JPH05294623A - Production of zinc oxide thin film - Google Patents
Production of zinc oxide thin filmInfo
- Publication number
- JPH05294623A JPH05294623A JP10436192A JP10436192A JPH05294623A JP H05294623 A JPH05294623 A JP H05294623A JP 10436192 A JP10436192 A JP 10436192A JP 10436192 A JP10436192 A JP 10436192A JP H05294623 A JPH05294623 A JP H05294623A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- zinc oxide
- zinc
- oxide thin
- substrate
- 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.)
- Pending
Links
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
(57)【要約】
【目的】 均一かつ緻密でＣ軸が基板の表面に垂直に配
向した酸化亜鉛薄膜を簡便かつ低コストで製造する方法
の開発。
【構成】 亜鉛化合物，溶媒および沸点２５０℃以下の
含窒素有機化合物を混合し、加温，攪拌して塗布液を調
製し、次いで該塗布液を基板に塗布したのち、熱処理し
てなる酸化亜鉛薄膜の製造方法。(57) [Abstract] [Purpose] Development of a simple and low-cost method for producing a zinc oxide thin film that is uniform and dense, with the C-axis oriented perpendicular to the surface of the substrate. [Structure] Zinc oxide obtained by mixing a zinc compound, a solvent and a nitrogen-containing organic compound having a boiling point of 250 ° C. or lower, heating and stirring to prepare a coating solution, and then applying the coating solution to a substrate and then heat-treating it. Thin film manufacturing method.
Description
【０００１】[0001]
【産業上の利用分野】本発明は酸化亜鉛薄膜の製造方法
に関し、さらに詳しくは、センサ，表面波デバイス，バ
リスタ，透明電極等の材料，γ線の発光材料，光導波路
素子，強誘電性薄膜作成用基板等として有用な均一かつ
緻密なＣ軸が基板の表面に垂直に配向した酸化亜鉛薄膜
を簡便かつ低コストで製造する方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a zinc oxide thin film, and more specifically, a material for a sensor, a surface wave device, a varistor, a transparent electrode, etc., a γ-ray emitting material, an optical waveguide device, a ferroelectric thin film. The present invention relates to a method for easily and inexpensively producing a zinc oxide thin film, which is useful as a substrate for preparation and has a uniform and dense C-axis perpendicular to the surface of the substrate.
【０００２】[0002]
【従来の技術】一般に、酸化亜鉛薄膜は、光学的に透明
で、圧電性やｎ−型半導体特性を有し、例えば表面波デ
バイス，バリスタ，透明電極等に幅広く利用できる材料
である。このように、酸化亜鉛薄膜は利用価値が高いた
め、簡便で安価な製造方法が望まれている。従来、金属
酸化物薄膜の製造方法、特にＣ軸が基板の表面に垂直に
配向している薄膜の製造方法としては、例えば真空蒸着
法，スパッタリング法，気相化学反応法（ＣＶＤ法），
噴霧熱分解法（スプレーパイロリシス法）等がよく用い
られている。しかしながら、従来の方法においては、薄
膜製造設備が大がかりとなり、大面積の薄膜を製造する
ことが困難であり、Ｃ軸が基板の表面に垂直に配向して
いない薄膜も製造されていた。また、高橋らは第３０回
セラミックス基礎科学討論会予稿集（１９９１年）にお
いて、イソプロパノールに亜鉛ｎ−プロポキシドおよび
／または酢酸亜鉛２水和物をジエタノールアミンと共に
溶解し、基板に塗布後熱処理することにより得られる酸
化亜鉛薄膜を開示している。この酸化亜鉛薄膜は、原料
であるジエタノールアミンの沸点が２７０℃と高温のた
め、配向薄膜が得られない。また、他のアミンを用いて
塗布液を調製しているが、加熱および攪拌処理を施して
いないため透明な塗布液が得られない。2. Description of the Related Art Generally, a zinc oxide thin film is a material which is optically transparent, has piezoelectricity and n-type semiconductor characteristics, and can be widely used in, for example, surface wave devices, varistors, transparent electrodes and the like. As described above, since the zinc oxide thin film has a high utility value, a simple and inexpensive manufacturing method is desired. Conventionally, as a method for producing a metal oxide thin film, particularly a method for producing a thin film in which the C axis is oriented perpendicular to the surface of the substrate, there are, for example, a vacuum vapor deposition method, a sputtering method, a vapor phase chemical reaction method (CVD method),
The spray pyrolysis method (spray pyrolysis method) and the like are often used. However, in the conventional method, the thin-film manufacturing equipment becomes large-scale, it is difficult to manufacture a large-area thin film, and a thin film in which the C axis is not oriented perpendicular to the surface of the substrate has also been manufactured. In addition, Takahashi et al., In the proceedings of the 30th Ceramic Science Symposium (1991), dissolve zinc n-propoxide and / or zinc acetate dihydrate together with diethanolamine in isopropanol and heat it after coating on the substrate. The zinc oxide thin film obtained by the above is disclosed. An oriented thin film cannot be obtained from this zinc oxide thin film because the boiling point of the raw material, diethanolamine, is 270 ° C. Further, although the coating solution is prepared using other amine, a transparent coating solution cannot be obtained because it is not subjected to heating and stirring treatment.
【０００３】[0003]
【発明が解決しようとする課題】そこで本発明者らは、
上記従来技術の欠点を解消し、均一かつ透明で緻密なＣ
軸が基板の表面に垂直な配向を有する亜鉛酸化薄膜を、
簡便かつ低コストで製造する方法を開発すべく鋭意研究
を重ねた。Therefore, the present inventors have found that
A uniform, transparent, and dense C that solves the above-mentioned drawbacks of the prior art
A zinc oxide thin film whose axis is oriented perpendicular to the surface of the substrate,
We have conducted intensive research to develop a simple and low-cost manufacturing method.
【０００４】[0004]
【課題を解決するための手段】その結果、亜鉛化合物，
沸点が２５０℃以下の溶媒および沸点が２５０℃以下の
添加剤を混合し、３５〜１２０℃に加温，攪拌して得ら
れる塗布液を用いることによって、上記目的を達成でき
ることを見出した。本発明はかかる知見に基いて完成し
たものである。すなわち本発明は、亜鉛化合物，沸点が
２５０℃以下の含酸素有機化合物および沸点が２５０℃
以下の含窒素有機化合物を混合し、３５〜１２０℃に加
温，攪拌して塗布液を調製し、次いで該塗布液を基板に
塗布したのち、熱処理することを特徴とする酸化亜鉛薄
膜の製造方法を提供するものである。As a result, a zinc compound,
It has been found that the above object can be achieved by using a coating solution obtained by mixing a solvent having a boiling point of 250 ° C. or lower and an additive having a boiling point of 250 ° C. or lower and heating the mixture to 35 to 120 ° C. and stirring. The present invention has been completed based on such findings. That is, the present invention includes a zinc compound, an oxygen-containing organic compound having a boiling point of 250 ° C or lower, and a boiling point of 250 ° C.
