JPH0383816A - Production of solution for producing compound oxide thin film - Google Patents
Production of solution for producing compound oxide thin filmInfo
- Publication number
- JPH0383816A JPH0383816A JP22016989A JP22016989A JPH0383816A JP H0383816 A JPH0383816 A JP H0383816A JP 22016989 A JP22016989 A JP 22016989A JP 22016989 A JP22016989 A JP 22016989A JP H0383816 A JPH0383816 A JP H0383816A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- producing
- thin film
- oxide thin
- titanium
- 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
- 239000010409 thin film Substances 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 17
- 229910052788 barium Inorganic materials 0.000 claims abstract description 15
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 abstract description 29
- 239000011248 coating agent Substances 0.000 abstract description 24
- 238000000576 coating method Methods 0.000 abstract description 24
- 239000010408 film Substances 0.000 abstract description 21
- -1 alkoxy alcohol Chemical compound 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 9
- 239000011259 mixed solution Substances 0.000 abstract description 6
- 235000019441 ethanol Nutrition 0.000 description 12
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 9
- 229940093475 2-ethoxyethanol Drugs 0.000 description 9
- 238000010304 firing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 4
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、誘電体材料等の電子材料として用いられる複
合酸化物薄膜を簡便且つ低温で製造することが可能な複
合酸化物薄膜製造用溶液の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a solution for producing a composite oxide thin film that can be easily produced at a low temperature to be used as an electronic material such as a dielectric material. Relating to a manufacturing method.
バリウム、チタンを主成分とする高誘電体材料は、コン
デンサー等の電子材料として広く用いられている。これ
らの材料は高周波や新しい用途を開発するため小型化、
集積化が検討されている。High dielectric materials containing barium and titanium as main components are widely used as electronic materials such as capacitors. These materials are becoming smaller and smaller to develop high frequencies and new applications.
Integration is being considered.
しかしながら、従来の粉末を焼結する方法ではその膜厚
を薄くすることに限界があるため、高密度化、高集積化
に限界がある。However, with the conventional method of sintering powder, there is a limit to reducing the thickness of the film, and therefore there is a limit to increasing the density and integration.
これに対して、化学蒸着、スパッタリング、イオンブレ
ーティング等の真空技術を用いた方法では、任意の膜厚
及び基板上への緻密な成膜が可能であり、電子材料関連
の重要な技術として用いられている。しかしながら、真
空技術による誘電体薄膜は、特に２種類以上の金属成分
を含む場合、目的の化学組成の薄膜を安定して作ること
は非常に困難であり、バルクの素材と異なった物性とな
ることがあることが良く知られている。また、複雑な形
状や大面積への成膜が困難であること、バッチ形状とな
るため生産性が悪く、設備費用が高いためコスト高にな
る。On the other hand, methods using vacuum techniques such as chemical vapor deposition, sputtering, and ion blating enable the formation of films of arbitrary thickness and denseness on substrates, and are used as important technologies related to electronic materials. It is being However, dielectric thin films made using vacuum technology are extremely difficult to stably produce with a desired chemical composition, especially when they contain two or more types of metal components, and their physical properties may differ from those of the bulk material. It is well known that there is. In addition, it is difficult to form a film on a complex shape or large area, the productivity is poor due to the batch shape, and the cost is high due to high equipment costs.
そこで、より低コストで生産性の高い方法として金属ア
ルコキシドを用いる方法が行われている。Therefore, a method using a metal alkoxide is being used as a method that is lower in cost and has higher productivity.
