JPS6335772A - Production of thin film of calcia-stabilized zirconia - Google Patents
Production of thin film of calcia-stabilized zirconiaInfo
- Publication number
- JPS6335772A JPS6335772A JP61178542A JP17854286A JPS6335772A JP S6335772 A JPS6335772 A JP S6335772A JP 61178542 A JP61178542 A JP 61178542A JP 17854286 A JP17854286 A JP 17854286A JP S6335772 A JPS6335772 A JP S6335772A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- calcia
- stabilized zirconia
- calcium
- zirconium
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000010409 thin film Substances 0.000 title claims abstract description 32
- 229910002084 calcia-stabilized zirconia Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011575 calcium Substances 0.000 claims abstract description 20
- -1 zirconium alkoxide Chemical class 0.000 claims abstract description 20
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000443 aerosol Substances 0.000 claims abstract description 8
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims abstract description 3
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012159 carrier gas Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 238000005229 chemical vapour deposition Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- 235000012255 calcium oxide Nutrition 0.000 description 6
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000000052 comparative effect 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
- 230000007423 decrease Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000012387 aerosolization Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
酸素イオン導電性を示し、かつ殿械的強度の大きいカル
シア安定化ジルコニアは固体電解質撚ｉｌｌ電池の隔膜
、酸素センサ、酸素ポンプ等として可能性の高い素材で
おる。DETAILED DESCRIPTION OF THE INVENTION Calcia-stabilized zirconia, which exhibits oxygen ion conductivity and has high mechanical strength, is a material with high potential as a diaphragm for solid electrolyte twisted-ill batteries, oxygen sensors, oxygen pumps, and the like.
カルシア安定化ジルコニアの厚膜または成型物はカルシ
ア安定化ジルコニアの粉末を成型することにより製造さ
れている。固体電解質燃料電池の隔膜、ｒ！ｉ素センサ
、酸素ポンプ等いずれの用途においても酸素イオンの移
動速度が重要であり、これを高めるためにはカルシア安
定化ジルコニアは１μもしくはこれ以下の厚さの薄膜で
あることが必要でおる。しかし、カルシア安定化ジルコ
ニア薄膜製造は困難でおり、（イ）プラズマスプレー法
か、もしくは（ロ）金属ジルコニウムと金属カルシウム
とを交互に数層蒸着した後これを酸素で酸化し、ついで
高温度で熱処理すると言う困難でかつ工業的には適して
いない方法が提供されているにすぎない。Thick films or molded products of calcia-stabilized zirconia are produced by molding calcia-stabilized zirconia powder. Solid electrolyte fuel cell diaphragm, r! The movement speed of oxygen ions is important in any application such as an i-element sensor or an oxygen pump, and in order to increase this speed, the calcia-stabilized zirconia needs to be a thin film with a thickness of 1 μm or less. However, it is difficult to produce a calcia-stabilized zirconia thin film; either (a) a plasma spray method or (b) several layers of metallic zirconium and metallic calcium are deposited alternately and then oxidized with oxygen, followed by high-temperature deposition. Only a difficult and industrially unsuitable method of heat treatment has been proposed.
上記（イ）の方法による厚膜ではカルシア安定化ジルコ
ニアが燃料電池隔膜として、または酸素ポンプ等として
作動する温度が高く、このため用途によっては種々の問
題が発生している。そのため作動温度の低下、したがっ
て薄膜化の要求が高い。また上記（ロ）の方法による薄
膜の製造はきわめて困難でおり高価なものとなり、工業
的な方法とは言えない。ジルコニアおよびカルシアは融
点が高く真空蒸着法、スパッタ法等でこれを薄膜化する
ことは不可能であり、またジルコニウムはともかく、カ
ルシウムは揮発性の化合物がなく、このため通常の化学
蒸着法（ＣＶＤ）は採用できない。In the thick film produced by the method (a) above, the temperature at which calcia-stabilized zirconia operates as a fuel cell membrane or an oxygen pump is high, which causes various problems depending on the application. Therefore, there is a strong demand for lower operating temperatures and therefore for thinner films. Furthermore, manufacturing a thin film by the method (b) above is extremely difficult and expensive, and cannot be called an industrial method. Zirconia and calcia have high melting points and cannot be made into thin films by vacuum evaporation, sputtering, etc. Also, apart from zirconium, calcium does not have any volatile compounds, so it cannot be made into thin films using the usual chemical vapor deposition method (CVD). ) cannot be adopted.
