JPH0688783B2 - Method for producing thin film from transparent aluminum oxide precursor gel-like material - Google Patents
Method for producing thin film from transparent aluminum oxide precursor gel-like materialInfo
- Publication number
- JPH0688783B2 JPH0688783B2 JP13110391A JP13110391A JPH0688783B2 JP H0688783 B2 JPH0688783 B2 JP H0688783B2 JP 13110391 A JP13110391 A JP 13110391A JP 13110391 A JP13110391 A JP 13110391A JP H0688783 B2 JPH0688783 B2 JP H0688783B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- transparent
- solution
- aluminum oxide
- precursor gel
- 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.)
- Expired - Fee Related
Links
- 239000010409 thin film Substances 0.000 title claims description 42
- 239000002243 precursor Substances 0.000 title claims description 24
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims description 18
- 239000000463 material Substances 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 239000010408 film Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000004703 alkoxides Chemical class 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 aluminum alkoxide Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Landscapes
- Producing Shaped Articles From Materials (AREA)
- Surface Treatment Of Glass (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Chemically Coating (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、長期保存可能な透明酸
化アルミニウム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 transparent aluminum oxide precursor gel material which can be stored for a long period of time.
【０００２】[0002]
【従来の技術】酸化アルミニウム薄膜は、耐熱性、耐薬
品性、耐摩耗性保護膜として種々の用途に利用されてい
る。また、透明な薄膜は無反射膜、赤外線透過膜として
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、ＣＶＤ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。2. Description of the Related Art Aluminum oxide thin films have been used for various purposes as heat-resistant, chemical-resistant and wear-resistant protective films. The transparent thin film is used as a non-reflective film and an infrared transmitting film. As a method for manufacturing an oxide ceramic thin film, there are a CVD method, a plasma spraying method, a high frequency sputtering method and the like, but dipping and spin coating are advantageous because of advantages such as high productivity, a low temperature process and a low device cost. Recently, a method of forming a thin oxide film by applying a solution containing a metal alkoxide to a molded article and heating it has been widely used.
【０００３】しかし、この方法で透明酸化アルミニウム
薄膜を作製する場合に、原料として用いるアルミニウム
アルコキシドは加水分解が非常に速いため、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、水
酸化アルミニウムを形成し、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
をキレート化剤、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 a transparent aluminum oxide thin film is produced by this method, the aluminum alkoxide used as a raw material is very rapidly hydrolyzed, so that the stability of the solution against water and moisture is poor and it is easily hydrolyzed. , Forms aluminum hydroxide and precipitates. Therefore, when applying the solution, it was difficult to obtain a uniform and transparent coating layer. Therefore, the moisture during application is strictly controlled, or a part or all of the alkoxy groups of the alkoxide is replaced with a chelating agent, such as acetylacetone, to significantly suppress hydrolysis and stabilize the solution. The method of doing 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。However, the thin film formed by using this solution contains a large amount of unreacted alkoxy groups and groups substituted with alkoxy groups, because hydrolysis-polycondensation has not progressed sufficiently, and it is applied to a molded article. When an oxide thin film is obtained by heating, there is a problem that a dense film cannot be formed due to pinholes and cracks generated by 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、アルミニウムアルコキシドから調製した薄膜作
製用酸化アルミニウム前駆体溶液の湿分に関する安定性
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
透明酸化アルミ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 problems to be solved are that the aluminum oxide precursor solution for forming a thin film prepared from aluminum alkoxide has poor stability with respect to moisture, and further, the application of the solution to a molded article, When forming an oxide thin film by firing, a large amount of residual organic substances that cause pinholes and cracks are present in the precursor, and a dense transparent aluminum oxide thin film cannot be obtained.
【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、Ａ１−
Ｏ−Ａ１結合を有する、透明な酸化アルミニウム系前駆
体ポリマーゲル状物を有機溶媒に溶解して、透明薄膜作
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 problems, the present inventors have previously invented A1-
The main feature is that a transparent aluminum oxide precursor polymer gel having an O-A1 bond is dissolved in an organic solvent to prepare a solution for forming a transparent thin film.