Ｍ、Ｉ、ヤノブスカヤ（Ｍ、 Ｉ、 Ｙａｎｏｖｓｋａ
ｙａ）らは、バリウムとチタンのアルコキシドのエチル
アルコール溶液を用い、コーテイング膜を得ている（「
インオルガニック マテリアル（ＩｎｏｒｇａｎｉｃＭ
ａｔｅｒｉａｌ） Ｊ第１７巻第２２１〜２２４頁（１
９８１）） 、作孔らは、バリウムとチタンの混合アル
コキシドを加水分解する際、多量の酢酸を用い均一なコ
ーティング溶液を得ている（Ｊａｐ、 Ｊ、 Ａｐｐｌ
、 Ｐｈｙｓｉｃｓ、 ２２＋Ｓｕｐｐｌｅｍｅｎｔ
２２−２． （１９８３） Ｐ３） 、また、バリウム
アルコキシドとチタンアシレート、又はチタンキレート
を用いてもコーティングが可能である。M, I, Yanovskaya
ya) et al. used an ethyl alcohol solution of barium and titanium alkoxide to obtain a coating film (``
Inorganic Material
material) J Vol. 17, pp. 221-224 (1
981)), Sakuko et al. used a large amount of acetic acid to obtain a uniform coating solution when hydrolyzing a mixed alkoxide of barium and titanium (Jap, J. Appl.
, Physics, 22+Supplement
22-2. (1983) P3), coating is also possible using barium alkoxide and titanium acylate or titanium chelate.
しかしながら、Ｍ、Ｉ、ヤノブスカヤらの方法は、コー
ティング、乾燥、焼成の操作をすべて乾燥窒素中で行う
必要があり、空気中で上記の操作を行うと剥離し、コー
テイング膜を得ることができない。However, in the method of M. I. Yanovskaya et al., the coating, drying, and firing operations must all be performed in dry nitrogen, and if the above operations are performed in air, the coating will peel off, making it impossible to obtain a coating film.
作孔らの方法では、大気中でのコーティングが可能であ
るが、多量の酢酸を使用しているためＢａが酢酸塩とし
て存在し、加熱過程において炭酸塩が生成する。また、
反応溶液に経時変化が見られるため安定したコーティン
グ溶液を得ることが難しい。The method of Sakuko et al. allows coating in the air, but since a large amount of acetic acid is used, Ba is present as acetate, and carbonate is generated during the heating process. Also,
It is difficult to obtain a stable coating solution because the reaction solution changes over time.
チタンアシレート、チタンキレートを用いる方法では、
大気中でのコーティングが可能であり、ゾルの経時変化
も少なく安定性に優れている。しかし、チタンアシレー
トやチタンキレートは、水に対して安定性が高く、成膜
後、有機物がコーテイング膜中に残存しやすい、このた
め、焼結を阻害し気孔が残りやすい。In the method using titanium acylate or titanium chelate,
Coating is possible in the atmosphere, and the sol has excellent stability with little change over time. However, titanium acylate and titanium chelate have high stability against water, and after film formation, organic substances tend to remain in the coating film, which inhibits sintering and tends to leave pores.
本発明の目的は、以上のような欠点を解決し、大気中で
のコーティングが可能で、安定性があり、かつそれから
形成したコーテイング膜が容易に焼結できるような、簡
便な複合酸化物薄膜製造用溶液の製造方法を提供するこ
とにある。The purpose of the present invention is to solve the above-mentioned drawbacks and to provide a simple composite oxide thin film that can be coated in the atmosphere, is stable, and allows the coating film formed from it to be easily sintered. An object of the present invention is to provide a method for producing a solution for production.
本発明は、金属バリウム及び／又はストロンチウムを一
般式ｈｏ（ＣＨｚ）ｇｏ）Ｉ （ただし、Ｒはメチル、
エチル、プロピル、ブチル、フェニル）で表わされる化
合物と反応溶解させ、この溶液にチタン及び／又はジル
コらラムのアルコキシドを混合し、加熱することを特徴
とする複合酸化物薄膜製造用溶液の製造方法によってそ
の目的を達成した。The present invention provides metal barium and/or strontium with the general formula ho(CHz)go)I (wherein R is methyl,
A method for producing a solution for producing a composite oxide thin film, which comprises reacting and dissolving a compound represented by (ethyl, propyl, butyl, phenyl), mixing titanium and/or zircoram alkoxide with this solution, and heating the mixture. achieved that purpose.
