JP2010126402A - Method for forming zinc oxide thin film - Google Patents

Method for forming zinc oxide thin film Download PDF

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JP2010126402A
JP2010126402A JP2008303132A JP2008303132A JP2010126402A JP 2010126402 A JP2010126402 A JP 2010126402A JP 2008303132 A JP2008303132 A JP 2008303132A JP 2008303132 A JP2008303132 A JP 2008303132A JP 2010126402 A JP2010126402 A JP 2010126402A
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thin film
zinc oxide
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JP5288464B2 (en
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Koichiro Inaba
孝一郎 稲葉
Koji Toyoda
浩司 豊田
Kenichi Haga
健一 羽賀
Koichi Tokutome
功一 徳留
Kenji Yoshino
賢二 吉野
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Tosoh Finechem Corp
University of Miyazaki NUC
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University of Miyazaki NUC
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a transparent zinc oxide thin film, which needs no heating or the heating to a temperature of 300°C or lower, in consideration of a heat-resistant temperature of a plastic substrate, a cost required for heating, etc. <P>SOLUTION: The method for forming the thin film includes a process of forming the thin film by spray coating of a solution containing an organozinc compound dissolved in an organic solvent, onto the surface of a substrate under an atmospheric pressure or a pressurized atmosphere, in the presence of water and at 300°C or lower temperature of the substrate. The organic solvent has an electron-donative property and the organozinc compound is expressed by the formula (1): R<SP>1</SP>-Zn-R<SP>1</SP>(wherein R<SP>1</SP>is a 1-7C linear or branched alkyl group). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、酸化亜鉛薄膜の製造方法に関する。特に本発明は、大気圧付近の圧力下、かつ３００℃以下の基板温度で行うスプレー塗布により、可視光線に対して高い透過率を有する透明酸化亜鉛薄膜を形成する、酸化亜鉛薄膜の製造方法に関する。   The present invention relates to a method for producing a zinc oxide thin film. In particular, the present invention relates to a method for producing a zinc oxide thin film, wherein a transparent zinc oxide thin film having a high transmittance with respect to visible light is formed by spray coating performed at a pressure near atmospheric pressure and at a substrate temperature of 300 ° C. or lower. .

可視光線に対して高い透過性を有する透明酸化亜鉛薄膜は、光触媒膜、紫外線カット膜、赤外線反射膜、ＣＩＧＳ太陽電池のバッファ層、色素増感太陽電池の電極膜、帯電防止膜、化合物半導体発光素子、薄膜トランジスタ等に使用され、幅広い用途を持つ。   Transparent zinc oxide thin film with high permeability to visible light is photocatalyst film, UV cut film, infrared reflective film, CIGS solar cell buffer layer, dye-sensitized solar cell electrode film, antistatic film, compound semiconductor light emission Used in devices, thin film transistors, etc., and has a wide range of uses.

透明酸化亜鉛薄膜の製造方法としては種々の方法が知られている（非特許文献１）が、有機亜鉛化合物を原料として用いる代表的な方法としては、化学気相成長（ＣＶＤ）法（非特許文献２）、スプレー熱分解法（非特許文献３）、およびスピンコート法（特許文献１）がある。   Various methods are known as a method for producing a transparent zinc oxide thin film (Non-Patent Document 1), but a typical method using an organic zinc compound as a raw material is a chemical vapor deposition (CVD) method (Non-patent Document 1). Document 2), spray pyrolysis method (Non-patent Document 3), and spin coating method (Patent Document 1).

しかしながら、化学気相成長（ＣＶＤ）法では、大型の真空容器を用いる必要があるため、および製膜速度が非常に遅いために製造コストが高くなり、また、真空容器の大きさにより形成することのできる酸化亜鉛薄膜の大きさが制限される為に大型のものを形成することができない、等の問題があった。   However, the chemical vapor deposition (CVD) method requires the use of a large vacuum vessel, and the film forming speed is very slow, resulting in high manufacturing costs and the formation of the vacuum vessel depending on the size of the vacuum vessel. There is a problem that a large-sized zinc oxide thin film cannot be formed because the size of the zinc oxide thin film that can be formed is limited.

上記スプレー熱分解法およびスピンコート法は、上記化学気相成長（ＣＶＤ）法に比べて装置が簡便で膜形成速度が速い為生産性が高く製造コストも低い。また、真空容器を用いる必要がなく真空容器による制約がない為大きな酸化亜鉛薄膜の作成も可能であるという利点がある。   The spray pyrolysis method and the spin coating method have a higher productivity and a lower manufacturing cost because the apparatus is simpler and the film formation rate is faster than the chemical vapor deposition (CVD) method. Further, there is an advantage that a large zinc oxide thin film can be formed because there is no need to use a vacuum container and there is no restriction by the vacuum container.

