JPH04280817A - Production of thin film from gelatinous material of zirconium oxide-based precursor - Google Patents
Production of thin film from gelatinous material of zirconium oxide-based precursorInfo
- Publication number
- JPH04280817A JPH04280817A JP4343291A JP4343291A JPH04280817A JP H04280817 A JPH04280817 A JP H04280817A JP 4343291 A JP4343291 A JP 4343291A JP 4343291 A JP4343291 A JP 4343291A JP H04280817 A JPH04280817 A JP H04280817A
- Authority
- JP
- Japan
- Prior art keywords
- zirconium oxide
- thin film
- precursor
- gelatinous material
- carboxylic acid
- 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.)
- Granted
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 41
- 239000002243 precursor Substances 0.000 title claims abstract description 34
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000463 material Substances 0.000 title abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000001476 alcoholic effect Effects 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 15
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- -1 zirconium alkoxide Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000001429 visible spectrum Methods 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GGROONUBGIWGGS-UHFFFAOYSA-N oxygen(2-);zirconium(4+);hydrate Chemical compound O.[O-2].[O-2].[Zr+4] GGROONUBGIWGGS-UHFFFAOYSA-N 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Chemically Coating (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、長期保存可能な酸化ジ
ルコニウム系前駆体ゲル状物から薄膜を作製する製造方
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 thin film from a zirconium oxide precursor gel that can be stored for a long period of time.
【０００２】0002
【従来の技術】酸化ジルコニウム及び安定化剤として酸
化イットリウム、酸化カルシウム、酸化マグネシウム等
をドープした安定化酸化ジルコニウム薄膜は、耐アルカ
リ性、耐摩耗性膜として種々の用途に利用されている。
また、透明な薄膜は高屈折率薄膜として選択光反射性被
膜または選択光透過性被膜の成分として利用されている
。酸化物セラミックス薄膜を製造する方法としては、Ｃ
ＶＤ法、プラズマ溶射法、高周波スパッタ法などがある
が、生産性が高い、低温プロセスである、装置のコスト
が安い等の利点から、ディッピングやスピンコーティン
グにより、金属アルコキシドを含む溶液を成形物に塗布
し、加熱を施して酸化物薄膜を形成させる方法が最近よ
く利用されている。BACKGROUND OF THE INVENTION Stabilized zirconium oxide thin films doped with zirconium oxide and stabilizers such as yttrium oxide, calcium oxide, magnesium oxide, etc. are used in various applications as alkali-resistant and wear-resistant films. Further, the transparent thin film is used as a high refractive index thin film as a component of a selective light reflecting coating or a selective light transmitting coating. As a method for manufacturing an oxide ceramic thin film, C
There are VD methods, plasma spraying methods, high frequency sputtering methods, etc., but due to the advantages such as high productivity, low temperature process, and low equipment cost, it is possible to mold a solution containing metal alkoxide by dipping or spin coating. Recently, a method of forming an oxide thin film by coating and heating has been frequently used.
【０００３】しかし、この方法で酸化ジルコニウム系薄
膜を作製する場合に、原料として用いるジルコニウムア
ルコキシドは加水分解−縮合が非常に速いため、水や湿
分に対する溶液の安定性が悪く、容易に加水分解されて
、酸化ジルコニウム水和物を形成し、沈澱する。従って
、溶液を塗布する場合に、均一で透明な塗布層を得るこ
とが困難であった。そのために、塗布の際の湿気をきび
しく制御したり、アルコキシドのアルコキシ基の一部ま
たは全部をキレート形成可能な基、例えば、アセチルア
セトン等で置換することにより、加水分解を著しく抑制
して、溶液を安定化する方法が提案された。However, when producing a zirconium oxide thin film using this method, the zirconium alkoxide used as a raw material undergoes hydrolysis and condensation very quickly, so the stability of the solution against water and moisture is poor, and it is easily hydrolyzed. to form and precipitate zirconium oxide hydrate. Therefore, when applying a solution, it has been difficult to obtain a uniform and transparent coating layer. To this end, hydrolysis can be significantly suppressed by strictly controlling the humidity during application and by substituting some or all of the alkoxy groups of the alkoxide with groups capable of forming chelates, such as acetylacetone. A stabilizing method was proposed.