前記の一般式ＲＯ（ＣＬ） ｚＯＦ！で表わされる化合
物は、アルコキシアルコールに属するが、Ｒがメチル、
エチル、プロピル、ブチル、フェニルであるものが用い
られる。後で行われる有機物の除去のしやすさを考える
と、特に２−メトキシエタノール（沸点；１２４°Ｃ）
、２−エトキシエタノール（沸点；１３５℃）の使用が
望ましい。The general formula RO(CL) zOF! The compound represented by belongs to alkoxy alcohol, but R is methyl,
Ethyl, propyl, butyl and phenyl are used. In particular, 2-methoxyethanol (boiling point: 124°C)
, 2-ethoxyethanol (boiling point: 135°C) is preferably used.
金属バリウム及び／又はストロンチウムに対する前記化
合物の使用量は、その金属バリウム及び／又はストロン
チウムがそれに全量反応してそれらのアルコキシドを生
成するのに十分な量であるだけでなく、最終的にチタン
又はジルコニウムのアルコキシドと反応させた時に完全
に溶かせるだけの量を用いる。The amount of the compound to be used relative to the metal barium and/or strontium is not only sufficient for the total amount of the metal barium and/or strontium to react with it to produce their alkoxides, but also to ultimately react with titanium or zirconium. Use an amount sufficient to completely dissolve it when reacting with the alkoxide.
チタン及び／又はジルコニウムのアルコキシドの種類は
、特に限定されるものではないが、有機溶剤への溶解性
、含有金属率の点から、炭素数１〜４のものが好ましい
。また、混合するバリウム及び／又はストロンチウム／
チタン及び／又はジルコニウムの比は特に限定されない
。チタン及び／又はジルコニウムのアルコキシドはその
ままで加えてもよいが、溶液として加えてもよく、前記
化合物（アルコキシアルコール）の溶液で加えるのが好
ましい０両者の混合後の加熱は、室温から還流温度の範
囲で行われ、その適正な温度及び時間は用いる金属の組
合せ、比率に依存する。The type of titanium and/or zirconium alkoxide is not particularly limited, but those having 1 to 4 carbon atoms are preferred from the viewpoint of solubility in organic solvents and metal content. Also, barium and/or strontium/
The ratio of titanium and/or zirconium is not particularly limited. The alkoxide of titanium and/or zirconium may be added as it is, or may be added as a solution, and it is preferable to add it as a solution of the compound (alkoxy alcohol).Heating after mixing the two is from room temperature to reflux temperature. The appropriate temperature and time depend on the combination and ratio of metals used.