このようにカルシア安定化ジルコニア薄膜の工業的製造
方法はまだ提案されていない。本発明はかかる従来技術
の欠点に鑑み、工業的価値のめる安価なカルシア安定化
ジルコニア簿膜の安価な製造方法が提案される。As described above, an industrial method for producing a calcia-stabilized zirconia thin film has not yet been proposed. In view of the drawbacks of the prior art, the present invention proposes an inexpensive method for producing a calcia-stabilized zirconia membrane that is industrially valuable.
（問題点を解決するための手段〕
本発明は、かかる従来技術の欠点を解消するために下記
の構成を有する。(Means for Solving the Problems) The present invention has the following configuration in order to eliminate the drawbacks of the prior art.
すなはち、本発明は、基板上で、ジルコニウムアルコキ
シドおよびカルシウムアルコキシド有する溶液のエアロ
ゾルと、水蒸気とを加熱下で反応させることを特徴とす
るカルシア安定化ジルコニア薄膜の製造方法。に関する
。Specifically, the present invention provides a method for producing a calcia-stabilized zirconia thin film, which comprises reacting an aerosol of a solution containing zirconium alkoxide and calcium alkoxide with water vapor on a substrate under heating. Regarding.
ここで、カルシアとは酸化カルシウムＣａＯをいい、ジ
ルコニアとは酸化ジルコニウムＺ，０２をいう。Here, calcia refers to calcium oxide CaO, and zirconia refers to zirconium oxide Z,02.
ジルコニウムアルコキシドおよびカルシウムアルコキシ
ドとしては種々のものが可能であるが、工業的に安価に
得られること、通常の有機溶媒に溶【ブ易いことから、
ジルコニウムテトラブトキシドとカルシウムエトキシド
が好適である。Various zirconium alkoxides and calcium alkoxides are possible, but because they can be obtained industrially at low cost and are easily soluble in ordinary organic solvents,
Zirconium tetrabutoxide and calcium ethoxide are preferred.
これらのジルコニウムアルコキシドおよびカルシウムア
ルコキシドの溶媒としてはこれらを溶解する能力を持つ
有機溶媒が一般に用いられるが、とくにアルコール、こ
のなかでもエチルアルコールとブチルアルコールとの混
合溶媒が、系の粘度およびアルコキシドの溶解度から判
断してより適している。エチルアルコールとブチルアル
コールとの割合は広い範囲において選択可能でおるが、
とくに、９〉エチルアルコール／ブチルアルコール（容
量比）〉１の範囲が好適に利用される。容量比が９以上
であると、アルコキシドの溶解度が低下し、逆に１以下
であると、系の粘度が高くなり、エアロゾルが生成しに
くくなるためである。Organic solvents that have the ability to dissolve these zirconium alkoxides and calcium alkoxides are generally used, but alcohols, especially mixed solvents of ethyl alcohol and butyl alcohol, are used because of the viscosity of the system and the solubility of the alkoxides. Judging from this, it is more suitable. Although the ratio of ethyl alcohol to butyl alcohol can be selected within a wide range,
In particular, a range of 9>ethyl alcohol/butyl alcohol (volume ratio)>1 is preferably used. This is because if the volume ratio is 9 or more, the solubility of the alkoxide decreases, whereas if it is 1 or less, the viscosity of the system increases and it becomes difficult to generate an aerosol.
ジルコニウムアルコキシドとカルシウムアルコキシドと
の割合は製造するカルシア安定化ジルコニアに含有され
るこれら成分の割合により決定されるものであるが、通
常カルシウムがジルコニウムの０．５％（重量）から１
０％の範囲であるカルシア安定化ジルコニアが安定化お
よび強度の点から好ましく、本発明における原料溶液組
成も、この範囲が適当でおる。原料溶液におけるジルコ
ニウムアルコキシドの濃度も広い範囲において選択可能
であるが、通常ジルコニウムが０．１〜１０重量％とな
る範囲で選択され、とくに好ましくはこの範囲は１〜５
％である。なぜなら、濃度が１０重量％より大きい範囲
では、系が高粘性となるためＣＶＤＬにくくなり、０．
１重量％より小さい範囲では、ＣＶＤ速度が低下するた
めである。The ratio of zirconium alkoxide to calcium alkoxide is determined by the ratio of these components contained in the calcia-stabilized zirconia to be produced, but usually calcium is 0.5% (by weight) of zirconium.