上記スプレー熱分解法では、スプレー塗布と同時に溶媒乾燥し、次いで基板温度を３６０℃以上に加熱することで酸化亜鉛薄膜塗膜を得ている。   In the spray pyrolysis method, solvent drying is performed simultaneously with spray coating, and then the substrate temperature is heated to 360 ° C. or higher to obtain a zinc oxide thin film coating film.

上記でスピンコート法は、スピンコート後に溶媒乾燥し、次いで基板温度を４００℃以上に加熱することで酸化亜鉛薄膜塗膜を得ている。
日本学術振興会透明酸化物光電子材料第１６６委員会編、透明導電膜の技術 改訂２版（２００６）、ｐ１６５〜１７３ K. Sorab, et al. Appl. Phys. Lett., 37(5), 1 September 1980 J. Aranovich, et al. J. Vac. Sci. Technol., 16(4), July/August 1979 特開平７−１８２９３９号公報 In the above spin coating method, the solvent is dried after spin coating, and then the substrate temperature is heated to 400 ° C. or higher to obtain a zinc oxide thin film coating film.
Japan Society for the Promotion of Science Transparent Oxide Optoelectronic Materials 166th Committee, Transparent Conductive Film Technology Revision 2 (2006), p165-173 K. Sorab, et al. Appl. Phys. Lett., 37 (5), 1 September 1980 J. Aranovich, et al. J. Vac. Sci. Technol., 16 (4), July / August 1979 JP 7-182939 A

透明酸化亜鉛薄膜は、基板としてプラスチック基板を用いるようになっている。そのため、透明酸化亜鉛薄膜の形成時に適用される加熱は、プラスチック基板の耐熱温度以下で実施されることが必要である。しかるに、上記非特許文献３に記載のスプレー熱分解法や特許文献１に記載のスピンコート法では、プラスチック基板の耐熱温度以下での加熱では、透明酸化亜鉛薄膜を得ることはできない。プラスチック基板の耐熱温度と加熱に要するコスト等を考慮すると、製膜時に要する加熱は、３００℃以下であることが望まれる。   The transparent zinc oxide thin film uses a plastic substrate as a substrate. Therefore, the heating applied at the time of forming the transparent zinc oxide thin film needs to be performed at a temperature lower than the heat resistance temperature of the plastic substrate. However, in the spray pyrolysis method described in Non-Patent Document 3 and the spin coating method described in Patent Document 1, a transparent zinc oxide thin film cannot be obtained by heating at a temperature lower than the heat-resistant temperature of the plastic substrate. Considering the heat-resistant temperature of the plastic substrate and the cost required for heating, it is desirable that the heating required for film formation is 300 ° C. or lower.

本発明者らの検討によれば、非特許文献３に記載のスプレー熱分解法で用いられている酢酸亜鉛の水溶液や特許文献１に記載のスピンコート法で用いられている有機亜鉛化合物の有機溶媒の溶液を用いて３００℃以下で製膜しても、透明な酸化亜鉛薄膜が得られず、不透明な酸化亜鉛薄膜しか得られなかった。特許文献１には、ジエチル亜鉛のヘキサン溶液を用いる方法も記載されているが、この溶液を用いて３００℃以下での製膜を試みたが、透明な酸化亜鉛薄膜は得られなかった。   According to studies by the present inventors, an aqueous solution of zinc acetate used in the spray pyrolysis method described in Non-Patent Document 3 and an organic zinc compound used in the spin coating method described in Patent Document 1 are used. Even when a film was formed at 300 ° C. or lower using a solvent solution, a transparent zinc oxide thin film was not obtained, and only an opaque zinc oxide thin film was obtained. Patent Document 1 also describes a method using a hexane solution of diethylzinc, but an attempt was made to form a film at 300 ° C. or lower using this solution, but a transparent zinc oxide thin film was not obtained.

ジエチル亜鉛は大気中で発火性があり、保管、使用時に非常な注意を払わねばならない化合物である。そのため、ジエチル亜鉛を希釈等することなしに、通常、水が存在する雰囲気中で行われることの多い、スプレー熱分解法、スピンコート法等で用いることは、実用上困難である。ジエチル亜鉛は、有機溶媒に溶解した状態では、発火性などの危険性は低減できるが、特許文献１に記載のように、アルコール系の有機溶媒に反応させながら溶解したジエチル亜鉛を用いた酸化亜鉛薄膜の製膜には、４００℃以上の高温で加熱が必要であった。   Diethyl zinc is a compound that is ignitable in the atmosphere and must be very carefully stored and used. For this reason, it is practically difficult to use it in a spray pyrolysis method, spin coating method, etc., which is often performed in an atmosphere containing water without diluting diethyl zinc. When diethyl zinc is dissolved in an organic solvent, the risk of ignition, etc. can be reduced. However, as disclosed in Patent Document 1, zinc oxide using diethyl zinc dissolved while reacting with an alcohol-based organic solvent is used. In order to form a thin film, heating was required at a high temperature of 400 ° C. or higher.