、また、チタン及び／又はジルコニウムがバリウム及び
／又はストロンチウムに対して２モル倍以下では、混合
後加熱する、ことにより目的とする性質の溶液が得られ
るが、その比が２モル倍以上になると透明な膜を形成し
うる溶液が得られにくくなるので、得られる加熱後の混
合溶液に対して水を添加しておくことが必要となる。こ
の水の添加により前記のアルコキシドが部分的に加水分
解される。この水の添加量を多くすると、金属濃度によ
りゾルまたはゲル状態となるため、安定なコーティング
溶液を得るためには、水の添加量はチタン及び／又はジ
ルコニウムのアルコキシドに対して２モル倍以下０．５
モル倍以上が望ましい、特に０．５〜１．５モル倍の間
がよい。また、そのさい水を直接添加すると溶液中に不
均一な加水分解が起こり、そのため部分的なゲル化が生
じる。従って、水を溶媒として用いたアルコキシアルコ
ールで希釈して添加することが好ましい。特に、水は５
０容量％以下に希釈するのが望ましい。このアルコキシ
アルコールとしては前記一般式ＲＯ（ＣＨｚ）ｚＯＨ（
ただし、Ｒはメチル、エチル、プロピル、ブチル、フェ
ニル）で表わされる化合物であるものが好ましく用いら
れる。Also, if the ratio of titanium and/or zirconium to barium and/or strontium is less than 2 times the mole ratio, a solution with the desired properties can be obtained by heating after mixing, but if the ratio is more than 2 times the mole ratio, a solution with the desired properties can be obtained. Since it becomes difficult to obtain a solution capable of forming a transparent film, it is necessary to add water to the resulting heated mixed solution. This addition of water partially hydrolyzes the alkoxide. If the amount of water added is increased, the metal will become in a sol or gel state depending on the concentration. Therefore, in order to obtain a stable coating solution, the amount of water added should be 0 or less than 2 times the mole of titanium and/or zirconium alkoxide. .5
It is desirable that the amount is more than twice the amount by mole, particularly between 0.5 and 1.5 times by mole. Also, if water is added directly at that time, non-uniform hydrolysis occurs in the solution, resulting in partial gelation. Therefore, it is preferable to dilute with an alkoxy alcohol using water as a solvent before adding. In particular, water is 5
It is desirable to dilute to 0% by volume or less. This alkoxy alcohol has the general formula RO(CHz)zOH(
However, R is preferably a compound represented by methyl, ethyl, propyl, butyl, or phenyl.
この複合酸化物薄膜製造用溶液には、それから得られる
複合酸化物の半導体化、キューリー点の移動のための微
量元素をアルキッド、金属塩として添加することができ
る。To this solution for producing a composite oxide thin film, trace elements can be added in the form of alkyds or metal salts to convert the composite oxide obtained therefrom into a semiconductor and to shift the Curie point.
本発明の複合酸化物薄膜製造用溶液は、これを基板上な
どにデイツプ・コーティング法、スピンコーティング法
などによりコーティング後′大気中の水蒸気などにより
加水分解し、ゲル化し、乾燥してコーテイング膜を得こ
れを焼成することにより複合酸化物薄膜を得ることがで
きる。The solution for manufacturing a composite oxide thin film of the present invention is coated onto a substrate by a dip coating method, a spin coating method, etc., then hydrolyzed by water vapor in the atmosphere, gelled, and dried to form a coating film. By firing this, a composite oxide thin film can be obtained.
本発明は、−ＩＩ弐ＲＯ（ＣＦｌ糞）ｔＯＨで表わされ
るアルコキシアルコールを用いることにより、金属アル
コキシドの溶解度が向上する。そのため、通常のアルコ
ール、例えばエチルアルコールの溶液の場合に較べて高
濃度の複合酸化物薄膜製造用溶液を得ることが可能とな
る。In the present invention, the solubility of the metal alkoxide is improved by using an alkoxy alcohol represented by -II2RO (CFl excrement) tOH. Therefore, it is possible to obtain a solution for manufacturing a composite oxide thin film with a higher concentration than in the case of a solution of ordinary alcohol, for example, ethyl alcohol.
このアルコキシアルコールを用いたさいには、アルコキ
シアルコールのもう一つの酸素が金属原子に対して配位
することにより、通常のアルコールより得られたアルコ
キシドに較べ水に対して安定化され、加水分解速度が抑
制されると考えられる。さらに、このアルコキシアルコ
ールは、１００°Ｃ以上の沸点を持っているため、生成
膜の乾燥速度を抑制する効果もある。When using this alkoxy alcohol, the other oxygen in the alkoxy alcohol coordinates to the metal atom, making it more stable against water than alkoxides obtained from ordinary alcohols, and resulting in a faster hydrolysis rate. is thought to be suppressed. Furthermore, since this alkoxy alcohol has a boiling point of 100°C or higher, it also has the effect of suppressing the drying rate of the formed film.