Calcia-stabilized zirconia in the range of 0% is preferred from the viewpoint of stability and strength, and this range is also suitable for the raw material solution composition in the present invention. The concentration of zirconium alkoxide in the raw material solution can be selected within a wide range, but it is usually selected in a range where zirconium is 0.1 to 10% by weight, and particularly preferably this range is 1 to 5% by weight.
%. This is because when the concentration is greater than 10% by weight, the system becomes highly viscous, making CVDL difficult.
This is because in a range smaller than 1% by weight, the CVD rate decreases.
しかしこれに限定されるものではない。このようにして
得られる原料溶液は組成成分が均一に蒸発 ゛しないの
で、通常の減圧ＣＶＤによりＣＶＤすることはできない
。この溶液は超音波または霧吹の原理等ににリエアロゾ
ル化することにより均一にＣＶＤ反応系に供給すること
ができることを見いだした。エアロゾルとしたのち、適
当量のキャリアガスと混合し、反応系に供給可能である
。キャリアガスとしては通常ＣＶＤで使用される水素、
窒素等が使用される。ＣＶＤ反応系の中で適当量の水分
と高温で反応され、カルシア安定化ジルコニア薄膜とな
る。However, it is not limited to this. Since the constituent components of the raw material solution obtained in this manner do not evaporate uniformly, it cannot be subjected to CVD using ordinary low pressure CVD. It has been found that this solution can be uniformly supplied to the CVD reaction system by re-aerosolizing it using ultrasound or atomizing principles. After being made into an aerosol, it can be mixed with an appropriate amount of carrier gas and supplied to the reaction system. Hydrogen, which is usually used in CVD, is used as a carrier gas.
Nitrogen etc. are used. It is reacted with an appropriate amount of moisture at high temperature in a CVD reaction system to form a calcia-stabilized zirconia thin film.
反応系に供給される水分の量は原料成分であるジルコニ
ウムアルコキシド、およびカルシウムアルコキシドを分
解するに足る量でも良いが、通常反応を促進するためこ
の量の数倍から数十倍程度以上の川がキャリアガスとと
もに系に供給される。反応温度は原料成分と水の反応を
促進するに足る温度であれば良いが、通常３００〜２０
００°Ｃ１好ましくは、５００〜１０００℃が適当であ
る。未反応のアルコール成分を分解するために空気およ
び酸素等を反応系に添加することも可能である。反応時
間は原料濃度、作製する薄膜の厚さ等により適宜選択さ
れる゛が、通常数分から数１０分の範囲で充分でおる。The amount of water supplied to the reaction system may be sufficient to decompose the raw material components zirconium alkoxide and calcium alkoxide, but it is usually several times to several tens of times this amount to accelerate the reaction. Supplied to the system along with carrier gas. The reaction temperature may be any temperature that is sufficient to promote the reaction between the raw material components and water, but is usually 300 to 20°C.
00°C1 Preferably, 500 to 1000°C is appropriate. It is also possible to add air, oxygen, etc. to the reaction system in order to decompose unreacted alcohol components. The reaction time is appropriately selected depending on the raw material concentration, the thickness of the thin film to be produced, etc., but a range of several minutes to several tens of minutes is usually sufficient.
ＣＶＤＩ、：あける基板の加熱は反応管の外から加熱す
るいわゆる外熱式でも良いが、これでは反応管の内壁が
加熱されここに薄膜が生成することになり、経済的では
ない。したがって、反応管内壁の加熱されにくい誘導加
熱方式がより適当である。CVDI: The substrate to be opened may be heated by a so-called external heating method in which the substrate is heated from outside the reaction tube, but this method heats the inner wall of the reaction tube and forms a thin film there, which is not economical. Therefore, an induction heating method in which the inner wall of the reaction tube is less likely to be heated is more suitable.