【０００４】しかし、この溶液を用いて形成した薄膜は
、加水分解−重縮合が十分に進んでいないため、未反応
アルコキシ基及びアルコキシ基と置換した基を多量に含
んでおり、成形物に塗布、加熱して酸化物薄膜を得る場
合、それらの基の分解のために発生するピンホールやク
ラックにより、緻密な膜を形成できないという問題点が
ある。[0004] However, the thin film formed using this solution contains a large amount of unreacted alkoxy groups and groups substituted for alkoxy groups because hydrolysis and polycondensation have not progressed sufficiently, and it is difficult to apply it to molded products. When an oxide thin film is obtained by heating, there is a problem in that a dense film cannot be formed due to pinholes and cracks that occur due to the decomposition of these groups.
【０００５】[0005]
【発明が解決しようとする問題点】解決しようとする問
題点は、ジルコニウムアルコキシドから調製した薄膜作
製用酸化ジルコニウム系前駆体溶液の湿分に対する安定
性が悪く、しかも、成形物への溶液の塗布、焼成による
酸化物薄膜形成の際に、ピンホールやクラックの原因と
なる残留有機物が前駆体中に多量に存在しており、緻密
な酸化ジルコニウム系薄膜が得られないという点である
。[Problems to be Solved by the Invention] The problem to be solved is that the zirconium oxide precursor solution prepared from zirconium alkoxide for thin film production has poor stability against moisture, and furthermore, it is difficult to apply the solution to molded objects. The problem is that a large amount of residual organic matter that causes pinholes and cracks is present in the precursor when forming an oxide thin film by firing, making it impossible to obtain a dense zirconium oxide thin film.
【０００６】[0006]
【課題を解決するための手段】上記の問題点を解決する
ための手段として、本発明者が、先に発明した、Ｚｒ−
Ｏ−Ｚｒ結合を有する、透明な酸化ジルコニウム系前駆
体ポリマーゲル状物を、カルボン酸の少量の添加により
、有機溶媒に溶解して、薄膜作製用溶液とすることを主
要な特徴とする。[Means for Solving the Problems] As a means for solving the above-mentioned problems, the present inventor has previously invented Zr-
The main feature is that a transparent zirconium oxide precursor polymer gel having an O-Zr bond is dissolved in an organic solvent by adding a small amount of carboxylic acid to prepare a solution for forming a thin film.
【０００７】酸化ジルコニウム系前駆体ポリマーゲル状
物は、未反応アルコキシ基がほとんどないために、大気
中の湿分に対して、長期にわたり、きわめて安定である
。この前駆体ポリマーを溶液状にすることができれば、
湿分に対して安定な溶液が得られ、かつ、その溶液を塗
布して得られる薄膜は、ピンホールやクラックの原因と
なる残留有機物のほとんどないものとなると考えられる
。しかし、この前駆体ゲル状物は、有機溶媒に対して、
溶解性が低い。そこで、本発明者は研究の結果、有機溶
媒中に前駆体ゲル状物を入れ、カルボン酸を少量添加し
て、加熱することにより、前駆体ゲル状物が完全に溶解
し、透明な溶液となることを見出した。カルボン酸の添
加は、前駆体ポリマーの末端基を溶媒親和性の高いＯＣ
ＯＲ基に置換することで、前駆体ポリマーをアルコール
系溶媒に溶解可能なものとしたと考えられる。この発明
により、従来のジルコニウムアルコキシドの加水分解を
抑制して調製された溶液に比べて、湿分に対して非常に
安定な薄膜作製用溶液を調製するという目的を実現でき
た。また、この溶液を成形物に塗布し、加熱することに
より、今まで得られなかった残留有機物のほとんどない
、緻密な酸化ジルコニウム系薄膜を得るという目的も実
現できた。Since the zirconium oxide precursor polymer gel has almost no unreacted alkoxy groups, it is extremely stable against atmospheric moisture for a long period of time. If this precursor polymer can be made into a solution,
It is believed that a solution that is stable against moisture can be obtained, and that the thin film obtained by applying the solution will have almost no residual organic matter that causes pinholes or cracks. However, this precursor gel-like material is difficult to react to organic solvents.
Poor solubility. Therefore, as a result of research, the present inventor found that by placing a precursor gel in an organic solvent, adding a small amount of carboxylic acid, and heating, the precursor gel was completely dissolved and a transparent solution was formed. I discovered that. Addition of carboxylic acid converts the end groups of the precursor polymer into OCs with high solvent affinity.
