrating this solution under reduced pressure, it was adjusted to a solution having a concentration of 3% by weight with n-butyl alcohol to obtain a composition for forming a transparent conductive film.
【００２５】[0025]
【実施例２〜４】アルコールをそれぞれメチルアルコー
ル、ｔ−ブチルアルコール、メトキシエチルアルコール
に変えた以外は実施例１と同様に反応を行い、反応で得
られた溶液をｎ−ブチルアルコールにより３重量％溶液
に調整して、透明導電膜形成用組成物を得た。Examples 2 to 4 The reaction was performed in the same manner as in Example 1 except that the alcohol was changed to methyl alcohol, t-butyl alcohol, and methoxyethyl alcohol, and the solution obtained by the reaction was mixed with n-butyl alcohol in an amount of 3% by weight. % Solution to obtain a transparent conductive film-forming composition.
【００２６】[0026]
【実施例５】実施例１〜４で調製した透明導電膜形成用
組成物を、石英ガラス基板上に、1000 rpm、30秒の条件
でスピンコートにより塗布し、塗膜を150 ℃で10分間乾
燥させた後、大気中で600 ℃×１時間の焼成を行って酸
化亜鉛の透明導電膜を得た。この塗布・焼成を３回繰り
返し、膜厚を2000Åとした。その後、500 ℃で１時間の
水素処理をさらに行った。得られた透明導電膜につい
て、直流四端針法による体積抵抗率と日本分光製UBEST
55型分光光度計を用いた可視域での透過率とを求めた。
その測定結果を表１に示す。Example 5 The transparent conductive film-forming compositions prepared in Examples 1 to 4 were applied onto a quartz glass substrate by spin coating under the conditions of 1000 rpm and 30 seconds, and the coating film was formed at 150 ° C. for 10 minutes. After drying, baking was performed in the air at 600 ° C. for 1 hour to obtain a transparent conductive film of zinc oxide. This coating / baking was repeated 3 times to give a film thickness of 2000Å. After that, hydrogen treatment was further performed at 500 ° C. for 1 hour. About the obtained transparent conductive film, the volume resistivity by the DC four-end needle method and the JASCO UBEST
The transmittance in the visible region was measured using a 55 type spectrophotometer.
The measurement results are shown in Table 1.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【実施例６】実施例１〜４で調製した溶液に、ドーパン
トとして表２に示した各金属化合物を有機亜鉛化合物中
の亜鉛に対するドーパント中の金属が２原子％となるよ
うに添加し、実施例５と同様にして基板への塗布および
焼成を行い、酸化亜鉛系の透明導電膜を得た。ドーパン
トには、以下に示す金属化合物を用いた。Example 6 To the solutions prepared in Examples 1 to 4, each metal compound shown in Table 2 was added as a dopant so that the metal in the dopant with respect to zinc in the organozinc compound was 2 atom%, and The substrate was coated and baked in the same manner as in Example 5 to obtain a zinc oxide-based transparent conductive film. The metal compound shown below was used for the dopant.
【００２９】 Ｂ： H3BO3、B(OC2H5)3 、B(OC2H5)2OH Al： Al[O(CH2)3CH3]3、Al[O(CH2)3CH3]2NH(C2H4O) Ga： Ga[OCH(CH3)2]3 、Ga[O(CH2)3CH3]3 、 Ga[OCH(CH
3)2]2(C5H7O2) In： In[O(CH2)3CH3]3、In[O(CH2)3CH3]2NH(C2H4O) 得られた薄膜について、実施例５と同様な方法で評価を
行った。結果は表２に示す通りである。ドーパントの添
加により、体積抵抗率は低下（導電性は増大）したが、
透明性はいくらか低下した。B: H 3 BO 3 , B (OC 2 H 5 ) 3 , B (OC 2 H 5 ) 2 OH Al: Al [O (CH 2 ) 3 CH 3 ] 3 , Al [O (CH 2 ). 3 CH 3 ] 2 NH (C 2 H 4 O) Ga: Ga [OCH (CH 3 ) 2 ] 3 , Ga [O (CH 2 ) 3 CH 3 ] 3 , Ga [OCH (CH
3 ) 2 ] 2 (C 5 H 7 O 2 ) In: In [O (CH 2 ) 3 CH 3 ] 3 , In [O (CH 2 ) 3 CH 3 ] 2 NH (C 2 H 4 O) The thin film was evaluated in the same manner as in Example 5. The results are shown in Table 2. Although the volume resistivity decreased (the conductivity increased) due to the addition of the dopant,
The transparency was somewhat reduced.