本発明でいう基板とは、石英、アルミナ、ジルコニア、
ガラス等をいう。The substrate referred to in the present invention includes quartz, alumina, zirconia,
Glass, etc.
本発明の方法により作製される薄膜の厚さは薄膜作製条
件により広く選択可能で市、たとえば数１０人から数１
０μまで幅広く選択可能でおる。The thickness of the thin film produced by the method of the present invention can be selected widely depending on the thin film production conditions.
It is possible to select from a wide range up to 0μ.
（実施例）
実施例１
Ｚｒ （ＢｕＯ）４を８０％含有するブチルアルコール
溶液１０．４ｍｌに、ブチルアルコール２３ｍ１、エチ
ルアルコール１９０ｍ１、金属カルシウム０．０９８Ｃ
１を加え８時間還流し、やや黄色をおびた均一な溶液を
作製した。この溶液６ｍ１を超音波発生器（５０Ｗ＞の
容器に入れ、窒素を１５０ｍ１／分の流量で容器に流し
、発生したエアロゾルを随伴させＣＶＤ反応器（直径３
０ｍｍ、長さ５００ｍｍの石英反応管）に供給した。(Example) Example 1 To 10.4 ml of a butyl alcohol solution containing 80% Zr (BuO)4, add 23 ml of butyl alcohol, 190 ml of ethyl alcohol, and 0.098 C of metallic calcium.
1 was added and refluxed for 8 hours to prepare a slightly yellow homogeneous solution. 6 ml of this solution was placed in a container with an ultrasonic generator (50 W), nitrogen was flowed into the container at a flow rate of 150 ml/min, the aerosol generated was entrained, and a CVD reactor (diameter 3
0 mm and a length of 500 mm).
ＣＶＤ反応器には別のノズルから窄温で水を飽和させた
空気を１０００ｍ１７分の流量で供給し、石英基板の直
前でこれらの二つのガスを混合し、反応させた。基板の
温度は外熱式により５００℃に加熱した。２３分反応を
継続した後、原料ガスの供給を停止し、さらに空気を供
給しながら１０００′Ｃで６０分焼成した。基板に強固
に付着した、干渉色のある綺麗な薄膜が生成していた。Air saturated with water at a constricted temperature was supplied to the CVD reactor from another nozzle at a flow rate of 1000 ml/min, and these two gases were mixed and reacted just in front of the quartz substrate. The temperature of the substrate was heated to 500° C. using an external heating method. After continuing the reaction for 23 minutes, the supply of raw material gas was stopped, and the mixture was fired at 1000'C for 60 minutes while supplying air. A beautiful thin film with interference colors was formed that firmly adhered to the substrate.
このＪ：うにして得た薄膜に含有されるジルコニアおよ
びカルシアをＸＰＳ （Ｘ−Ｒａｙｐｈｏｔｏｅｌｅｃ
ｔｒｏｎ ３ｐｅｃｔｒｏ −ｓ ｃ ｏ ｐ ”ｙ
＞ ；Ｉ−３よびＡＥＳ （ＡｕｑｅｒＥｌｅｃｔｒ
ｏｎ ５ｐｅｃｔｒｏｓｃｏｐＶ）の手法により分析
した結果、ｃａｏ １２ｍ０Ｉ％、ＺｒＯ２ｓａｍｏ
１％の結果を得た。アルゴンで薄膜をエツチングしなが
ら測定した結果、表面から８０００Ａの位置で基板であ
る石英の分析値を得た。理学電気（株）のＸ線薄膜デフ
ラクトメータによりＣｕＫαを線源とし、５０ｋＶ、２
００ｍＡの条件で得たチャートを第１図のＡ（仝体図）
３δよび第２図（拡大図〉に示す。２θ＝３１度のピー
クから結晶は立方晶もしくは正方品であると判断され、
カルシア安定化ジルコニアが生成していることが理解さ
れる。The zirconia and calcia contained in the thin film obtained by this J:
tron 3pectro-s cop”y
>;I-3 and AES (AuqerElectr
As a result of analysis using the method of
A result of 1% was obtained. As a result of measurement while etching the thin film with argon, an analytical value of the quartz substrate was obtained at a position of 8000 A from the surface. Using an X-ray thin film defractometer from Rigaku Denki Co., Ltd., CuKα was used as the radiation source, 50 kV, 2
The chart obtained under the 00mA condition is A (body diagram) in Figure 1.