チタン及び／またはジルコニウムが過剰である組成のも
のは、全てのアルコキシドがダブルアルコキシドを形威
し、安定化することができないため、コーテイング後、
チタン及び／又はジルコニウムのアルコキシドの急激な
加水分解が起こり、コーテイング膜の失透が起こる。こ
れらのアルコキシドに少量の水をあらかじめ添加するこ
とにより、部分的に加水分解、重合を進行させることが
でき、結果としてアルコキシドの急激な加水分解を抑え
ることができる。If the composition has an excess of titanium and/or zirconium, all the alkoxides will form double alkoxides and cannot be stabilized, so after coating,
Rapid hydrolysis of titanium and/or zirconium alkoxide occurs, resulting in devitrification of the coating film. By adding a small amount of water to these alkoxides in advance, hydrolysis and polymerization can proceed partially, and as a result, rapid hydrolysis of the alkoxides can be suppressed.
以上の３つのことにより大気中でのコーティングが可能
となった。The above three factors made it possible to perform coating in the atmosphere.
（実施例） 以下、実施例により本発明を具体的に説明する。(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.
ただし、本発明はこれらの実施例に限定されるものでは
ない。However, the present invention is not limited to these examples.
実施例 １
金属バリウム６．８７ｇを２−エトキシエタノールＬｏ
ｏＩ１１に溶解反応させた。チタンエトキシド１１．４
ｇを加え、窒素雰囲気下、１００°Ｃで３０分加熱した
。Example 1 6.87 g of metallic barium was dissolved in 2-ethoxyethanol Lo
A dissolution reaction was carried out in oI11. Titanium ethoxide 11.4
g was added thereto, and the mixture was heated at 100°C for 30 minutes under a nitrogen atmosphere.
それに水１−と２−エトキシエタノール４９１ｎ１との
混合溶液を滴下した。得られた溶液を用い、デイツプコ
ーター（引き上げ速度０．５ｍｍ／分、浸漬回数６回）
でＹ２Ｏ，安定化Ｚｒ０ｍ基板上にコーティングし、透
明かつ割れのない薄膜を得た。１０００°Ｃ１１時間の
焼成でＸ線的にペロブスカイト単相、かつ厚さ０．６−
の緻密な膜を得た。A mixed solution of 1-1 water and 491 n1 of 2-ethoxyethanol was added dropwise thereto. Using the obtained solution, dip coater (pulling speed 0.5 mm/min, number of immersions 6 times)
was coated on a Y2O, stabilized Zr0m substrate to obtain a transparent and crack-free thin film. After firing at 1000°C for 11 hours, X-rays showed perovskite single phase and a thickness of 0.6-
A dense film was obtained.
実施例 ２
金属バリウム４．２２ ｇと金属ストロンチウム１．７
１ｇを２−エトキシエタノール１ＯＯ−に溶解反応させ
た。チタンエトキシド１１．４ ｇを加え、窒素雰囲気
下、１００℃で３０分加熱した。それに水１ｄと２−エ
トキシエタノール４Ｍの混合溶液を滴下した。Example 2 4.22 g of barium metal and 1.7 g of strontium metal
1 g was dissolved in 100 - of 2-ethoxyethanol and reacted. 11.4 g of titanium ethoxide was added and heated at 100° C. for 30 minutes under a nitrogen atmosphere. A mixed solution of 1 d of water and 4 M of 2-ethoxyethanol was added dropwise thereto.
得られた溶液を用いデイツプコーター（引き上げ速度０
．５ｍｍ／分、１０回）でアルミナ基板上にコーティン
グし、透明かつ割れのないｉ［を得た。１時間の焼成で
Ｘ線的にペロブスカイト単相、かつ厚さ約０．６ｍの緻
密な膜を得た。Using the obtained solution, dip coater (pulling speed 0
．． 5 mm/min, 10 times) on an alumina substrate to obtain transparent and crack-free i[. After firing for 1 hour, a dense film with a perovskite single phase and a thickness of about 0.6 m was obtained as seen by X-rays.