It is thought that the substitution with the OR group made the precursor polymer soluble in alcoholic solvents. This invention has achieved the objective of preparing a solution for forming a thin film that is much more stable against moisture than conventional solutions prepared by suppressing the hydrolysis of zirconium alkoxide. Furthermore, by applying this solution to a molded product and heating it, we were able to achieve the objective of obtaining a dense zirconium oxide thin film with almost no residual organic matter, which had not been possible until now.
【０００８】[0008]
【実施例１】ジルコニウムｎ−プロポキシドと酢酸及び
水（ジルコニウムｎ−プロポキシド：酢酸：水＝１：１
．３３：１〔ｍｏｌ比〕）の反応により、調製した酸化
ジルコニウム前駆体ゲル状物と酢酸及びｎ−ブチルアル
コールを混合（前駆体ゲル状物：酢酸：ｎ−ブチルアル
コール＝１０：１：１０〔重量比〕）し、６０℃に加熱
することにより、前駆体ゲル状物は完全に溶解して、透
明な溶液を形成した。この溶液にガラス板を浸漬し、６
０ｍｍ／ｍｉｎ の速度で引き上げることにより、前駆
体薄膜が形成した。室温で１時間乾燥後、５００℃で３
０分間焼成したところ、透明な正方晶酸化ジルコニウム
薄膜が得られた。この、引き上げ、乾燥、焼成という操
作を３回繰り返して作製した薄膜もまた透明で正方晶で
あった。この酸化ジルコニウム薄膜は、電子顕微鏡観察
の結果、クラックやピンホールのない、緻密な膜である
ことが確認された。膜厚は約３００ｎｍであった。図１
にこの薄膜の可視スペクトルを示す。なお、調製した、
透明な薄膜作製用溶液は、大気中においても、非常に安
定で、６カ月放置後も、粘度変化や沈澱生成といった変
化は、まったく見られなかった。[Example 1] Zirconium n-propoxide, acetic acid and water (zirconium n-propoxide: acetic acid: water = 1:1
．． The prepared zirconium oxide precursor gel was mixed with acetic acid and n-butyl alcohol by a reaction of 33:1 [molar ratio] (precursor gel: acetic acid: n-butyl alcohol = 10:1:10). By heating to 60° C., the precursor gel was completely dissolved to form a clear solution. Immerse a glass plate in this solution and
A precursor thin film was formed by pulling up at a speed of 0 mm/min. After drying at room temperature for 1 hour, drying at 500℃ for 3
After firing for 0 minutes, a transparent tetragonal zirconium oxide thin film was obtained. The thin film produced by repeating this operation of pulling, drying, and firing three times was also transparent and tetragonal. As a result of electron microscopic observation, this zirconium oxide thin film was confirmed to be a dense film with no cracks or pinholes. The film thickness was approximately 300 nm. Figure 1
shows the visible spectrum of this thin film. In addition, the prepared
The transparent thin film-forming solution was extremely stable even in the atmosphere, and no changes such as viscosity changes or precipitate formation were observed even after being left for 6 months.