The following nitrogen-containing organic compounds are mixed, heated to 35 to 120 ° C. and stirred to prepare a coating solution, which is then coated on a substrate and then heat-treated, to produce a zinc oxide thin film. It provides a method.
【０００５】本発明において、原料の亜鉛化合物は、特
に限定されないが、例えば塩化亜鉛，硝酸亜鉛，硫酸亜
鉛等の無機化合物や酢酸亜鉛，蟻酸亜鉛，アセチルアセ
トナト亜鉛，亜鉛アルコキシド等の有機化合物が挙げら
れる。好ましくは、酢酸亜鉛および亜鉛アルコキシドで
ある。また、沸点が２５０℃以下の含酸素有機化合物は
上記亜鉛化合物を溶解する溶媒として用いられる。この
溶媒は、特に限定されないが、例えばメタノール，エタ
ノール，ｎ−プロパノール，イソプロパノール，ｎ−ブ
タノール，イソブタノール，ｓｅｃ−ブタノール，ｔ−
ブタノール，エチレングリコールモノメチルエーテル，
エチレングリコールモノエチルエーテル等の炭素数１〜
５の脂肪族アルコール類あるいはその誘導体、アセト
ン，アセチルアセトン，メチルエチルケトン等のケトン
類、ジメチルエーテル，ジエチルエーテル等のエーテ
ル、酢酸，プロピオン酸等のカルボン酸等を挙げること
ができる。これらの中で特に炭素数１〜５の脂肪族アル
コールが好適である。また、上記溶媒は、場合に応じて
それぞれ単独で用いてもよく、二種以上を組合わせて用
いてもよい。In the present invention, the raw material zinc compound is not particularly limited, but examples thereof include inorganic compounds such as zinc chloride, zinc nitrate and zinc sulfate, and organic compounds such as zinc acetate, zinc formate, zinc acetylacetonato and zinc alkoxide. Can be mentioned. Preferred are zinc acetate and zinc alkoxide. An oxygen-containing organic compound having a boiling point of 250 ° C. or lower is used as a solvent for dissolving the zinc compound. The solvent is not particularly limited, but for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-
Butanol, ethylene glycol monomethyl ether,
1 to 1 carbon atoms such as ethylene glycol monoethyl ether
5, aliphatic alcohols or derivatives thereof, ketones such as acetone, acetylacetone and methyl ethyl ketone, ethers such as dimethyl ether and diethyl ether, and carboxylic acids such as acetic acid and propionic acid. Of these, aliphatic alcohols having 1 to 5 carbon atoms are particularly preferable. The above solvents may be used alone or in combination of two or more depending on the case.
【０００６】さらに本発明においては、上記溶媒に対す
る亜鉛化合物の溶解性を向上させるために、沸点が２５
０℃以下の含窒素有機化合物が添加剤として用いられ
る。この添加剤としては、アミンが好ましく、例えばモ
ノエタノールアミン，２−アミノ−２−メチル−１−プ
ロパノール等の水酸基含有アミン、ｎ−プロピルアミ
ン，イソプロピルアミン等の炭素数１〜１５のアルキル
アミン、アニリン等の芳香族アミン等が挙げられる。こ
れらの中で特に水酸基含有アミンが好適である。また、
上記添加剤はそれぞれ単独で用いてもよく、場合に応じ
て二種以上を組合わせて用いてもよい。ここで、上記沸
点が２５０℃を超える溶媒および添加物を用いた場合、
得られる酸化亜鉛薄膜中に溶媒および添加物が残留し、
薄膜の配向を阻害する。Further, in the present invention, in order to improve the solubility of the zinc compound in the above solvent, the boiling point is 25
A nitrogen-containing organic compound having a temperature of 0 ° C. or lower is used as an additive. The additive is preferably an amine, for example, a hydroxyl group-containing amine such as monoethanolamine or 2-amino-2-methyl-1-propanol, an alkylamine having 1 to 15 carbon atoms such as n-propylamine or isopropylamine, Examples thereof include aromatic amines such as aniline. Of these, hydroxyl group-containing amines are particularly preferable. Also,
The above additives may be used alone or in combination of two or more depending on the case. Here, when using the solvent and the additive having the boiling point above 250 ° C.,
Solvents and additives remain in the resulting zinc oxide thin film,
It hinders the orientation of the thin film.
【０００７】本発明は、まず亜鉛化合物，溶媒，添加剤
を混合して塗布液を調製する。この塗布液の調製におい
て、各成分の混合順序については特に制限はなく、任意
の順序で混合を行ってもよい。例えば、亜鉛化合物と溶
媒を混合した後、添加剤を添加する調製方法が挙げられ
る。また、混合時には３５〜１２０℃に加温し、各成分
を混合して配向した薄膜の作成に必要な均一透明溶液を
調製する。ここで、溶媒および添加剤の沸点以上で加温
する場合は、還流して行うのがよい。また、この加温は
溶媒に対して溶解性の低い亜鉛化合物の溶解度を増加さ
せ、添加剤との反応を促進させるためにも重要な操作で
ある。好ましい加温は、４０〜９５℃である。その後、
溶媒を蒸発させて濃縮し、濃度を高めてもよい。In the present invention, first, a zinc compound, a solvent and an additive are mixed to prepare a coating solution. In the preparation of this coating liquid, the order of mixing the respective components is not particularly limited, and they may be mixed in any order. For example, there may be mentioned a preparation method in which an additive is added after mixing a zinc compound and a solvent. Further, at the time of mixing, the mixture is heated to 35 to 120 ° C., and each component is mixed to prepare a uniform transparent solution necessary for forming an oriented thin film. Here, when heating is performed at a temperature not lower than the boiling points of the solvent and the additive, it is preferable to carry out reflux. This heating is also an important operation for increasing the solubility of the zinc compound having low solubility in the solvent and promoting the reaction with the additive. The preferable heating is 40 to 95 ° C. afterwards,
The solvent may be evaporated and concentrated to increase the concentration.