実施例３
金属バリウム１．２７ｇを２−エトキシエタノール５０
ｄに溶解反応させた。チタンエトキシド１０．３２ｇを
加え、窒素雰囲気下、１００°Ｃで３０分加熱した。Example 3 1.27 g of metallic barium was added to 50 g of 2-ethoxyethanol.
d was subjected to a dissolution reaction. 10.32 g of titanium ethoxide was added and heated at 100°C for 30 minutes under a nitrogen atmosphere.
それに水１ｄと２−エトキシエタノール９Ｊｄの混合溶
液を滴下した。得られた溶液を用い、デイツプコーター
（引き上げ速度０．５ｍ／分、１０回）でアルミナ基板
上にコーティングし、透明且つ割れのない薄膜を得た。A mixed solution of 1 d of water and 9 Jd of 2-ethoxyethanol was added dropwise thereto. The obtained solution was coated on an alumina substrate using a dip coater (pulling speed 0.5 m/min, 10 times) to obtain a transparent and crack-free thin film.
１０００″ＣＳ１時間の焼成でＢａＴｉ５Ｏ＋＋単相
、かつ厚さ（１，６−の緻密なコーテイング膜を得た。By firing at 1000''CS for 1 hour, a dense coating film of BaTi5O++ single phase and thickness (1,6-) was obtained.
実施例４
金属バリウム１．４６ｇを２−エトキシエタノール５０
ｍに溶解反応させた。チタンエトキシド１０．９７ｇを
加え、窒素雰囲気下、１００″Ｃで３０分加熱した。Example 4 1.46 g of metallic barium was mixed with 50 g of 2-ethoxyethanol.
m was dissolved and reacted. 10.97 g of titanium ethoxide was added and heated at 100''C for 30 minutes under a nitrogen atmosphere.
水ｌｌｌ１１と２−エトキシエタノール９−の混合溶液
を滴下した。得られた溶液を用い、デイツプコーター（
引き上げ速度０．５ｗｍ／分、１０回）でジルコニア基
板上にコーティングし、透明かつ割れのない薄膜を得た
。 １２００”Ｃ，１時間の焼成でＢａｚＴｉ＊Ｏｚ。A mixed solution of 1111 water and 99 2-ethoxyethanol was added dropwise. Using the obtained solution, dip coater (
The film was coated on a zirconia substrate at a pulling rate of 0.5 wm/min (10 times) to obtain a transparent and crack-free thin film. BazTi*Oz after firing at 1200"C for 1 hour.
単相、かつ厚さ０．５−の緻密なコーテイング膜を得た
。A dense coating film having a single phase and a thickness of 0.5 mm was obtained.
上記の各実施例におけるコーティング操作はすべて大気
中で行われた。All coating operations in the above examples were performed in air.
本発明によれば、大気雰囲気下で、均一で割れ、むらが
ない透明なコーテイング膜が作成可能な複合酸化物薄膜
製造用溶液を得ることができる。この得られたコーテイ
ング膜を焼成することにより、組成にずれがない高純度
のペロブスカイト型複合酸化物薄膜を簡便、かつ低温で
得ることができる。According to the present invention, it is possible to obtain a solution for producing a composite oxide thin film that can produce a transparent coating film that is uniform, free of cracks, and free from unevenness in the atmosphere. By firing the obtained coating film, a highly pure perovskite-type composite oxide thin film with no deviation in composition can be easily obtained at a low temperature.
Claims (4)
ＲＯ（ＣＨ＿２）＿２ＯＨ（ただし、Ｒはメチル、エチ
ル、プロピル、ブチル、フェニル）で表わされる化合物
と反応溶解させ、この溶液にチタン及び／又はジルコニ
ウムのアルコキシドを混合し、加熱することを特徴とす
る複合酸化物薄膜製造用溶液の製造方法。(1) Metallic barium and/or strontium is reacted and dissolved with a compound represented by the general formula RO(CH_2)_2OH (where R is methyl, ethyl, propyl, butyl, phenyl), and titanium and/or zirconium are added to this solution. A method for producing a solution for producing a composite oxide thin film, which comprises mixing alkoxides and heating the mixture.