【０００９】[0009]
【実施例２】ジルコニウムｎ−プロポキシドと無水酢酸
イットリウム（イットリウム／ジルコニウム＝０．１８
５〔原子比〕）をｎ−ブチルアルコール中で混合、還流
して得られた溶液と、酢酸（酢酸／ジルコニウムアルコ
キシド＝１〔ｍｏｌ比〕）及び硝酸（硝酸／酢酸イット
リウム＝４〔ｍｏｌ比〕）及び水（水／ジルコニウムア
ルコキシド＝２〔ｍｏｌ比〕）の混合溶液から調製した
、酸化イットリウムドープ酸化ジルコニウム前駆体ゲル
状物を使用した。前駆体ゲル状物と酢酸及びｎ−ブチル
アルコールを混合（前駆体ゲル状物：酢酸：ｎ−ブチル
アルコール＝１０：１：１０〔重量比〕）し、６０℃に
加熱することにより、前駆体ゲル状物は完全に溶解して
、透明な溶液を形成した。この溶液にガラス板を浸漬し
、６０ｍｍ／ｍｉｎ の速度で引き上げることにより、
前駆体薄膜が形成した。室温で１時間乾燥後、５００℃
で３０分間焼成したところ、透明な酸化イットリウムド
ープ酸化ジルコニウム薄膜が得られた。この、引き上げ
、乾燥、焼成という操作を５回繰り返して作製した薄膜
も、また、透明であった。この薄膜は、電子顕微鏡観察
の結果、クラックやピンホールのない、緻密な膜である
ことが確認された。図２にこの薄膜の可視スペクトルを
示す。なお、調製した、透明な薄膜作製用溶液は、大気
中においても、非常に安定で、６カ月放置後も、粘度変
化や沈澱生成といった変化は、まったく見られなかった
。[Example 2] Zirconium n-propoxide and yttrium acetate anhydride (yttrium/zirconium = 0.18
A solution obtained by mixing and refluxing 5 [atomic ratio]) in n-butyl alcohol, acetic acid (acetic acid/zirconium alkoxide = 1 [mol ratio]) and nitric acid (nitric acid/yttrium acetate = 4 [mol ratio]) ) and water (water/zirconium alkoxide = 2 [molar ratio]), an yttrium oxide-doped zirconium oxide precursor gel was used. The precursor gel is mixed with acetic acid and n-butyl alcohol (precursor gel: acetic acid: n-butyl alcohol = 10:1:10 [weight ratio]) and heated to 60°C. The gel completely dissolved to form a clear solution. By immersing a glass plate in this solution and pulling it up at a speed of 60 mm/min,
A precursor film was formed. After drying at room temperature for 1 hour, 500℃
After firing for 30 minutes, a transparent yttrium oxide-doped zirconium oxide thin film was obtained. The thin film produced by repeating this operation of pulling up, drying, and firing five times was also transparent. As a result of electron microscopic observation, this thin film was confirmed to be a dense film with no cracks or pinholes. Figure 2 shows the visible spectrum of this thin film. The prepared solution for producing a transparent thin film was very stable even in the atmosphere, and no changes such as viscosity change or precipitate formation were observed even after being left for 6 months.
【００１０】0010
【発明の効果】酸化ジルコニウム系前駆体ゲル状物は、
有機溶媒への溶解性が低く、この前駆体ゲル状物から薄
膜作製用溶液を調製することは困難であったが、実施例
に述べたように、本発明により、酢酸を添加するだけで
、ゲル状物は容易に有機溶媒に溶解し、透明な薄膜作製
用前駆体溶液を調製することが可能になった。また、こ
の発明により、未反応アルコキシ基をほとんど含まない
、前駆体ゲル状物を溶解して、薄膜作製用溶液として使
用できるようになったため、この溶液をディッピングや
スピンコートにより、成形物に塗布、焼成することで、
従来のアルコキシド溶液からでは不可能だった、残留有
機物の少ない、緻密な酸化ジルコニウム系薄膜を得るこ
とが可能となった。さらに、本発明の前駆体ゲル状物を
溶解した透明溶液は、加水分解可能な未反応アルコキシ
基を有するアルコキシド分子を含んでいないため、従来
の薄膜作製用のアルコキシド溶液とは異なり、大気中の
湿分の影響を受けることなく、安定に長期間の保存がで
きるという利点もある。本発明の薄膜製造方法は、透明
で緻密な酸化ジルコニウム系薄膜が得られるため、酸化
ジルコニウム系薄膜の光学材料としての用途を大いにひ
ろげるものである。[Effect of the invention] The zirconium oxide precursor gel is
It has been difficult to prepare a solution for forming a thin film from this precursor gel due to its low solubility in organic solvents, but as described in the examples, the present invention enables the preparation of thin film by simply adding acetic acid. The gel-like material was easily dissolved in an organic solvent, making it possible to prepare a transparent precursor solution for thin film production. Furthermore, with this invention, it has become possible to dissolve the precursor gel, which contains almost no unreacted alkoxy groups, and use it as a solution for forming thin films, so this solution can be applied to molded objects by dipping or spin coating. , by firing,
It has become possible to obtain a dense zirconium oxide thin film with little residual organic matter, which was not possible with conventional alkoxide solutions. Furthermore, the transparent solution in which the precursor gel of the present invention is dissolved does not contain alkoxide molecules having unreacted hydrolyzable alkoxy groups. Another advantage is that it can be stored stably for a long time without being affected by moisture. The thin film manufacturing method of the present invention yields a transparent and dense zirconium oxide thin film, and thus greatly expands the use of zirconium oxide thin films as optical materials.