本発明の目的は、プラスチック基板の耐熱温度と加熱に要するコスト等を考慮して、製膜時に加熱を必要としないか、あるいは加熱しても３００℃以下の加熱で、透明酸化亜鉛薄膜を得ることができる方法を提供するという課題を解決することにある。   An object of the present invention is to obtain a transparent zinc oxide thin film by heating at 300 ° C. or less even if heating is not required at the time of film formation in consideration of heat resistance temperature of plastic substrate and cost required for heating. It is to solve the problem of providing a method that can.

上記課題を解決するための本発明は、以下のとおりである。
［１］
有機溶媒に有機亜鉛化合物を溶解した溶液を、大気圧または加圧下、水が存在する雰囲気下、かつ３００℃以下の基板温度で、基板表面にスプレー塗布して、酸化亜鉛薄膜を形成すること、
前記有機溶媒が、電子供与性を有する溶媒であること、
前記有機亜鉛化合物が、一般式（１）で表される化合物であること
Ｒ1−Ｚｎ−Ｒ1 （１）
（式中、Ｒ1は炭素数１〜７の直鎖または分岐したアルキル基である）
を特徴とする酸化亜鉛薄膜の製造方法。
［２］
前記溶液の有機亜鉛化合物濃度は、１５質量％以下である［１］に記載の製造方法。
［３］
前記溶液のスプレー塗布は、塗布液をスプレーノズルより液滴の大きさが１〜３０μｍの範囲になるように吐出し、かつスプレーノズルと基板との距離を５０ｃｍ以内として行う［１］または［２］に記載の製造方法。
［４］
スプレー塗布をする雰囲気温度が４０℃以下である［１］〜［３］のいずれかに記載の製造方法。
［５］
前記有機亜鉛化合物は、Ｒ1が炭素数１、２、３、４、５、または６のアルキル基である化合物である［１］〜［４］のいずれかに記載の製造方法。
［６］
前記有機亜鉛化合物がジエチル亜鉛である［１］〜［４］のいずれかに記載の製造方法。
［７］
前記有機溶媒がジイソプロピルエーテルである［１］〜［６］のいずれかに記載の製造方法。
［８］
前記酸化亜鉛薄膜は、可視光線に対して８０％以上の平均透過率を有する［１］〜［７］のいずれかに記載の製造方法。 The present invention for solving the above problems is as follows.
[1]
Forming a zinc oxide thin film by spray-coating a solution in which an organic zinc compound is dissolved in an organic solvent on the surface of the substrate at atmospheric pressure or under pressure, in an atmosphere containing water, and at a substrate temperature of 300 ° C. or lower;
The organic solvent is an electron-donating solvent;
The organozinc compound is a compound represented by the general formula (1) R 1 —Zn—R 1 (1)
(In the formula, R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms)
A method for producing a zinc oxide thin film.
[2]
The method according to [1], wherein the concentration of the organic zinc compound in the solution is 15% by mass or less.
[3]
The spray application of the solution is performed by discharging the application liquid from the spray nozzle so that the droplet size is in the range of 1 to 30 μm, and the distance between the spray nozzle and the substrate is within 50 cm [1] or [2 ] The manufacturing method of description.
[4]
The manufacturing method according to any one of [1] to [3], wherein an atmospheric temperature for spray coating is 40 ° C. or lower.
[5]
The organozinc compound is The process according to any one of the R 1 is a compound which is an alkyl group of 1, 2, 3, 4 carbon atoms, or 6, [1] to [4].
[6]
The production method according to any one of [1] to [4], wherein the organic zinc compound is diethyl zinc.
[7]
The production method according to any one of [1] to [6], wherein the organic solvent is diisopropyl ether.
[8]
The said zinc oxide thin film is a manufacturing method in any one of [1]-[7] which has an average transmittance | permeability of 80% or more with respect to visible light.

本発明によれば、３００℃以下の低温の基板温度で製膜しても透明酸化亜鉛薄膜を製造することができる。   According to the present invention, a transparent zinc oxide thin film can be produced even if a film is formed at a low substrate temperature of 300 ° C. or lower.