【０００８】上記塗布液における亜鉛化合物の濃度につ
いては特に制限はなく、低濃度でもよいが、0.００１モ
ル／リットル以上が好ましい。また、添加剤の添加量
は、通常、亜鉛化合物１モルに対し、0.５モル以上であ
ればよい。さらに、上記塗布液には、本発明の目的が損
なわれない範囲で、所望に応じ酢酸等の酸や上記含酸素
有機化合物以外のアルカリ等の添加剤、あるいは水を添
加してもよいし、粘度等を調整する目的で他の有機溶媒
を添加してもよく、さらには使用する溶媒に溶解する他
の金属の化合物、例えばアルミニウム，インジウム，ス
ズ，ビスマス等の金属化合物を添加してもよい。The concentration of the zinc compound in the coating solution is not particularly limited and may be a low concentration, but it is preferably 0.001 mol / liter or more. Further, the amount of the additive added is usually 0.5 mol or more per 1 mol of the zinc compound. Further, to the above coating liquid, an additive such as an acid such as acetic acid or an alkali other than the oxygen-containing organic compound, or water may be added, if desired, within a range not impairing the object of the present invention, Other organic solvent may be added for the purpose of adjusting viscosity and the like, and further, a compound of another metal soluble in the solvent used, for example, a metal compound such as aluminum, indium, tin or bismuth may be added. ..
【０００９】このようにして調製された塗布液は加水分
解が起こりにくく、安定性に優れている。次に、この塗
布液を基板上に塗布するが、この塗布方法については特
に制限はなく、溶液からの薄膜の形成に従来慣用されて
いる方法、例えば、スプレー法，ディップコート法，ス
ピンコート法等を用いることができる。基板上に塗布さ
れたゲル膜は熱処理が施されるが、この熱処理は通常２
００〜８００℃、好ましくは３００〜７００℃の範囲で
行われる。また、熱処理時間は１０分ないし５時間程度
で充分である。この熱処理によって、ゲル膜は、熱処理
温度が２５０℃付近より結晶化を開始する。このように
して形成された酸化亜鉛薄膜はサイズの均一な酸化亜鉛
粒子からなるため透明性が良好であり、Ｃ軸が基板の表
面に垂直な配向を有するものである。また、その膜厚は
通常0.０１〜１０μｍの範囲である。本発明において用
いられる基板は、塗布液及び熱処理に耐えるものであれ
ばよく、例えば耐熱ガラス，石英ガラス，単結晶，セラ
ミックス，プラスチック等の基板を用いることができ
る。The coating liquid thus prepared is less susceptible to hydrolysis and has excellent stability. Next, the coating solution is coated on the substrate, but the coating method is not particularly limited, and a method conventionally used for forming a thin film from a solution, for example, a spray method, a dip coating method, a spin coating method is used. Etc. can be used. The gel film coated on the substrate is heat-treated, but this heat treatment is usually 2
The temperature is in the range of 00 to 800 ° C, preferably 300 to 700 ° C. A heat treatment time of about 10 minutes to 5 hours is sufficient. By this heat treatment, the gel film starts to crystallize at a heat treatment temperature of around 250 ° C. The zinc oxide thin film thus formed has good transparency because it is composed of zinc oxide particles of uniform size, and the C axis has an orientation perpendicular to the surface of the substrate. The film thickness is usually in the range of 0.01 to 10 μm. The substrate used in the present invention may be one that can withstand the coating liquid and the heat treatment, and for example, a substrate such as heat-resistant glass, quartz glass, single crystal, ceramics, plastic can be used.
【００１０】[0010]
【実施例】次に実施例および比較例により本発明をさら
に詳しく説明するが、本発明はこれらの例によって何ら
限定されるものではない。 実施例１ エチレングリコールモノメチルエーテルに酢酸亜鉛２水
和物を濃度0.７５モル／リットルとなるように加え、更
にモノエタノールアミン（沸点：１７０℃）を酢酸亜鉛
２水和物と同じモル量をスターラーで攪拌しながら添加
し、６０℃で３０分間攪拌して塗布液を得た。得られた
塗布液にシリカガラス基板を室温で浸漬した後、約3.５
ｃｍ／分で基板を塗布液から引上げ電気炉で５００℃，
１０分間熱処理して透明なゲル膜を得た。この浸漬−引
上げ−熱処理を３回繰り返して行った。得られた薄膜
は、Ｘ線回折測定によるとＣ軸が基板の表面に垂直に配
向した酸化亜鉛薄膜であった。膜厚は、約１１００Å
（走査型電子顕微鏡による測定）であった。The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Example 1 Zinc acetate dihydrate was added to ethylene glycol monomethyl ether to a concentration of 0.75 mol / liter, and monoethanolamine (boiling point: 170 ° C.) was added in the same molar amount as zinc acetate dihydrate. The mixture was added with stirring with a stirrer and stirred at 60 ° C. for 30 minutes to obtain a coating liquid. After soaking the silica glass substrate in the obtained coating solution at room temperature, about 3.5
The substrate is pulled up from the coating liquid at 500 cm / min in an electric furnace at 500 ° C,
It was heat-treated for 10 minutes to obtain a transparent gel film. This dipping-pulling-heat treatment was repeated three times. The obtained thin film was a zinc oxide thin film in which the C axis was oriented perpendicular to the surface of the substrate according to X-ray diffraction measurement. The film thickness is about 1100Å
(Measurement with a scanning electron microscope).
【００１１】実施例２ エチレングリコールモノメチルエーテルの代わりにメタ
ノールを用いた以外は、実施例１と同様にして酸化亜鉛
薄膜を得た。得られた薄膜は、Ｘ線回折測定によるとＣ
軸が基板の表面に垂直に配向した酸化亜鉛薄膜であっ
た。膜厚は、約７７０Å（走査型電子顕微鏡による測
定）であった。Example 2 A zinc oxide thin film was obtained in the same manner as in Example 1 except that methanol was used instead of ethylene glycol monomethyl ether. The obtained thin film was C according to X-ray diffraction measurement.
It was a zinc oxide thin film whose axis was oriented perpendicular to the surface of the substrate. The film thickness was about 770Å (measured by a scanning electron microscope).
【００１２】実施例３ エチレングリコールモノメチルエーテルの代わりにｎ−
ブタノールを用いた以外は、実施例１と同様にして酸化
亜鉛薄膜を得た。得られた薄膜は、Ｘ線回折測定による
とＣ軸が基板の表面に垂直に配向した酸化亜鉛薄膜であ
った。膜厚は、約１６００Å（走査型電子顕微鏡による
測定）であった。Example 3 Instead of ethylene glycol monomethyl ether, n-
A zinc oxide thin film was obtained in the same manner as in Example 1 except that butanol was used. The obtained thin film was a zinc oxide thin film in which the C axis was oriented perpendicular to the surface of the substrate according to X-ray diffraction measurement. The film thickness was about 1600Å (measured by a scanning electron microscope).