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【実施例７】ジエチル亜鉛（関東化学社製）12.4 g (0.
10 mol) をｎ−ヘキサン300 mLに溶解した溶液を、メト
キシエチルアルコール（関東化学社製）7.6 g (0.11 mo
l)に滴下し、得られた溶液を30℃で４時間攪拌した。こ
の溶液を減圧濃縮後、メトキシエチルアルコールおよび
ｎ−ブチルアルコールにて５重量％濃度に調整した。次
いで、亜鉛と等モル量のジエタノールアミン（関東化学
社製）を加えたところ、均一で透明な有機亜鉛化合物溶
液を得た。得られた有機亜鉛化合物は、[C2H5-Zn-OC2H4
NHC2H4OH]4である。Example 7 Diethyl zinc (manufactured by Kanto Chemical Co., Inc.) 12.4 g (0.
A solution prepared by dissolving 10 mol) in 300 mL of n-hexane was added with 7.6 g (0.11 mo) of methoxyethyl alcohol (Kanto Chemical Co., Inc.).
l) and the resulting solution was stirred at 30 ° C. for 4 hours. This solution was concentrated under reduced pressure and then adjusted to a concentration of 5% by weight with methoxyethyl alcohol and n-butyl alcohol. Then, when diethanolamine (manufactured by Kanto Chemical Co., Inc.) in an equimolar amount to zinc was added, a uniform and transparent organic zinc compound solution was obtained. The obtained organozinc compound is [C 2 H 5 -Zn-OC 2 H 4
NHC 2 H 4 OH] 4 .
【００３２】この溶液を密封容器内で室温にて３か月間
保存した後、溶液の状態を調べた。沈殿、分離等は認め
られず、極めて安定であることが判明した。After the solution was stored in a sealed container at room temperature for 3 months, the state of the solution was examined. No precipitation or separation was observed, and it was found to be extremely stable.
【００３３】[0033]
【実施例８】実施例７で調製した溶液を用い、実施例５
と同様にして基板への塗布および焼成を行い、透明導電
膜を得た。その薄膜について実施例５と同様な方法で評
価を行ったところ、体積抵抗率3.4 ×10-1Ω・cm、光透
過率95％以上であった。この溶液は、基板への濡れ性に
優れており、この溶液によって得られた透明導電膜は、
圧電フィルターおよび振動子として利用できる。Example 8 Using the solution prepared in Example 7, Example 5
Application and baking were performed on the substrate in the same manner as in 1. to obtain a transparent conductive film. When the thin film was evaluated in the same manner as in Example 5, the volume resistivity was 3.4 × 10 −1 Ω · cm and the light transmittance was 95% or more. This solution has excellent wettability to the substrate, and the transparent conductive film obtained by this solution is
It can be used as a piezoelectric filter and vibrator.
【００３４】[0034]
【実施例９】実施例７で調製した溶液に、ドーパントと
してＢ、Al、Ga、またはInのアルコキシドを、それぞれ
有機亜鉛化合物中の亜鉛に対してドーパント金属が２原
子％となるように添加し、実施例５と同様にして基板へ
の塗布および焼成を行い、酸化亜鉛系の透明導電膜を得
た。その薄膜について実施例５と同様な方法で評価を行
った。結果は表３に示す通りである。Example 9 To the solution prepared in Example 7, an alkoxide of B, Al, Ga or In was added as a dopant so that the dopant metal was 2 atom% with respect to zinc in the organozinc compound. Then, coating and baking were performed on the substrate in the same manner as in Example 5 to obtain a zinc oxide-based transparent conductive film. The thin film was evaluated in the same manner as in Example 5. The results are shown in Table 3.