本発明は、酸化亜鉛薄膜の製造方法であって、この方法は、有機溶媒に有機亜鉛化合物を溶解した溶液を、大気圧または加圧下、水の存在する雰囲気下、かつ３００℃以下の基板温度で、基板表面にスプレー塗布して、酸化亜鉛薄膜を形成すること、
前記有機溶媒が、電子供与性を有する溶媒であること、
前記有機亜鉛化合物が、一般式（１）で表される化合物であること
Ｒ1−Ｚｎ−Ｒ1 （１）
（式中、Ｒ1は炭素数１〜７の直鎖または分岐したアルキル基である）
を特徴とする。 The present invention is a method for producing a zinc oxide thin film, which comprises a solution obtained by dissolving an organic zinc compound in an organic solvent, at atmospheric pressure or under pressure, in an atmosphere containing water, and at a substrate temperature of 300 ° C. or lower. And spray coating on the substrate surface to form a zinc oxide thin film,
The organic solvent is an electron-donating solvent;
The organozinc compound is a compound represented by the general formula (1) R 1 —Zn—R 1 (1)
(In the formula, R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms)
It is characterized by.

本発明の酸化亜鉛薄膜の製造方法は、スプレー塗布法を用いるが、スプレー塗布に用いる溶液(以下、塗布液ということもある)は、有機溶媒に有機亜鉛化合物を溶解した溶液であり、有機亜鉛化合物は上記一般式（１）で表される化合物であり、かつ有機溶媒は電子供与性を有する溶媒である。   The method for producing a zinc oxide thin film of the present invention uses a spray coating method. A solution used for spray coating (hereinafter sometimes referred to as a coating solution) is a solution in which an organic zinc compound is dissolved in an organic solvent. The compound is a compound represented by the general formula (1), and the organic solvent is a solvent having an electron donating property.

一般式（１）で表される化合物におけるＲ1として表されるアルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ヘキシル基、イソヘキシル基、ｓｅｃ−ヘキシル基、ｔｅｒｔ−ヘキシル基、２−ヘキシル基、およびヘプチル基を挙げることができる。一般式（１）で表される化合物は、Ｒ1が炭素数が１、２、３、４、５、または６の化合物であることが好ましい。一般式（１）で表される化合物は、特にジエチル亜鉛であることが好ましい。 Specific examples of the alkyl group represented by R 1 in the compound represented by the general formula (1) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert- Mention may be made of butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, sec-hexyl, tert-hexyl, 2-hexyl and heptyl. In the compound represented by the general formula (1), R 1 is preferably a compound having 1, 2, 3, 4, 5, or 6 carbon atoms. The compound represented by the general formula (1) is particularly preferably diethyl zinc.

電子供与性を有する溶媒の例として、トリメチルアミン、トリエチルアミン、トリフェニルアミン等のアミン系溶媒、ジエチルエーテル、ジｎ−プロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン、グライム、ジグライム、トリグライム等のエーテル系溶媒等を挙げることができる。電子供与性を有する溶媒としては、ジイソプロピルエーテルが好ましい。   Examples of solvents having electron donating properties include amine solvents such as trimethylamine, triethylamine and triphenylamine, ethers such as diethyl ether, di-n-propyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, glyme, diglyme and triglyme. Examples thereof include system solvents. As the solvent having an electron donating property, diisopropyl ether is preferable.

本発明においては、上記塗布液の有機亜鉛化合物濃度は、１５質量％以下の濃度であることが、透明な酸化亜鉛薄膜を製造するという観点から好ましい。塗布液の有機亜鉛化合物濃度は、好ましくは、1〜１０質量％、より好ましくは３〜１０質量％である。塗布液の有機亜鉛化合物濃度は、発火などの酸化亜鉛薄膜製造時の危険性に影響があり、上記範囲とすることで、良好な透明性の酸化亜鉛薄膜を特別な注意を払わず安全に製造することができる。   In the present invention, the concentration of the organic zinc compound in the coating solution is preferably 15% by mass or less from the viewpoint of producing a transparent zinc oxide thin film. The concentration of the organic zinc compound in the coating solution is preferably 1 to 10% by mass, more preferably 3 to 10% by mass. The concentration of the organic zinc compound in the coating solution has an impact on the risk of zinc oxide thin film production such as ignition, and by making it within the above range, a transparent zinc oxide thin film with good transparency can be produced safely without paying special attention can do.

基板表面へのスプレー塗布は、大気圧または加圧下で、酸化亜鉛薄膜の酸素源である水が存在する雰囲気下で行う。加圧下とは、圧力が１０１．３〜２０２．６ｋPaの範囲の場合である。尚、本発明の方法におけるスプレー塗布は、減圧下でも実施できるが、減圧下で実施するメリットはなく、大気圧で実施するのが、装置上も簡便であり好ましい。   Spray coating on the substrate surface is performed under an atmosphere containing water that is an oxygen source of the zinc oxide thin film under atmospheric pressure or pressure. Under pressure is when the pressure is in the range of 101.3-202.6 kPa. The spray coating in the method of the present invention can be carried out even under reduced pressure, but there is no merit to carry out under reduced pressure, and it is preferable to carry out at atmospheric pressure because the apparatus is simple and preferable.