【００１３】実施例４ モノエタノールアミンの代わりにｎ−プロピルアミン
（沸点：４８℃）を用いた以外は、実施例１と同様にし
て酸化亜鉛薄膜を得た。得られた薄膜は、Ｘ線回折測定
によるとＣ軸が基板の表面に垂直に配向した酸化亜鉛薄
膜であった。膜厚は、約１６００Å（走査型電子顕微鏡
による測定）であった。Example 4 A zinc oxide thin film was obtained in the same manner as in Example 1 except that n-propylamine (boiling point: 48 ° C.) was used instead of monoethanolamine. The obtained thin film was a zinc oxide thin film in which the C axis was oriented perpendicular to the surface of the substrate according to X-ray diffraction measurement. The film thickness was about 1600Å (measured by a scanning electron microscope).
【００１４】実施例５ 実施例１で得られた塗布液にアルミニウムイソプロポキ
シドを含有亜鉛に対して３モル％添加し塗布液として用
いた以外は、実施例１と同様にして酸化亜鉛薄膜を得
た。得られた薄膜は、Ｘ線回折測定によるとＣ軸が基板
の表面に垂直に配向した酸化亜鉛薄膜であった。膜厚
は、約７７０Å（走査型電子顕微鏡による測定）であっ
た。Example 5 A zinc oxide thin film was prepared in the same manner as in Example 1 except that 3 mol% of aluminum isopropoxide-containing zinc was added to the coating solution obtained in Example 1 to prepare a coating solution. Obtained. The obtained thin film was a zinc oxide thin film in which the C axis was oriented perpendicular to the surface of the substrate according to X-ray diffraction measurement. The film thickness was about 770Å (measured by a scanning electron microscope).
【００１５】実施例６ エチレングリコールモノメチルエーテルの代わりにエタ
ノールを用いて得られた塗布液に酢酸インジウムを含有
亜鉛に対して３モル％添加し塗布液として用いた以外
は、実施例１と同様にして酸化亜鉛薄膜を得た。得られ
た薄膜は、Ｘ線回折測定によるとＣ軸が基板の表面に垂
直に配向した酸化亜鉛薄膜であった。膜厚は、約１１０
０Å（走査型電子顕微鏡による測定）であった。Example 6 The same as Example 1 except that 3 mol% of zinc containing indium acetate was added to a coating solution obtained by using ethanol instead of ethylene glycol monomethyl ether, and the resulting coating solution was used. To obtain a zinc oxide thin film. The obtained thin film was a zinc oxide thin film in which the C axis was oriented perpendicular to the surface of the substrate according to X-ray diffraction measurement. The film thickness is about 110
It was 0Å (measurement with a scanning electron microscope).
【００１６】比較例１ モノエタノールアミンの代わりにジエタノールアミン
（沸点：２７０℃）を用いた以外は、実施例１と同様に
して酸化亜鉛薄膜を得た。得られた薄膜は、Ｘ線回折に
よると配向性のない酸化亜鉛薄膜であった。膜厚は、約
１１００Å（走査型電子顕微鏡による測定）であった。Comparative Example 1 A zinc oxide thin film was obtained in the same manner as in Example 1 except that diethanolamine (boiling point: 270 ° C.) was used instead of monoethanolamine. The obtained thin film was a zinc oxide thin film having no orientation according to X-ray diffraction. The film thickness was about 1100Å (measured by a scanning electron microscope).
【００１７】比較例２ 加熱しなかった以外は、実施例３と同様にして塗布液を
作成した。得られた塗布液には沈澱が生じ、均一で透明
な塗布液を得ることはできなかった。Comparative Example 2 A coating solution was prepared in the same manner as in Example 3 except that heating was not performed. Precipitation occurred in the obtained coating liquid, and a uniform and transparent coating liquid could not be obtained.
【００１８】[0018]
【発明の効果】本発明によれば、均一透明で緻密なＣ軸
が基板の表面に垂直な配向を有する（導電性，圧電性に
優れている）亜鉛酸化薄膜を、簡便かつ低コストで製造
することができる。本発明によって製造される酸化亜鉛
薄膜は、センサ，表面波デバイス，バリスタ，透明電極
等の材料やγ線の発光材料，光導波路素子，強誘電性薄
膜作成用基板等として有効な利用が期待される。EFFECTS OF THE INVENTION According to the present invention, a uniform and transparent zinc oxide thin film having a dense C-axis perpendicular to the surface of the substrate (excellent in conductivity and piezoelectricity) can be produced easily and at low cost. can do. The zinc oxide thin film produced by the present invention is expected to be effectively used as a material for a sensor, a surface wave device, a varistor, a transparent electrode, a γ-ray emitting material, an optical waveguide element, a substrate for forming a ferroelectric thin film, and the like. It
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年４月２８日[Submission date] April 28, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の詳細な説明[Name of item to be amended] Detailed explanation of the invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は酸化亜鉛薄膜の製造方法
に関し、さらに詳しくは、センサ，表面波デバイス，バ
リスタ，透明電極等の材料，γ線の発光材料，光導波路
素子，強誘電性薄膜作成用基板等として有用な均一かつ
緻密なＣ軸が基板の表面に垂直に配向した酸化亜鉛薄膜
を簡便かつ低コストで製造する方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a zinc oxide thin film, and more specifically, a material for a sensor, a surface wave device, a varistor, a transparent electrode, etc., a γ-ray emitting material, an optical waveguide device, a ferroelectric thin film. The present invention relates to a method for easily and inexpensively producing a zinc oxide thin film, which is useful as a substrate for preparation and has a uniform and dense C-axis perpendicular to the surface of the substrate.