【０００７】透明酸化アルミニウム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、室温では溶解性が低い。そこで、本発明者は研究の
結果、このゲル状物が加熱することにより、溶液状にな
ることを見出し、有機溶媒中に前駆体ゲル状物を入れ、
加熱すると前駆体ゲル状物が完全に溶解し、透明な溶液
となることを発明した。また、この様にして調製した透
明溶液は室温まで冷却しても溶液状を保っており、ポリ
マーゲルが析出することはなかった。この発明により、
従来のアルミ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透
明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、
緻密な透明酸化アルミニウム薄膜を得るという目的も実
現できた。The transparent aluminum oxide precursor polymer gel is extremely stable against moisture in the air for a long period of time because it has almost no unreacted alkoxy groups. If this precursor polymer can be made into a solution, a solution that is stable against moisture can be obtained, and the thin film obtained by applying the solution is almost free of residual organic substances that cause pinholes and cracks. It is thought that there will be nothing. However, this precursor gel-like material has low solubility in organic solvents at room temperature. Therefore, as a result of research, the present inventor has found that the gel-like material is heated to a solution state, and puts the precursor gel-like material in an organic solvent,
It was invented that when heated, the precursor gel-like substance was completely dissolved to form a transparent solution. Further, the transparent solution thus prepared was kept in a solution state even when cooled to room temperature, and polymer gel was not deposited. According to this invention,
The object of preparing a transparent thin film-forming solution that is extremely stable against moisture compared to the conventional solution prepared by suppressing the hydrolysis of aluminum alkoxide was achieved.
In addition, by applying this solution to a molded article and heating it, there is almost no residual organic matter that could not be obtained until now,
The purpose of obtaining a dense transparent aluminum oxide thin film was also realized.
【０００８】[0008]
【実施例】以下に本発明の具体例を実施例として例示す
る。EXAMPLES Specific examples of the present invention will be illustrated below as examples.
【０００９】[0009]
【実施例１】アルミニウムｉ−プロポキシドと酢酸及び
水（アルミニウムｉ−プロポキシド：酢酸：水＝１：
１．５：０．５〔ｍｏｌ比〕）の反応により、調製した
透明酸化アルミニウム前駆体ゲル状物と酢酸及びｉ−ブ
チルアルコールを混合（前駆体ゲル状物：ｉ−ブチルア
ルコール＝１：２〔重量比〕）し、７０℃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、１２０mm
/minの速度で引き上げることにより、透明前駆体薄膜が
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γ−酸化アルミニウム薄膜ガ得ら
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γ相単相であった。こ
の酸化アルミニウム薄膜は、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２００nm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 Aluminum i-propoxide, acetic acid and water (aluminum i-propoxide: acetic acid: water = 1: 1)
1.5: 0.5 [molar ratio]), and the transparent aluminum oxide precursor gel-like material prepared was mixed with acetic acid and i-butyl alcohol (precursor gel-like material: i-butyl alcohol = 1: 2). [Weight ratio]) and heating to 70 ° C., the precursor gel-like material was completely dissolved to form a transparent solution. Dip a glass plate in this solution, 120 mm
A transparent precursor thin film was formed by pulling up at a speed of / min. After drying at room temperature for 1 hour and baking at 500 ° C. for 30 minutes, a transparent γ-aluminum oxide thin film was obtained. The thin film produced by repeating the operation of pulling up, drying, and firing three times was also transparent and had a γ-phase single phase. As a result of electron microscope observation, this aluminum oxide thin film was confirmed to be a dense film without cracks or pinholes. The film thickness was about 200 nm. The visible spectrum of this thin film is shown in FIG. The prepared solution for forming a transparent thin film was very stable even in the atmosphere, and no change in viscosity or formation of precipitate was observed even after standing for 6 months.
【００１０】[0010]
【実施例２】実施例１において、有機溶媒として、ｉ−
ブチルアルコールの代わりにトルエンを使用し、その他
は実施例１と同様の条件で、透明薄膜作製用溶液の調製
を行った。透明前駆体ポリマー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、透明前
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γ−酸化アルミニウム
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。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、3 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 In Example 1, as the organic solvent, i-
A solution for forming a transparent thin film was prepared under the same conditions as in Example 1 except that toluene was used instead of butyl alcohol. The transparent precursor polymer gel completely dissolved to form a clear solution. A glass plate was immersed in this solution and pulled up at a rate of 60 mm / min to form a transparent precursor thin film. After drying at room temperature for 1 hour and baking at 500 ° C. for 30 minutes, a transparent γ-aluminum oxide thin film was obtained. The thin film produced by repeating this operation of pulling up, drying, and firing 5 times was also transparent. As a result of electron microscope observation, this thin film was confirmed to be a dense film without cracks or pinholes. The prepared solution for forming a transparent thin film was very stable even in the air, and no change in viscosity or precipitation was observed even after standing for 3 months.
【００１１】[0011]
【実施例３】実施例１及び実施例２において、調製され
た透明溶液に、それぞれＳｉＯ2 ガラス基板を浸漬し、
１２０mm/min速度で引き上げることにより、透明前駆体
薄膜を形成させた。室温で１時間乾燥後、８００℃で３
０分間焼成したところ、透明なα−酸化アルミニウム薄
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。Example 3 A SiO 2 glass substrate was dipped in each of the prepared transparent solutions in Examples 1 and 2,
A transparent precursor thin film was formed by pulling up at a speed of 120 mm / min. Dry at room temperature for 1 hour, then at 800 ℃ for 3 hours
When baked for 0 minutes, a transparent α-aluminum oxide thin film was obtained. The thin film produced by repeating this operation of pulling up, drying, and firing three times was also transparent.