3δ and Figure 2 (enlarged view). From the peak at 2θ = 31 degrees, the crystal is judged to be cubic or tetragonal.
It is understood that calcia-stabilized zirconia is produced.
比較例１
カルシウムを添加しない原料溶液を用いて作製した薄膜
のＸ線チャートを第１図のＢおよび第３図に示す。第３
図からカルシウムを添加しない原料を用いる場合には薄
膜の結晶は主として単斜品系であり、この場合はジルコ
ニアは安定化されていない。Comparative Example 1 X-ray charts of a thin film produced using a raw material solution to which no calcium is added are shown in FIG. 1B and FIG. 3. Third
As can be seen from the figure, when a raw material to which no calcium is added is used, the crystals of the thin film are mainly monoclinic, and in this case the zirconia is not stabilized.
実施例２
Ｚｒ （ＢｕＯ）４を８０％含有するブチルアルコール
溶液２０．２ｍｌに、ブチルアルコール２３ｍ１、エチ
ルアルコ−シフ５ｍ腰金属カルシウム０．５５ＣＩを加
え８時間還流し、やや黄色をおびた均一な溶液を作製し
た。この溶液を原料とし、実施例１と同じ方法で薄膜を
作製し分析した。Example 2 To 20.2 ml of a butyl alcohol solution containing 80% Zr (BuO)4, 23 ml of butyl alcohol and 0.55 CI of ethyl alcohol Schiff 5m metal calcium were added and refluxed for 8 hours to form a slightly yellowish homogeneous solution. was created. Using this solution as a raw material, a thin film was prepared and analyzed in the same manner as in Example 1.
薄膜はＣａＯを２６ｍｏ＋％、ＺｒＯ２を７４ｍ０１％
含有しており、Ｘ線分析の結果（第１図のＣおよび第４
図〉結晶は立方または正方品系であリ、カルシア安定化
ジルコニアが生成していることが理解される。The thin film contains 26mo+% CaO and 74m01% ZrO2.
The results of X-ray analysis (C and 4 in Figure 1)
Figure: The crystals are cubic or tetragonal, and it is understood that calcia-stabilized zirconia is produced.
実施例３
Ｚｒ （ＢｕＯ）４を８０％含有するブチルアルコール
溶液２０．２ｍｌに、ブチルアルコール９０ｍ１、エチ
ルアルコール６０ｍ−金属カルシウム０．５５（ｊを加
え８時間還流し、やや黄色をおびた均一な溶液を作製し
た。この溶液を原料とし実施例１と同じ方法で石英基板
にＣＶＤした。Example 3 To 20.2 ml of a butyl alcohol solution containing 80% Zr (BuO)4 were added 90 ml of butyl alcohol, 60 m of ethyl alcohol, and 0.55 mL of metallic calcium, and refluxed for 8 hours to form a slightly yellowish homogeneous solution. A solution was prepared. Using this solution as a raw material, CVD was performed on a quartz substrate in the same manner as in Example 1.
しかし、この方法では薄膜は生成せず、粉状の生成物し
か得られなかった。However, this method did not produce a thin film and only a powdery product was obtained.
実施例４
Ｚｒ（ＢｕＯ）４を８０％含有するブチルアルコール溶
）夜８０．２ｍｌに、ブチルアルコール４０ｍ１ 、エ
チルアルコール６０ｍ腰金属カルシウム２．０ＣＩを加
え８時間還流し、やや黄色をおびた均一な溶液を作製し
た。この溶液を原料とし実施例１と同じ方法で石英基板
にＣＶＤした。しかし、この方法ではほとんどＣＶＤ生
成物は得られなかった。Example 4 To 80.2 ml of a butyl alcohol solution containing 80% Zr(BuO)4, 40 ml of butyl alcohol, 60 ml of ethyl alcohol, and 2.0 CI of metallic calcium were added and refluxed for 8 hours to form a slightly yellowish homogeneous solution. A solution was prepared. Using this solution as a raw material, CVD was performed on a quartz substrate in the same manner as in Example 1. However, this method yielded very little CVD product.