【０００２】[0002]
【従来の技術】一般に、酸化亜鉛薄膜は、光学的に透明
で、圧電性やｎ−型半導体特性を有し、例えば表面波デ
バイス，バリスタ，透明電極等に幅広く利用できる材料
である。このように、酸化亜鉛薄膜は利用価値が高いた
め、簡便で安価な製造方法が望まれている。従来、金属
酸化物薄膜の製造方法、特にＣ軸が基板の表面に垂直に
配向している薄膜の製造方法としては、例えば真空蒸着
法，スパッタリング法，気相化学反応法（ＣＶＤ法），
噴霧熱分解法（スプレーパイロリシス法）等がよく用い
られている。しかしながら、従来の方法においては、薄
膜製造設備が大がかりとなり、大面積の薄膜を製造する
ことが困難であり、Ｃ軸が基板の表面に垂直に配向して
いない薄膜も製造されていた。また、高橋らは第３０回
セラミックス基礎科学討論会予稿集（１９９１年）にお
いて、イソプロパノールに亜鉛ｎ−プロポキシドおよび
／または酢酸亜鉛２水和物をジエタノールアミンと共に
溶解し、基板に塗布後熱処理することにより得られる酸
化亜鉛薄膜を開示している。この酸化亜鉛薄膜は、原料
であるジエタノールアミンの沸点が２７０℃と高温のた
め、配向薄膜が得られない。また、他のアミンを用いて
塗布液を調製しているが、加熱および攪拌処理を施して
いないため透明な塗布液が得られない。2. Description of the Related Art Generally, a zinc oxide thin film is a material which is optically transparent, has piezoelectricity and n-type semiconductor characteristics, and can be widely used in, for example, surface wave devices, varistors, transparent electrodes and the like. As described above, since the zinc oxide thin film has a high utility value, a simple and inexpensive manufacturing method is desired. Conventionally, as a method for producing a metal oxide thin film, particularly a method for producing a thin film in which the C axis is oriented perpendicular to the surface of the substrate, there are, for example, a vacuum vapor deposition method, a sputtering method, a vapor phase chemical reaction method (CVD method),
The spray pyrolysis method (spray pyrolysis method) and the like are often used. However, in the conventional method, the thin-film manufacturing equipment becomes large-scale, it is difficult to manufacture a large-area thin film, and a thin film in which the C axis is not oriented perpendicular to the surface of the substrate has also been manufactured. In addition, Takahashi et al., In the proceedings of the 30th Ceramic Science Symposium (1991), dissolve zinc n-propoxide and / or zinc acetate dihydrate together with diethanolamine in isopropanol and heat it after coating on the substrate. The zinc oxide thin film obtained by the above is disclosed. An oriented thin film cannot be obtained from this zinc oxide thin film because the boiling point of the raw material, diethanolamine, is 270 ° C. Further, although the coating solution is prepared using other amine, a transparent coating solution cannot be obtained because it is not subjected to heating and stirring treatment.
【０００３】[0003]
【発明が解決しようとする課題】そこで本発明者らは、
上記従来技術の欠点を解消し、均一かつ透明で緻密なＣ
軸が基板の表面に垂直な配向を有する亜鉛酸化薄膜を、
簡便かつ低コストで製造する方法を開発すべく鋭意研究
を重ねた。Therefore, the present inventors have found that
A uniform, transparent, and dense C that solves the above-mentioned drawbacks of the prior art
A zinc oxide thin film whose axis is oriented perpendicular to the surface of the substrate,
We have conducted intensive research to develop a simple and low-cost manufacturing method.
【０００４】[0004]
【課題を解決するための手段】その結果、亜鉛化合物，
沸点が２５０℃以下の溶媒および沸点が２５０℃以下の
添加剤を混合し、３５〜１２０℃に加温，攪拌して得ら
れる塗布液を用いることによって、上記目的を達成でき
ることを見出した。本発明はかかる知見に基いて完成し
たものである。すなわち本発明は、亜鉛化合物，沸点が
２５０℃以下の含酸素有機化合物および沸点が２５０℃
以下の含窒素有機化合物を混合し、３５〜１２０℃に加
温，攪拌して塗布液を調製し、次いで該塗布液を基板に
塗布したのち、熱処理することを特徴とする酸化亜鉛薄
膜の製造方法を提供するものである。As a result, a zinc compound,
It has been found that the above object can be achieved by using a coating solution obtained by mixing a solvent having a boiling point of 250 ° C. or lower and an additive having a boiling point of 250 ° C. or lower and heating the mixture to 35 to 120 ° C. and stirring. The present invention has been completed based on such findings. That is, the present invention includes a zinc compound, an oxygen-containing organic compound having a boiling point of 250 ° C or lower, and a boiling point of 250 ° C.
The following nitrogen-containing organic compounds are mixed, heated to 35 to 120 ° C. and stirred to prepare a coating solution, which is then coated on a substrate and then heat-treated, to produce a zinc oxide thin film. It provides a method.
【０００５】本発明において、原料の亜鉛化合物は、特
に限定されないが、例えば塩化亜鉛，硝酸亜鉛，硫酸亜
鉛等の無機化合物や酢酸亜鉛，蟻酸亜鉛，アセチルアセ
トナト亜鉛，亜鉛アルコキシド等の有機化合物が挙げら
れる。好ましくは、酢酸亜鉛および亜鉛アルコキシドで
ある。また、沸点が２５０℃以下の含酸素有機化合物は
上記亜鉛化合物を溶解する溶媒として用いられる。この
溶媒は、特に限定されないが、例えばメタノール，エタ
ノール，ｎ−プロパノール，イソプロパノール，ｎ−ブ
タノール，イソブタノール，ｓｅｃ−ブタノール，ｔ−
ブタノール，エチレングリコールモノメチルエーテル，
エチレングリコールモノエチルエーテル等の炭素数１〜
５の脂肪族アルコール類あるいはその誘導体、アセト
ン，アセチルアセトン，メチルエチルケトン等のケトン
類、ジメチルエーテル，ジエチルエーテル等のエーテ
ル、酢酸，プロピオン酸等のカルボン酸等を挙げること
ができる。これらの中で特に炭素数１〜５の脂肪族アル
コールが好適である。また、上記溶媒は、場合に応じて
それぞれ単独で用いてもよく、二種以上を組合わせて用
いてもよい。In the present invention, the raw material zinc compound is not particularly limited, but examples thereof include inorganic compounds such as zinc chloride, zinc nitrate and zinc sulfate, and organic compounds such as zinc acetate, zinc formate, zinc acetylacetonato and zinc alkoxide. Can be mentioned. Preferred are zinc acetate and zinc alkoxide. An oxygen-containing organic compound having a boiling point of 250 ° C. or lower is used as a solvent for dissolving the zinc compound. The solvent is not particularly limited, but for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-
Butanol, ethylene glycol monomethyl ether,
1 to 1 carbon atoms such as ethylene glycol monoethyl ether
5, aliphatic alcohols or derivatives thereof, ketones such as acetone, acetylacetone and methyl ethyl ketone, ethers such as dimethyl ether and diethyl ether, and carboxylic acids such as acetic acid and propionic acid. Of these, aliphatic alcohols having 1 to 5 carbon atoms are particularly preferable. The above solvents may be used alone or in combination of two or more depending on the case.