基板表面へのスプレー塗布における「水が存在する雰囲気」とは、例えば、相対湿度２０〜９０％分の水を含有した空気の雰囲気であることができる。空気の雰囲気で行う代わり窒素と水を混合させた混合ガスの雰囲気下で行ってもよい。相対湿度は、酸化亜鉛薄膜の生成がスムーズであるという観点からは、より好ましくは３０〜７０％である。   The “atmosphere in which water exists” in spray coating on the substrate surface can be, for example, an air atmosphere containing water having a relative humidity of 20 to 90%. Instead of performing in an air atmosphere, it may be performed in an atmosphere of a mixed gas in which nitrogen and water are mixed. The relative humidity is more preferably 30 to 70% from the viewpoint that the formation of the zinc oxide thin film is smooth.

基板表面へのスプレー塗布は、３００℃以下の基板温度でおこなうことができる。より具体的には、スプレー塗布をする雰囲気温度を４０℃以下とし、かつ基板温度を３００℃以下とすることが好ましい。酸化亜鉛薄膜の生成がスムーズであるという観点からは、スプレー塗布をする雰囲気温度は、好ましくは１０〜３０℃の範囲であり、基板温度は、好ましくは１０〜２００℃、さらに好ましくは２０〜１００℃の範囲である。   Spray coating on the substrate surface can be performed at a substrate temperature of 300 ° C. or lower. More specifically, it is preferable that the atmospheric temperature for spray coating is 40 ° C. or lower and the substrate temperature is 300 ° C. or lower. From the viewpoint of smooth production of the zinc oxide thin film, the atmospheric temperature for spray coating is preferably in the range of 10 to 30 ° C, and the substrate temperature is preferably 10 to 200 ° C, more preferably 20 to 100. It is in the range of ° C.

図1に、本発明で用いることができるスプレー製膜装置を示す。図中、１は塗布液を充填したスプレーボトル、２は基板ホルダ、３スプレーノズル、４はコンプレッサ、５は基板を示す。スプレー塗布は、基板を基板ホルダ２に設置し、必要によりヒーターを用いて３００℃以下の所定の温度まで加熱し、その後、大気中（大気圧下、空気中）で、基板の上方に配置したスプレーノズル３から圧縮した不活性ガスと塗布液を同時供給し、塗布液を霧化、噴霧させることにより基板上に酸化亜鉛薄膜を形成することができる。酸化亜鉛薄膜は、スプレー塗布することで、追加の加熱等することなしに形成される。   FIG. 1 shows a spray film forming apparatus that can be used in the present invention. In the figure, 1 is a spray bottle filled with a coating solution, 2 is a substrate holder, 3 spray nozzles, 4 is a compressor, and 5 is a substrate. In spray coating, the substrate is placed on the substrate holder 2 and heated to a predetermined temperature of 300 ° C. or lower using a heater if necessary, and then placed in the atmosphere (at atmospheric pressure and in air) above the substrate. A zinc oxide thin film can be formed on the substrate by simultaneously supplying the compressed inert gas and the coating liquid from the spray nozzle 3 and atomizing and spraying the coating liquid. The zinc oxide thin film is formed by spray coating without additional heating.

塗布液のスプレー塗布は、塗布液をスプレーノズルより液滴の大きさが１〜１５μｍの範囲になるように吐出し、かつスプレーノズルと基板との距離を５０ｃｍ以内として行うことが、良好な透明性の酸化亜鉛薄膜を製造することができるという観点から好ましい。さらに、スプレー塗布をする雰囲気温度が４０℃以下であり、かつ基板の温度が３００℃以下であることが、基板への熱の影響とエネルギーコストの観点から好ましい。   Spray coating of the coating solution is performed by discharging the coating solution from the spray nozzle so that the droplet size is in the range of 1 to 15 μm and keeping the distance between the spray nozzle and the substrate within 50 cm. From the viewpoint that a functional zinc oxide thin film can be produced. Furthermore, it is preferable that the atmospheric temperature for spray coating is 40 ° C. or less and the temperature of the substrate is 300 ° C. or less from the viewpoint of the influence of heat on the substrate and energy cost.

基板への付着性、溶媒の蒸発の容易性等を考慮すると、スプレーノズルより吐出される液滴の大きさについては、全ての液滴の大きさが１〜３０μｍの範囲にあることが好ましい。液滴の大きさは、より好ましくは３〜２０μｍの範囲にある。   In consideration of adhesion to the substrate, easiness of evaporation of the solvent, etc., it is preferable that the size of all the droplets ejected from the spray nozzle is in the range of 1 to 30 μm. The size of the droplet is more preferably in the range of 3 to 20 μm.