【００３５】[0035]
【表３】 [Table 3]
【００３６】[0036]
【実施例10】実施例４で調製した有機亜鉛化合物と表４
に示すドーパント化合物とを用いて、透明導電膜形成用
組成物溶液の調製を行った。この液を超音波式ミスト発
生器によりミスト化された透明導電膜形成用組成物溶液
を、酸素をキャリアーガスとして、 400〜600 ℃の基板
上に輸送した。基板上で組成物溶液は熱分解され、酸化
亜鉛系の透明導電膜が形成された。ミスト化された透明
導電膜形成用組成物溶液を20分間輸送して0.８μｍの膜
とした後、500 ℃で１時間の水素処理を行った。得られ
た透明導電膜について、直流四端針法による体積抵抗率
と日本分光製UBEST55 型分光光度計を用いた可視域での
透過率とを求めた。結果を表４に示す。Example 10 Organozinc compounds prepared in Example 4 and Table 4
A transparent conductive film-forming composition solution was prepared using the dopant compound shown in 1 above. The composition solution for forming a transparent conductive film, which was misted from this liquid with an ultrasonic mist generator, was transported onto a substrate at 400 to 600 ° C. using oxygen as a carrier gas. The composition solution was thermally decomposed on the substrate to form a zinc oxide-based transparent conductive film. The composition solution for forming a transparent conductive film in mist was transported for 20 minutes to form a 0.8 μm film, and then hydrogen treatment was performed at 500 ° C. for 1 hour. With respect to the obtained transparent conductive film, the volume resistivity by the DC four-end needle method and the transmittance in the visible region using a JASCO UBE S55 spectrophotometer were determined. The results are shown in Table 4.
【００３７】[0037]
【表４】 [Table 4]
【００３８】[0038]
【比較例１】ジエチル亜鉛 12.4 g (0.10 mol)を、発火
しないように窒素雰囲気のグローブボックス中でヘキサ
ンに溶解して３重量％の溶液とし、透明導電膜形成用組
成物とした。Comparative Example 1 12.4 g (0.10 mol) of diethylzinc was dissolved in hexane in a glove box in a nitrogen atmosphere so as not to ignite, and a 3% by weight solution was prepared to obtain a composition for forming a transparent conductive film.
【００３９】この溶液を用いて、石英ガラス基板上に、
1000 rpm、30秒の条件でスピンコートにより塗布し、塗
膜を試みたが、溶液の加水分解が非常に速く膜厚が不均
一になり、良好な膜は得られなかった。Using this solution, on a quartz glass substrate,
An attempt was made to apply a film by spin coating under the conditions of 1000 rpm and 30 seconds, but the hydrolysis of the solution was so rapid that the film thickness became uneven, and a good film could not be obtained.
【００４０】なお、本発明の透明導電膜形成用組成物を
用いた場合には、塗布液の調製・保管時および焼成時の
発火のおそれがなく溶液の安定性も良好なので、取扱い
および膜の作製が容易であった。When the composition for forming a transparent conductive film of the present invention is used, there is no risk of ignition during preparation / storage of the coating solution and baking, and the stability of the solution is good, so handling and film formation It was easy to make.
【００４１】[0041]
【比較例２】ジエトキシ亜鉛15.55g (0.10 mol) を、エ
タノールに溶解し、膜形成用組成物の調製を試みた。し
かし、難溶性のため溶液濃度は0.01重量％にしか調整で
きなかった。Comparative Example 2 15.55 g (0.10 mol) of diethoxyzinc was dissolved in ethanol to try to prepare a film-forming composition. However, due to its poor solubility, the solution concentration could only be adjusted to 0.01% by weight.
【００４２】この溶液を用いて、石英ガラス基板上に、
1000 rpm、30秒の条件でスピンコートにより塗布し、塗
膜を150 ℃で10分間乾燥させた後、大気中で600 ℃×１
時間の焼成を行って透明導電膜を得た。その膜厚は僅か
50Åであり、実施例５と同様の膜厚を得るのに20回の繰
り返し作業を要した。その後、500 ℃で１時間の水素処
理をさらに行った。得られた透明導電膜について、直流
四端針法による体積抵抗率と日本分光製UBEST 55型分光
光度計を用いた可視域での透過率とを求めた。その測定
結果は体積抵抗率は4.2 Ω・cm、光透過率80％であっ
た。Using this solution, on a quartz glass substrate,
After spin coating at 1000 rpm for 30 seconds, the coating film is dried at 150 ° C for 10 minutes and then 600 ° C x 1 in air.