【０００６】さらに本発明においては、上記溶媒に対す
る亜鉛化合物の溶解性を向上させるために、沸点が２５
０℃以下の含窒素有機化合物が添加剤として用いられ
る。この添加剤としては、アミンが好ましく、例えばモ
ノエタノールアミン，２−アミノ−２−メチル−１−プ
ロパノール等の水酸基含有アミン、ｎ−プロピルアミ
ン，イソプロピルアミン等の炭素数１〜１５のアルキル
アミン、アニリン等の芳香族アミン等が挙げられる。こ
れらの中で特に水酸基含有アミンが好適である。また、
上記添加剤はそれぞれ単独で用いてもよく、場合に応じ
て二種以上を組合わせて用いてもよい。ここで、上記沸
点が２５０℃を超える溶媒および添加物を用いた場合、
得られる酸化亜鉛薄膜中に溶媒および添加物が残留し、
薄膜の配向を阻害する。Further, in the present invention, in order to improve the solubility of the zinc compound in the above solvent, the boiling point is 25
A nitrogen-containing organic compound having a temperature of 0 ° C. or lower is used as an additive. The additive is preferably an amine, for example, a hydroxyl group-containing amine such as monoethanolamine or 2-amino-2-methyl-1-propanol, an alkylamine having 1 to 15 carbon atoms such as n-propylamine or isopropylamine, Examples thereof include aromatic amines such as aniline. Of these, hydroxyl group-containing amines are particularly preferable. Also,
The above additives may be used alone or in combination of two or more depending on the case. Here, when using the solvent and the additive having the boiling point above 250 ° C.,
Solvents and additives remain in the resulting zinc oxide thin film,
It hinders the orientation of the thin film.
【０００７】本発明は、まず亜鉛化合物，溶媒，添加剤
を混合して塗布液を調製する。この塗布液の調製におい
て、各成分の混合順序については特に制限はなく、任意
の順序で混合を行ってもよい。例えば、亜鉛化合物と溶
媒を混合した後、添加剤を添加する調製方法が挙げられ
る。また、混合時には３５〜１２０℃に加温し、各成分
を混合して配向した薄膜の作成に必要な均一透明溶液を
調製する。ここで、溶媒および添加剤の沸点以上で加温
する場合は、還流して行うのがよい。また、この加温は
溶媒に対して溶解性の低い亜鉛化合物の溶解度を増加さ
せ、添加剤との反応を促進させるためにも重要な操作で
ある。好ましい加温は、４０〜９５℃である。その後、
溶媒を蒸発させて濃縮し、濃度を高めてもよい。In the present invention, first, a zinc compound, a solvent and an additive are mixed to prepare a coating solution. In the preparation of this coating liquid, the order of mixing the respective components is not particularly limited, and they may be mixed in any order. For example, there may be mentioned a preparation method in which an additive is added after mixing a zinc compound and a solvent. Further, at the time of mixing, the mixture is heated to 35 to 120 ° C., and each component is mixed to prepare a uniform transparent solution necessary for forming an oriented thin film. Here, when heating is performed at a temperature not lower than the boiling points of the solvent and the additive, it is preferable to carry out reflux. This heating is also an important operation for increasing the solubility of the zinc compound having low solubility in the solvent and promoting the reaction with the additive. The preferable heating is 40 to 95 ° C. afterwards,
The solvent may be evaporated and concentrated to increase the concentration.
【０００８】上記塗布液における亜鉛化合物の濃度につ
いては特に制限はなく、低濃度でもよいが、0.００１モ
ル／リットル以上が好ましい。また、添加剤の添加量
は、通常、亜鉛化合物１モルに対し、0.５モル以上であ
ればよい。さらに、上記塗布液には、本発明の目的が損
なわれない範囲で、所望に応じ酢酸等の酸や上記含酸素
有機化合物以外のアルカリ等の添加剤、あるいは水を添
加してもよいし、粘度等を調整する目的で他の有機溶媒
を添加してもよく、さらには使用する溶媒に溶解する他
の金属の化合物、例えばアルミニウム，インジウム，ス
ズ，ビスマス等の金属化合物を添加してもよい。The concentration of the zinc compound in the coating solution is not particularly limited and may be a low concentration, but it is preferably 0.001 mol / liter or more. Further, the amount of the additive added is usually 0.5 mol or more per 1 mol of the zinc compound. Further, to the above coating liquid, an additive such as an acid such as acetic acid or an alkali other than the oxygen-containing organic compound, or water may be added, if desired, within a range not impairing the object of the present invention, Other organic solvent may be added for the purpose of adjusting viscosity and the like, and further, a compound of another metal soluble in the solvent used, for example, a metal compound such as aluminum, indium, tin or bismuth may be added. ..
【０００９】このようにして調製された塗布液は加水分
解が起こりにくく、安定性に優れている。次に、この塗
布液を基板上に塗布するが、この塗布方法については特
に制限はなく、溶液からの薄膜の形成に従来慣用されて
いる方法、例えば、スプレー法，ディップコート法，ス
ピンコート法等を用いることができる。基板上に塗布さ
れたゲル膜は熱処理が施されるが、この熱処理は通常２
００〜８００℃、好ましくは３００〜７００℃の範囲で
行われる。また、熱処理時間は１０分ないし５時間程度
で充分である。この熱処理によって、ゲル膜は、熱処理
温度が２５０℃付近より結晶化を開始する。このように
して形成された酸化亜鉛薄膜はサイズの均一な酸化亜鉛
粒子からなるため透明性が良好であり、Ｃ軸が基板の表
面に垂直な配向を有するものである。また、その膜厚は
通常0.０１〜１０μｍの範囲である。本発明において用
いられる基板は、塗布液及び熱処理に耐えるものであれ
ばよく、例えば耐熱ガラス，石英ガラス，単結晶，セラ
ミックス，プラスチック等の基板を用いることができ
る。The coating liquid thus prepared is less susceptible to hydrolysis and has excellent stability. Next, the coating solution is coated on the substrate, but the coating method is not particularly limited, and a method conventionally used for forming a thin film from a solution, for example, a spray method, a dip coating method, a spin coating method is used. Etc. can be used. The gel film coated on the substrate is heat-treated, but this heat treatment is usually 2
The temperature is in the range of 00 to 800 ° C, preferably 300 to 700 ° C. A heat treatment time of about 10 minutes to 5 hours is sufficient. By this heat treatment, the gel film starts to crystallize at a heat treatment temperature of around 250 ° C. The zinc oxide thin film thus formed has good transparency because it is composed of zinc oxide particles of uniform size, and the C axis has an orientation perpendicular to the surface of the substrate. The film thickness is usually in the range of 0.01 to 10 μm. The substrate used in the present invention may be one that can withstand the coating liquid and the heat treatment, and for example, a substrate such as heat-resistant glass, quartz glass, single crystal, ceramics, plastic can be used.