スプレーノズルから基板に到達するまでに溶媒が幾分蒸発し液滴の大きさが減少すること等を考慮すると、スプレーノズルと基板との距離は５０ｃｍ以内であることが好ましい。スプレーノズルと基板との距離は、酸化亜鉛薄膜の形成が良好にできるという観点から、好ましくは２〜４０ｃｍの範囲である。   Considering that the solvent evaporates somewhat before reaching the substrate from the spray nozzle and the size of the droplet is reduced, the distance between the spray nozzle and the substrate is preferably within 50 cm. The distance between the spray nozzle and the substrate is preferably in the range of 2 to 40 cm from the viewpoint that the zinc oxide thin film can be satisfactorily formed.

さらに、基板および雰囲気温度を加熱することなく、基板の上方に配置したスプレーノズル３から圧縮した不活性ガスと塗布液を同時供給し、塗布液を霧化、噴霧させることだけでも基板上に透明性の酸化亜鉛薄膜を形成することができる。   Furthermore, without heating the substrate and the ambient temperature, the compressed inert gas and the coating solution are simultaneously supplied from the spray nozzle 3 disposed above the substrate, and the coating solution is atomized and sprayed. A zinc oxide thin film can be formed.

本発明の製造方法により形成される酸化亜鉛薄膜は、好ましくは可視光線に対して８０％以上の平均透過率を有するものであり、より好ましくは可視光線に対して８５％以上の平均透過率を有する。尚、「可視光線に対する平均透過率」とは、以下のように定義され、かつ測定される。可視光線に対する平均透過率とは、３８０〜７８０ｎｍの範囲の光線の透過率の平均を云い、紫外可視分光光度計により測定される。   The zinc oxide thin film formed by the production method of the present invention preferably has an average transmittance of 80% or more with respect to visible light, and more preferably has an average transmittance of 85% or more with respect to visible light. Have. The “average transmittance for visible light” is defined and measured as follows. The average transmittance for visible light refers to the average of the transmittance of light in the range of 380 to 780 nm, and is measured by an ultraviolet-visible spectrophotometer.

本発明において基板として用いられるのは、例えば、透明基材フィルムであることができ、透明基材フィルムは、プラスチックフィルムであることができる。プラスチックフィルムを形成するポリマーには、ポリエステル（例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート）、ポリ（メタ）アクリル（例えば、ポリメチルメタクリレート（ＰＭＭＡ））、ポリカーボネート（ＰＣ）、ポリスチレン、ポリビニルアルコール、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリエチレン、環状ポリオレフィン（ＣＯＰ）、エチレン− 酢酸ビニル共重合体、ポリウレタン、トリアセテート、セロファンを例示することができる。これら中、ＰＥＴ、ＰＣ、ＰＭＭＡが好ましい。透明基材フィルムはポリマーの種類によって無延伸フィルムであっても、延伸フィルムであってもよい。例えば、ポリエステルフィルム例えばＰＥＴフィルムは、通常、二軸延伸フィルムであり、またＰＣフィルム、トリアセテートフィルム、セロファンフィルム等は、通常、無延伸フィルムである。   What is used as a board | substrate in this invention can be a transparent base film, for example, and a transparent base film can be a plastic film. Polymers forming the plastic film include polyesters (eg, polyethylene terephthalate (PET), polyethylene naphthalate), poly (meth) acrylic (eg, polymethyl methacrylate (PMMA)), polycarbonate (PC), polystyrene, polyvinyl alcohol, Examples thereof include polyvinyl chloride, polyvinylidene chloride, polyethylene, cyclic polyolefin (COP), ethylene-vinyl acetate copolymer, polyurethane, triacetate, and cellophane. Of these, PET, PC, and PMMA are preferable. The transparent substrate film may be an unstretched film or a stretched film depending on the type of polymer. For example, a polyester film such as a PET film is usually a biaxially stretched film, and a PC film, a triacetate film, a cellophane film and the like are usually unstretched films.

以下に本発明を実施例によってさらに詳細に説明するが、これらの実施例は本発明を限定するものではない。   EXAMPLES The present invention will be described in more detail with reference to examples below, but these examples do not limit the present invention.

［実施例１］
塗布液の調製は窒素ガス雰囲気下で行い、溶媒は全て脱水および脱気して使用した。ジイソプロピルエーテル２０４．４ｇにジエチル亜鉛１０．７６ｇを加えた。十分攪拌した後ろ過することで塗布液を得た。 [Example 1]
The coating solution was prepared in a nitrogen gas atmosphere, and all solvents were dehydrated and degassed before use. 10.76 g of diethyl zinc was added to 204.4 g of diisopropyl ether. After sufficiently stirring, a coating solution was obtained by filtration.