A transparent conductive film was obtained by baking for a period of time. Its film thickness is small
It was 50Å, and 20 times of repeated work was required to obtain the same film thickness as in Example 5. After that, hydrogen treatment was further performed at 500 ° C. for 1 hour. With respect to the obtained transparent conductive film, the volume resistivity by the DC four-end needle method and the transmittance in the visible region using a JASCO UBEST 55 type spectrophotometer were determined. As a result of the measurement, the volume resistivity was 4.2 Ω · cm and the light transmittance was 80%.
【００４３】[0043]
【比較例３】比較例１で調製した透明導電膜形成用組成
物を密封容器内で室温にて保存した。３カ月後に、液中
で沈殿物が生じており、分離が認められた。Comparative Example 3 The composition for forming a transparent conductive film prepared in Comparative Example 1 was stored at room temperature in a sealed container. After 3 months, a precipitate had formed in the liquid and separation was observed.
【００４４】[0044]
【発明の効果】本発明の透明導電膜形成用組成物は、使
用する有機亜鉛化合物の基板への濡れ性と有機溶媒への
溶解性が良好であることから、溶液の貯蔵安定性に優れ
ている。また、アルキル亜鉛を用いて透明導電膜を得て
いた従来法で問題であった発火性においても全く心配な
く、操作が簡略化できる。本発明の組成物を用いて透明
導電膜を形成すると、平滑で透明性が高く低抵抗（４×
10-1Ω・cm以下) 、すなわち従来の透明導電膜と何ら遜
色のない、透明電極として有用な透明導電膜が形成され
る。なお、本発明の透明導電膜形成用組成物を用いて、
ミスト化し加熱した基板と接触させて透明導電膜を形成
すると、膜特性が若干劣化するが、基板の形状を選ば
ず、成膜速度が速い、すなわち厚膜作製が短時間で可能
となる透明導電膜が得られる。EFFECTS OF THE INVENTION The composition for forming a transparent conductive film of the present invention is excellent in storage stability of a solution because the organozinc compound used has good wettability to a substrate and solubility in an organic solvent. There is. Further, there is no concern about the ignitability, which was a problem in the conventional method in which a transparent conductive film was obtained using alkylzinc, and the operation can be simplified. When a transparent conductive film is formed using the composition of the present invention, it is smooth and highly transparent and has low resistance (4 ×
10 −1 Ω · cm or less), that is, a transparent conductive film which is comparable to a conventional transparent conductive film and is useful as a transparent electrode is formed. In addition, using the composition for forming a transparent conductive film of the present invention,
When a transparent conductive film is formed by bringing it into contact with a mist-heated and heated substrate, the film characteristics are slightly degraded, but the transparent conductive film enables the film formation rate to be fast regardless of the substrate shape, that is, a thick film can be produced in a short time. A film is obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宮澤 芳美 埼玉県大宮市北袋町１丁目297番地 三菱 マテリアル株式会社中央研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshimi Miyazawa 1-297, Kitabukuro-cho, Omiya-shi, Saitama Mitsubishi Materials Corporation Central Research Laboratory
Claims (4)
たはアラルキル基であり、R3は多座配位子である）で表
される有機亜鉛化合物の有機溶媒溶液からなる、透明導
電膜形成用組成物。1. The following general formula (1) or (2) [R 1 −Zn− (OR 2 )] 4 (1) [R 1 −Zn ← R 3 ] 4 (2) (wherein R 1 and R 2 is each an alkyl, aryl, or aralkyl group, and R 3 is a polydentate ligand).
Ｂ、Al、Ga、またはInの化合物を含有する、請求項１記
載の透明導電膜形成用組成物。2. The solution further as a dopant,
The composition for forming a transparent conductive film according to claim 1, which contains a compound of B, Al, Ga, or In.
用組成物を、基板に塗布し、焼成して透明導電膜を形成
することを特徴とする、透明導電膜形成方法。3. A method for forming a transparent conductive film, which comprises applying the composition for forming a transparent conductive film according to claim 1 or 2 to a substrate and baking the composition to form a transparent conductive film.
用組成物をミスト化し、このミストを加熱した基板と接
触させることにより透明導電膜を形成することを特徴と
する、透明導電膜形成方法。4. A transparent conductive film is formed by forming a mist from the composition for forming a transparent conductive film according to claim 1 or 2 and bringing the mist into contact with a heated substrate to form a transparent conductive film. Method.
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