【図１】作製した酸化ジルコニウム薄膜の可視スペクト
ルを示した図である。FIG. 1 is a diagram showing the visible spectrum of the produced zirconium oxide thin film.
【図２】作製した酸化イットリウムドープ酸化ジルコニ
ウム薄膜の可視スペクトルを示した図である。FIG. 2 is a diagram showing the visible spectrum of the produced yttrium oxide-doped zirconium oxide thin film.
Claims (3)
にＯＣＯＲ基（ここで、Ｒは炭素数１〜４までの直鎖ま
たは分岐のあるアルキル基を示す）を有する重合体から
成る、酸化ジルコニウム前駆体ゲル状物をカルボン酸及
び有機溶媒に溶解することにより、得られる透明溶液を
成形物に塗布、加熱することを特徴とする酸化ジルコニ
ウム薄膜製造方法。Claim 1: From a polymer having a Zr-O-Zr bond as the main chain and an OCOR group (here, R represents a linear or branched alkyl group having 1 to 4 carbon atoms) in the side chain. 1. A method for producing a zirconium oxide thin film, which comprises dissolving a zirconium oxide precursor gel in a carboxylic acid and an organic solvent, applying the resulting transparent solution to a molded article, and heating.
にＯＣＯＲ基を有する重合体及びＹ、Ｌａ、Ｍｇ、Ｃａ
、Ｓｒ、Ｂａのうち、一種または二種以上の金属イオン
を含む酸化ジルコニウム系複合酸化物前駆体ゲル状物を
、カルボン酸及び有機溶媒に溶解することにより、得ら
れる透明溶液を成形物に塗布、加熱することを特徴とす
る酸化ジルコニウム系複合酸化物薄膜製造方法。[Claim 2] A polymer having a Zr-O-Zr bond as the main chain and an OCOR group in the side chain, and Y, La, Mg, Ca
, Sr, and Ba, by dissolving a zirconium oxide complex oxide precursor gel containing one or more metal ions in a carboxylic acid and an organic solvent, and applying the resulting transparent solution to a molded article. A method for producing a zirconium oxide-based composite oxide thin film, the method comprising heating.
ール類である特許請求の範囲第１項及び特許請求の範囲
第２項記載の製造方法。3. The manufacturing method according to claim 1 and claim 2, wherein the organic solvent is an alcohol having 1 to 5 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4343291A JPH0761871B2 (en) | 1991-03-08 | 1991-03-08 | Method for producing thin film from zirconium oxide-based precursor gel-like material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4343291A JPH0761871B2 (en) | 1991-03-08 | 1991-03-08 | Method for producing thin film from zirconium oxide-based precursor gel-like material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04280817A true JPH04280817A (en) | 1992-10-06 |
| JPH0761871B2 JPH0761871B2 (en) | 1995-07-05 |
Family
ID=12663539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4343291A Expired - Fee Related JPH0761871B2 (en) | 1991-03-08 | 1991-03-08 | Method for producing thin film from zirconium oxide-based precursor gel-like material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0761871B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06101067A (en) * | 1992-09-24 | 1994-04-12 | Tsuchiya:Kk | Ceramic coating liquid for preventing high temperature oxidation of stainless steel |
| EP0747506A1 (en) * | 1995-06-05 | 1996-12-11 | International Business Machines Corporation | Plating on nonmetallic disks |
-
1991
- 1991-03-08 JP JP4343291A patent/JPH0761871B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06101067A (en) * | 1992-09-24 | 1994-04-12 | Tsuchiya:Kk | Ceramic coating liquid for preventing high temperature oxidation of stainless steel |
| EP0747506A1 (en) * | 1995-06-05 | 1996-12-11 | International Business Machines Corporation | Plating on nonmetallic disks |
| US5871810A (en) * | 1995-06-05 | 1999-02-16 | International Business Machines Corporation | Plating on nonmetallic disks |
| KR100235087B1 (en) * | 1995-06-05 | 1999-12-15 | 포만 제프리 엘 | Method for plating on nonmetallic disks and recording-reproducing apparatus using it |
| US6183828B1 (en) | 1995-06-05 | 2001-02-06 | International Business Machines Corporation | Plating on nonmetallic disks |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0761871B2 (en) | 1995-07-05 |
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