上記のようにして得た塗布液を、図１のスプレー製膜装置中スプレーボトルに充填した。スライドガラス基板を基板ホルダに設置した。ガラス基板を６０℃に加熱した後、大気圧下、２５℃、相対湿度６０％と水が存在する空気中で、スプレーノズルより塗布液を８ｍｌ／ｍｉｎで８分間噴霧した。スプレーノズルより吐出する液滴の大きさは、３〜２０μｍの範囲であり、かつスプレーノズルと基板との距離を４０ｃｍとして行った。基板上に形成された薄膜の膜厚はＳＥＭ測定により求め、約１００ｎｍであった。基板上に形成された薄膜は、図２に示すとおり、XRDにより酸化亜鉛であることが確認された。また、可視光の平均透過率は８７％であり、透過率８０％以上の透明な酸化亜鉛薄膜を得られた。   The coating solution obtained as described above was filled in a spray bottle in the spray film forming apparatus of FIG. A slide glass substrate was placed on the substrate holder. After heating the glass substrate to 60 ° C., the coating solution was sprayed at 8 ml / min for 8 minutes from the spray nozzle in air containing 25 ° C., 60% relative humidity and water at atmospheric pressure. The size of the liquid droplets discharged from the spray nozzle was in the range of 3 to 20 μm, and the distance between the spray nozzle and the substrate was 40 cm. The film thickness of the thin film formed on the substrate was determined by SEM measurement and was about 100 nm. As shown in FIG. 2, the thin film formed on the substrate was confirmed to be zinc oxide by XRD. Further, the average transmittance of visible light was 87%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.

［実施例２］
塗布液の調製は窒素ガス雰囲気下で行い、溶媒は全て脱水および脱気して使用した。ジイソプロピルエーテル２０４．４ｇにジエチル亜鉛２１．４９ｇを加えた。十分攪拌した後ろ過することで塗布液を得た。 [Example 2]
The coating solution was prepared in a nitrogen gas atmosphere, and all solvents were dehydrated and degassed before use. Diethyl zinc (21.49 g) was added to diisopropyl ether (204.4 g). After sufficiently stirring, a coating solution was obtained by filtration.

基板を加熱せず室温で噴霧した以外は全て実施例１と同様に行った。基板上に形成された薄膜の膜厚はＳＥＭ測定により求め、約２１０ｎｍであった。基板上に形成された薄膜は、図３に示すとおり、XRDにより酸化亜鉛であることが確認された。また、可視光の平均透過率は８３％であり、透過率８０％以上の透明な酸化亜鉛薄膜を得られた。   The same procedure as in Example 1 was performed except that the substrate was sprayed at room temperature without heating. The film thickness of the thin film formed on the substrate was determined by SEM measurement and was about 210 nm. As shown in FIG. 3, the thin film formed on the substrate was confirmed to be zinc oxide by XRD. The average visible light transmittance was 83%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.

［比較例１］
エタノール、水の体積比が３：１である混合溶媒２０４．４ｇに酢酸亜鉛二水和物１９．０２ｇを加え、十分攪拌することで塗布液を得た。 [Comparative Example 1]
19.20 g of zinc acetate dihydrate was added to 204.4 g of a mixed solvent having a volume ratio of ethanol and water of 3: 1 and sufficiently stirred to obtain a coating solution.

上記のようにして得た塗布液を、図１のスプレー製膜装置中スプレーボトルに充填した。スライドガラス基板を基板ホルダに設置した。ガラス基板を６０℃に加熱した後、ノズルより塗布液を８ｍｌ／ｍｉｎで８分間噴霧した。XRDからは酸化亜鉛由来のピークは確認されなかった（図示せず）。また、可視光の平均透過率は１％であり、不透明な酸化亜鉛薄膜しか得られなかった。   The coating solution obtained as described above was filled in a spray bottle in the spray film forming apparatus of FIG. A slide glass substrate was placed on the substrate holder. After heating the glass substrate to 60 ° C., the coating solution was sprayed from the nozzle at 8 ml / min for 8 minutes. A peak derived from zinc oxide was not confirmed from XRD (not shown). Further, the average visible light transmittance was 1%, and only an opaque zinc oxide thin film was obtained.

［比較例２］
実施例１で調製した塗布液に基板を浸漬した後に回収して、基板に塗布液を塗布した。基板上には、不透明な酸化亜鉛薄膜しか得られなかった。 [Comparative Example 2]
The substrate was immersed in the coating solution prepared in Example 1 and then collected, and the coating solution was applied to the substrate. Only an opaque zinc oxide thin film was obtained on the substrate.