ＲＯ（ＣＨ＿２）＿２ＯＨ（ただし、Ｒはメチル、エチ
ル、プロピル、ブチル、フェニル）で表わされる化合物
と反応溶解させ、この溶液にチタン及び／又はジルコニ
ウムのアルコキシドを混合し、加熱した後、チタン及び
／又はジルコニウムに対して０．５〜２モル倍の水を加
えることを特徴とする複合酸化物薄膜製造用溶液の製造
方法。(2) Metallic barium and/or strontium is reacted and dissolved with a compound represented by the general formula RO(CH_2)_2OH (where R is methyl, ethyl, propyl, butyl, phenyl), and titanium and/or zirconium is added to this solution. 1. A method for producing a solution for producing a composite oxide thin film, which comprises mixing alkoxides, heating the mixture, and then adding water in an amount of 0.5 to 2 times the mole of titanium and/or zirconium.
たものであることを特徴とする請求項（２）記載の複合
酸化物薄膜製造用溶液の製造方法。(3) The method for producing a solution for producing a composite oxide thin film according to claim (2), wherein the water is diluted with alcohol to 50% by volume or less.
合物としてＲがメチル又はエチルである化合物を用いる
ことを特徴とする請求項（１）〜（３）のいずれか１項
に記載の複合酸化物薄膜製造用溶液の製造方法。(4) The composite oxide according to any one of claims (1) to (3), characterized in that the compound represented by the general formula RO(CH_2)_2OH is a compound in which R is methyl or ethyl. A method for producing a solution for producing a thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22016989A JPH0383816A (en) | 1989-08-29 | 1989-08-29 | Production of solution for producing compound oxide thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22016989A JPH0383816A (en) | 1989-08-29 | 1989-08-29 | Production of solution for producing compound oxide thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0383816A true JPH0383816A (en) | 1991-04-09 |
Family
ID=16746969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22016989A Pending JPH0383816A (en) | 1989-08-29 | 1989-08-29 | Production of solution for producing compound oxide thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0383816A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008041725A (en) * | 2006-08-02 | 2008-02-21 | Sumitomo Metal Mining Co Ltd | Coating composition for forming high dielectric thin film, and its manufacturing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62265118A (en) * | 1986-05-10 | 1987-11-18 | Mitsubishi Mining & Cement Co Ltd | Production of precursor sol of barium titanate |
| JPH01111724A (en) * | 1987-10-22 | 1989-04-28 | Mitsui Petrochem Ind Ltd | Production of barium titanate |
| JPH01286922A (en) * | 1988-05-12 | 1989-11-17 | Toray Ind Inc | Method for forming barium titanate thin film |
-
1989
- 1989-08-29 JP JP22016989A patent/JPH0383816A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62265118A (en) * | 1986-05-10 | 1987-11-18 | Mitsubishi Mining & Cement Co Ltd | Production of precursor sol of barium titanate |
| JPH01111724A (en) * | 1987-10-22 | 1989-04-28 | Mitsui Petrochem Ind Ltd | Production of barium titanate |
| JPH01286922A (en) * | 1988-05-12 | 1989-11-17 | Toray Ind Inc | Method for forming barium titanate thin film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008041725A (en) * | 2006-08-02 | 2008-02-21 | Sumitomo Metal Mining Co Ltd | Coating composition for forming high dielectric thin film, and its manufacturing method |
| JP4702215B2 (en) * | 2006-08-02 | 2011-06-15 | 住友金属鉱山株式会社 | Coating composition for forming high dielectric thin film and method for producing the same |
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