As a result of electron microscope observation, this thin film was confirmed to be a dense film without cracks or pinholes.
【００１２】[0012]
【実施例４】実施例１において、調製された透明溶液を
用いて、ステンレス基板に７５０ｒｐｍで１分間、スピ
ンコートを施し、前駆体薄膜を得た。室温で１時間乾燥
後、５００℃で３０分間焼成したところ、γ−酸化アル
ミニウム薄膜が得られた。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。Example 4 Using the transparent solution prepared in Example 1, a stainless steel substrate was spin-coated at 750 rpm for 1 minute to obtain a precursor thin film. After drying at room temperature for 1 hour and baking at 500 ° C. for 30 minutes, a γ-aluminum oxide thin film was obtained. As a result of electron microscope observation, this thin film was confirmed to be a dense film without cracks or pinholes.
【００１３】[0013]
【発明の効果】透明酸化アルミニウム系前駆体ゲル状物
は、室温で有機溶媒での溶解性が低く、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、加熱によっ
て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、緻密な透明酸化アルミニウム薄膜を
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、透明で緻密な酸化アルミニウム薄膜が得られるた
め、酸化アルミニウム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 transparent aluminum oxide-based precursor gel-like material has low solubility in an organic solvent at room temperature, and it was difficult to prepare a thin film-forming solution from this precursor gel-like material. As described in the examples, the present invention makes it possible to easily dissolve the gel-like material in an organic solvent by heating, and to prepare a transparent precursor solution for forming a thin film. Further, according to the present invention, a precursor gel-like material containing almost no unreacted alkoxy group can be dissolved and used as a solution for forming a thin film. Therefore, this solution is applied to a molded product by dipping or spin coating. By firing, it became possible to obtain a dense transparent aluminum oxide thin film with a small amount of residual organics, which was impossible with a conventional alkoxide solution. Furthermore, since the transparent solution in which the precursor gel-like material of the present invention is dissolved does not contain an alkoxide molecule having a hydrolyzable unreacted alkoxy group, unlike the conventional alkoxide solution for thin film production,
There is also an advantage that it can be stably stored for a long period of time without being affected by atmospheric moisture. INDUSTRIAL APPLICABILITY The thin film manufacturing method of the present invention can obtain a transparent and dense aluminum oxide thin film, and thus can greatly expand the use of the aluminum oxide thin film as an optical material.
【図１】作製した酸化アルミ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 a visible spectrum of a manufactured aluminum oxide thin film.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ２３Ｃ 18/12 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C23C 18/12
Claims (2)
ＯＣＯＲ基（ここで、Ｒは炭素数１〜４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透
明酸化アルミニウム前駆体ゲル状物を、加熱して有機溶
媒に溶解することによって、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透明酸化アルミニ
ウム薄膜製造方法。1. A polymer having an A1-O-A1 bond as a main chain and an OCOR group (wherein R represents a linear or branched alkyl group having 1 to 4 carbon atoms) in a side chain. A method for producing a transparent aluminum oxide thin film, which comprises applying a transparent solution obtained by heating a transparent aluminum oxide precursor gel-like material to an organic solvent and heating the solution, and heating the solution.
及び炭素数６〜８までの直鎖または分岐または環式炭化
水素である特許請求の範囲第１項記載の製造方法。2. The production method according to claim 1, wherein the organic solvent is an alcohol having 1 to 5 carbon atoms and a linear, branched or cyclic hydrocarbon having 6 to 8 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13110391A JPH0688783B2 (en) | 1991-06-03 | 1991-06-03 | Method for producing thin film from transparent aluminum oxide precursor gel-like material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13110391A JPH0688783B2 (en) | 1991-06-03 | 1991-06-03 | Method for producing thin film from transparent aluminum oxide precursor gel-like material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0570122A JPH0570122A (en) | 1993-03-23 |
| JPH0688783B2 true JPH0688783B2 (en) | 1994-11-09 |
Family
ID=15050052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13110391A Expired - Fee Related JPH0688783B2 (en) | 1991-06-03 | 1991-06-03 | Method for producing thin film from transparent aluminum oxide precursor gel-like material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0688783B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07171813A (en) * | 1993-07-28 | 1995-07-11 | Nec Corp | Production of ceramic green sheet |
| US6495709B1 (en) * | 2000-03-16 | 2002-12-17 | Symetrix Corporation | Liquid precursors for aluminum oxide and method making same |
-
1991
- 1991-06-03 JP JP13110391A patent/JPH0688783B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0570122A (en) | 1993-03-23 |
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