［比較例３］
ヘキサン２０４．３ｇにジエチル亜鉛１０．７６ｇを加えた。十分攪拌した後ろ過することで塗布液を得た。得られた塗布液を実施例１と同様の方法および条件で基板にスプレー塗布した。基板上には、不透明な酸化亜鉛薄膜しか得られなかった。 [Comparative Example 3]
Diethylzinc (10.76 g) was added to hexane (204.3 g). After sufficiently stirring, a coating solution was obtained by filtration. The obtained coating solution was spray-coated on the substrate by the same method and conditions as in Example 1. Only an opaque zinc oxide thin film was obtained on the substrate.

本発明は、酸化亜鉛薄膜の製造分野に有用である。   The present invention is useful in the field of manufacturing zinc oxide thin films.

スプレー製膜装置を示す図である。It is a figure which shows a spray film forming apparatus. 実施例１で得られた酸化亜鉛薄膜のＸＲＤスペクトルXRD spectrum of the zinc oxide thin film obtained in Example 1 実施例２で得られた酸化亜鉛薄膜のＸＲＤスペクトルXRD spectrum of the zinc oxide thin film obtained in Example 2

符号の説明Explanation of symbols

１・・・スプレーボトル、２・・・基板ホルダ（ヒーター付）、３・・・スプレーノズル、４・・・コンプレッサ−、５・・・無アルカリガラス基板 DESCRIPTION OF SYMBOLS 1 ... Spray bottle, 2 ... Substrate holder (with heater), 3 ... Spray nozzle, 4 ... Compressor, 5 ... Non-alkali glass substrate

Claims (8)

有機溶媒に有機亜鉛化合物を溶解した溶液を、大気圧または加圧下、水が存在する雰囲気下、かつ３００℃以下の基板温度で、基板表面にスプレー塗布して、酸化亜鉛薄膜を形成すること、
前記有機溶媒が、電子供与性を有する溶媒であること、
前記有機亜鉛化合物が、一般式（１）で表される化合物であること
Ｒ1−Ｚｎ−Ｒ1 （１）
（式中、Ｒ1は炭素数１〜７の直鎖または分岐したアルキル基である）
を特徴とする酸化亜鉛薄膜の製造方法。 Forming a zinc oxide thin film by spray-coating a solution in which an organic zinc compound is dissolved in an organic solvent, at atmospheric pressure or under pressure, in an atmosphere in which water is present, and at a substrate temperature of 300 ° C. or lower, on the substrate surface;
The organic solvent is an electron-donating solvent;
The organozinc compound is a compound represented by the general formula (1) R 1 —Zn—R 1 (1)
(In the formula, R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms)
A method for producing a zinc oxide thin film. 前記溶液の有機亜鉛化合物濃度は、１５質量％以下である請求項１に記載の製造方法。 The manufacturing method according to claim 1, wherein the concentration of the organic zinc compound in the solution is 15% by mass or less. 前記溶液のスプレー塗布は、塗布液をスプレーノズルより液滴の大きさが１〜３０μｍの範囲になるように吐出し、かつスプレーノズルと基板との距離を５０ｃｍ以内として行う請求項１または２に記載の製造方法。 The spray application of the solution is performed by discharging the application liquid from the spray nozzle so that the droplet size is in the range of 1 to 30 μm, and the distance between the spray nozzle and the substrate is 50 cm or less. The manufacturing method as described. スプレー塗布をする雰囲気温度が４０℃以下である請求項１〜３のいずれかに記載の製造方法。 The manufacturing method according to any one of claims 1 to 3, wherein an atmospheric temperature for spray coating is 40 ° C or lower. 前記有機亜鉛化合物は、Ｒ1が炭素数１、２、３、４、５、または６のアルキル基である化合物である請求項１〜４のいずれかに記載の製造方法。 The organozinc compound is The process according to any one of claims 1 to 4 R 1 is a compound which is an alkyl group of 1, 2, 3, 4 carbon atoms, or 6,. 前記有機亜鉛化合物がジエチル亜鉛である請求項１〜４のいずれかに記載の製造方法。 The production method according to claim 1, wherein the organic zinc compound is diethyl zinc. 前記有機溶媒がジイソプロピルエーテルである請求項１〜６のいずれかに記載の製造方法。 The production method according to claim 1, wherein the organic solvent is diisopropyl ether. 前記酸化亜鉛薄膜は、可視光線に対して８０％以上の平均透過率を有する請求項１〜７のいずれかに記載の製造方法。 The said zinc oxide thin film is a manufacturing method in any one of Claims 1-7 which has an average transmittance | permeability of 80% or more with respect to visible light.
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