【００１０】[0010]
【実施例】次に実施例および比較例により本発明をさら
に詳しく説明するが、本発明はこれらの例によって何ら
限定されるものではない。 実施例１ エチレングリコールモノメチルエーテルに酢酸亜鉛２水
和物を濃度0.７５モル／リットルとなるように加え、更
にモノエタノールアミン（沸点：１７０℃）を酢酸亜鉛
２水和物と同じモル量をスターラーで攪拌しながら添加
し、６０℃で３０分間攪拌して塗布液を得た。得られた
塗布液にシリカガラス基板を室温で浸漬した後、約3.５
ｃｍ／分で基板を塗布液から引上げ電気炉で５００℃，
１０分間熱処理して透明なゲル膜を得た。この浸漬−引
上げ−熱処理を３回繰り返して行った。得られた薄膜
は、Ｘ線回折測定によるとＣ軸が基板の表面に垂直に配
向した酸化亜鉛薄膜であった。膜厚は、約１１００Å
（走査型電子顕微鏡による測定）であった。The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Example 1 Zinc acetate dihydrate was added to ethylene glycol monomethyl ether to a concentration of 0.75 mol / liter, and monoethanolamine (boiling point: 170 ° C.) was added in the same molar amount as zinc acetate dihydrate. The mixture was added with stirring with a stirrer and stirred at 60 ° C. for 30 minutes to obtain a coating liquid. After soaking the silica glass substrate in the obtained coating solution at room temperature, about 3.5
The substrate is pulled up from the coating liquid at 500 cm / min in an electric furnace at 500 ° C,
It was heat-treated for 10 minutes to obtain a transparent gel film. This dipping-pulling-heat treatment was repeated three times. The obtained thin film was a zinc oxide thin film in which the C axis was oriented perpendicular to the surface of the substrate according to X-ray diffraction measurement. The film thickness is about 1100Å
(Measurement with a scanning electron microscope).
【００１１】実施例２ エチレングリコールモノメチルエーテルの代わりにメタ
ノールを用いた以外は、実施例１と同様にして酸化亜鉛
薄膜を得た。得られた薄膜は、Ｘ線回折測定によるとＣ
軸が基板の表面に垂直に配向した酸化亜鉛薄膜であっ
た。膜厚は、約７７０Å（走査型電子顕微鏡による測
定）であった。Example 2 A zinc oxide thin film was obtained in the same manner as in Example 1 except that methanol was used instead of ethylene glycol monomethyl ether. The obtained thin film was C according to X-ray diffraction measurement.
It was a zinc oxide thin film whose axis was oriented perpendicular to the surface of the substrate. The film thickness was about 770Å (measured by a scanning electron microscope).
【００１２】実施例３ エチレングリコールモノメチルエーテルの代わりにｎ−
ブタノールを用いた以外は、実施例１と同様にして酸化
亜鉛薄膜を得た。得られた薄膜は、Ｘ線回折測定による
とＣ軸が基板の表面に垂直に配向した酸化亜鉛薄膜であ
った。膜厚は、約１６００Å（走査型電子顕微鏡による
測定）であった。Example 3 Instead of ethylene glycol monomethyl ether, n-
A zinc oxide thin film was obtained in the same manner as in Example 1 except that butanol was used. The obtained thin film was a zinc oxide thin film in which the C axis was oriented perpendicular to the surface of the substrate according to X-ray diffraction measurement. The film thickness was about 1600Å (measured by a scanning electron microscope).
【００１３】実施例４ モノエタノールアミンの代わりにｎ−プロピルアミン
（沸点：４８℃）を用いた以外は、実施例１と同様にし
て酸化亜鉛薄膜を得た。得られた薄膜は、Ｘ線回折測定
によるとＣ軸が基板の表面に垂直に配向した酸化亜鉛薄
膜であった。膜厚は、約１６００Å（走査型電子顕微鏡
による測定）であった。Example 4 A zinc oxide thin film was obtained in the same manner as in Example 1 except that n-propylamine (boiling point: 48 ° C.) was used instead of monoethanolamine. The obtained thin film was a zinc oxide thin film in which the C axis was oriented perpendicular to the surface of the substrate according to X-ray diffraction measurement. The film thickness was about 1600Å (measured by a scanning electron microscope).
【００１４】実施例５ 実施例１で得られた塗布液にアルミニウムイソプロポキ
シドを含有亜鉛に対して３モル％添加し塗布液として用
いた以外は、実施例１と同様にして酸化亜鉛薄膜を得
た。得られた薄膜は、Ｘ線回折測定によるとＣ軸が基板
の表面に垂直に配向した酸化亜鉛薄膜であった。膜厚
は、約７７０Å（走査型電子顕微鏡による測定）であっ
た。Example 5 A zinc oxide thin film was prepared in the same manner as in Example 1 except that 3 mol% of aluminum isopropoxide-containing zinc was added to the coating solution obtained in Example 1 to prepare a coating solution. Obtained. The obtained thin film was a zinc oxide thin film in which the C axis was oriented perpendicular to the surface of the substrate according to X-ray diffraction measurement. The film thickness was about 770Å (measured by a scanning electron microscope).
【００１５】実施例６ エチレングリコールモノメチルエーテルの代わりにエタ
ノールを用いて得られた塗布液に酢酸インジウムを含有
亜鉛に対して３モル％添加し塗布液として用いた以外
は、実施例１と同様にして酸化亜鉛薄膜を得た。得られ
た薄膜は、Ｘ線回折測定によるとＣ軸が基板の表面に垂
直に配向した酸化亜鉛薄膜であった。膜厚は、約１１０
０Å（走査型電子顕微鏡による測定）であった。Example 6 The same as Example 1 except that 3 mol% of zinc containing indium acetate was added to a coating solution obtained by using ethanol instead of ethylene glycol monomethyl ether, and the resulting coating solution was used. To obtain a zinc oxide thin film. The obtained thin film was a zinc oxide thin film in which the C axis was oriented perpendicular to the surface of the substrate according to X-ray diffraction measurement. The film thickness is about 110
It was 0Å (measurement with a scanning electron microscope).
【００１６】比較例１ モノエタノールアミンの代わりにジエタノールアミン
（沸点：２７０℃）を用いた以外は、実施例１と同様に
して酸化亜鉛薄膜を得た。得られた薄膜は、Ｘ線回折に
よると配向性のない酸化亜鉛薄膜であった。膜厚は、約
１１００Å（走査型電子顕微鏡による測定）であった。Comparative Example 1 A zinc oxide thin film was obtained in the same manner as in Example 1 except that diethanolamine (boiling point: 270 ° C.) was used instead of monoethanolamine. The obtained thin film was a zinc oxide thin film having no orientation according to X-ray diffraction. The film thickness was about 1100Å (measured by a scanning electron microscope).
【００１７】比較例２ 加熱しなかった以外は、実施例３と同様にして塗布液を
作成した。得られた塗布液には沈澱が生じ、均一で透明
な塗布液を得ることはできなかった。Comparative Example 2 A coating solution was prepared in the same manner as in Example 3 except that heating was not performed. Precipitation occurred in the obtained coating liquid, and a uniform and transparent coating liquid could not be obtained.
【００１８】[0018]
【発明の効果】本発明によれば、均一透明で緻密なＣ軸
が基板の表面に垂直な配向を有する（導電性，圧電性に
優れている）亜鉛酸化薄膜を、簡便かつ低コストで製造
することができる。本発明によって製造される酸化亜鉛
薄膜は、センサ，表面波デバイス，バリスタ，透明電極
等の材料やγ線の発光材料，光導波路素子，強誘電性薄
膜作成用基板等として有効な利用が期待される。EFFECTS OF THE INVENTION According to the present invention, a uniform and transparent zinc oxide thin film having a dense C-axis perpendicular to the surface of the substrate (excellent in conductivity and piezoelectricity) can be produced easily and at low cost. can do. The zinc oxide thin film produced by the present invention is expected to be effectively used as a material for a sensor, a surface wave device, a varistor, a transparent electrode, a γ-ray emitting material, an optical waveguide element, a substrate for forming a ferroelectric thin film, and the like. It
Claims (1)
素有機化合物および沸点が２５０℃以下の含窒素有機化
合物を混合し、３５〜１２０℃に加温，攪拌して塗布液
を調製し、次いで該塗布液を基板に塗布したのち、熱処
理することを特徴とする酸化亜鉛薄膜の製造方法。1. A coating solution is prepared by mixing a zinc compound, an oxygen-containing organic compound having a boiling point of 250 ° C. or lower, and a nitrogen-containing organic compound having a boiling point of 250 ° C. or lower, and heating and stirring at 35 to 120 ° C. Next, a method for producing a zinc oxide thin film, which comprises applying the coating solution to a substrate and then performing heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10436192A JPH05294623A (en) | 1992-04-23 | 1992-04-23 | Production of zinc oxide thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10436192A JPH05294623A (en) | 1992-04-23 | 1992-04-23 | Production of zinc oxide thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05294623A true JPH05294623A (en) | 1993-11-09 |
Family
ID=14378697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10436192A Pending JPH05294623A (en) | 1992-04-23 | 1992-04-23 | Production of zinc oxide thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05294623A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004256377A (en) * | 2003-02-27 | 2004-09-16 | Nippon Shokubai Co Ltd | Method of manufacturing metal oxide film |
| KR20040107318A (en) * | 2003-06-13 | 2004-12-20 | 재단법인 포항산업과학연구원 | Electrochemical Preparation Method of ZnO |
| JP2006089293A (en) * | 2004-09-21 | 2006-04-06 | Nof Corp | Composition for forming zinc oxide thin film |
| JP2007022851A (en) * | 2005-07-15 | 2007-02-01 | National Institute Of Advanced Industrial & Technology | Porous zinc oxide film, production method thereof, dye-sensitized solar cell provided with porous zinc oxide film, photocatalyst, chemical sensor or phosphor, precursor for forming porous zinc oxide film, production method thereof |
| JP2008098637A (en) * | 2006-10-12 | 2008-04-24 | Xerox Corp | Thin film transistor |
| WO2010131621A1 (en) * | 2009-05-12 | 2010-11-18 | 国立大学法人 宮崎大学 | Composition for production of doped zinc oxide thin film, process for production of zinc oxide thin film, antistatic thin film, ultraviolet ray blocking thin film, and transparent electrode thin film |
| JP2010267383A (en) * | 2009-05-12 | 2010-11-25 | Tosoh Finechem Corp | Composition for forming doped zinc oxide thin film and method for producing doped zinc oxide thin film |
| JP2011512029A (en) * | 2008-01-31 | 2011-04-14 | ノースウエスタン ユニバーシティ | Solution processing type high mobility inorganic thin film transistor |
| JP2011170979A (en) * | 2010-02-16 | 2011-09-01 | Univ Of Miyazaki | Method for producing zinc oxide thin film, antistatic thin film produced by the same method, ultraviolet ray blocking thin film, and transparent electrode thin film |
| US9096441B2 (en) | 2009-04-21 | 2015-08-04 | Tosoh Finechem Corporation | Composition for manufacturing doped or undoped zinc oxide thin film and method for manufacturing zinc oxide thin film using same |
| CN115491194A (en) * | 2021-06-18 | 2022-12-20 | 广东聚华印刷显示技术有限公司 | Precursor solution of zinc oxide, preparation method thereof and luminescent device |
-
1992
- 1992-04-23 JP JP10436192A patent/JPH05294623A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004256377A (en) * | 2003-02-27 | 2004-09-16 | Nippon Shokubai Co Ltd | Method of manufacturing metal oxide film |
| KR20040107318A (en) * | 2003-06-13 | 2004-12-20 | 재단법인 포항산업과학연구원 | Electrochemical Preparation Method of ZnO |
| JP2006089293A (en) * | 2004-09-21 | 2006-04-06 | Nof Corp | Composition for forming zinc oxide thin film |
| JP2007022851A (en) * | 2005-07-15 | 2007-02-01 | National Institute Of Advanced Industrial & Technology | Porous zinc oxide film, production method thereof, dye-sensitized solar cell provided with porous zinc oxide film, photocatalyst, chemical sensor or phosphor, precursor for forming porous zinc oxide film, production method thereof |
| KR101452200B1 (en) * | 2006-10-12 | 2014-10-21 | 제록스 코포레이션 | Thin film transistor |
| JP2008098637A (en) * | 2006-10-12 | 2008-04-24 | Xerox Corp | Thin film transistor |
| JP2011512029A (en) * | 2008-01-31 | 2011-04-14 | ノースウエスタン ユニバーシティ | Solution processing type high mobility inorganic thin film transistor |
| US9096441B2 (en) | 2009-04-21 | 2015-08-04 | Tosoh Finechem Corporation | Composition for manufacturing doped or undoped zinc oxide thin film and method for manufacturing zinc oxide thin film using same |
| WO2010131621A1 (en) * | 2009-05-12 | 2010-11-18 | 国立大学法人 宮崎大学 | Composition for production of doped zinc oxide thin film, process for production of zinc oxide thin film, antistatic thin film, ultraviolet ray blocking thin film, and transparent electrode thin film |
| JP2010267383A (en) * | 2009-05-12 | 2010-11-25 | Tosoh Finechem Corp | Composition for forming doped zinc oxide thin film and method for producing doped zinc oxide thin film |
| JP2011170979A (en) * | 2010-02-16 | 2011-09-01 | Univ Of Miyazaki | Method for producing zinc oxide thin film, antistatic thin film produced by the same method, ultraviolet ray blocking thin film, and transparent electrode thin film |
| CN115491194A (en) * | 2021-06-18 | 2022-12-20 | 广东聚华印刷显示技术有限公司 | Precursor solution of zinc oxide, preparation method thereof and luminescent device |
| CN115491194B (en) * | 2021-06-18 | 2023-11-03 | 广东聚华印刷显示技术有限公司 | Precursor solution of zinc oxide, preparation method thereof and light-emitting device |
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