〔発明の効果〕
本発明は、エアロゾル化することにＪ：す、通常の化学
蒸着法の採用が可能となるため、安価でかつ膜厚が広く
選択可能なカルシア安定化ジルコニア薄膜の製造を可能
にするものである。[Effects of the Invention] The present invention makes it possible to use a normal chemical vapor deposition method for aerosolization, making it possible to produce a calcia-stabilized zirconia thin film at low cost and with a wide selection of film thicknesses. It is something to do.
第１図は、Ｘ線薄膜デフラクトメータにより、得たＸ線
チャートを示す。本発明実施例１の化合物のチャートを
Ａに、比較例１の化合物のチャートをＢに、実施例２の
化合物のチャートをＣにそれぞれ示す。
第２図は、第１図Ａの拡大図でおる。
第３図は、第１図Ｂの拡大図である。
第４図は、第１図Ｃの拡大図である。
特許出願人 東 し 株 式 会 社」ａ
Ｉ’ｌｌ叫FIG. 1 shows an X-ray chart obtained by an X-ray thin film defractometer. A chart of the compound of Example 1 of the present invention is shown in A, a chart of the compound of Comparative Example 1 is shown in B, and a chart of the compound of Example 2 is shown in C. FIG. 2 is an enlarged view of FIG. 1A. FIG. 3 is an enlarged view of FIG. 1B. FIG. 4 is an enlarged view of FIG. 1C. Patent applicant: Toshi Co., Ltd.
Claims (5)
シウムアルコキシドを含有する溶液のエアロゾルと、水
蒸気とを加熱下に反応させることを特徴とするカルシア
安定化ジルコニア薄膜の製造方法。(1) A method for producing a calcia-stabilized zirconia thin film, which comprises reacting an aerosol of a solution containing zirconium alkoxide and calcium alkoxide with water vapor on a substrate under heating.
ブトキシドであり、かつカルシウムアルコキシドが、カ
ルシウムエトキシドであることを特徴とする特許請求の
範囲第（１）項記載のカルシア安定化ジルコニア薄膜の
製造方法。(2) The method for producing a calcia-stabilized zirconia thin film according to claim (1), wherein the zirconium alkoxide is zirconium tetrabutoxide, and the calcium alkoxide is calcium ethoxide.
を混合溶媒とすることを特徴とする特許請求の範囲第（
１）項または第（２）項記載のカルシア安定化ジルコニ
ア薄膜の製造方法。(3) Claim No. 3, characterized in that the solution is a mixed solvent of ethyl alcohol and butyl alcohol.
A method for producing a calcia-stabilized zirconia thin film according to item 1) or item (2).
ら１０％の範囲であることを特徴とする特許請求の範囲
第（１）項または第（２）項記載のカルシア安定化ジル
コニア薄膜の製造方法。(4) Production of a calcia-stabilized zirconia thin film according to claim (1) or (2), characterized in that calcium is in the range of 0.5% (by weight) to 10% of zirconium. Method.
９＞エチルアルコール／ブチルアルコール（容量比）＞
１であることを特徴とする特許請求の範囲第（３）項ま
たは第（４）項記載のカルシア安定化ジルコニア薄膜の
製造方法。 （６〉加熱温度が、３００〜２０００℃であることを特
徴とする特許請求の範囲第（１）項記載のカルシア安定
化ジルコニア薄膜の製造方法。(5) The ratio of ethyl alcohol and butyl alcohol is 9 > ethyl alcohol/butyl alcohol (volume ratio) >
1. A method for producing a calcia-stabilized zirconia thin film according to claim (3) or (4). (6) The method for producing a calcia-stabilized zirconia thin film according to claim (1), wherein the heating temperature is 300 to 2000°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61178542A JPS6335772A (en) | 1986-07-29 | 1986-07-29 | Production of thin film of calcia-stabilized zirconia |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61178542A JPS6335772A (en) | 1986-07-29 | 1986-07-29 | Production of thin film of calcia-stabilized zirconia |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6335772A true JPS6335772A (en) | 1988-02-16 |
Family
ID=16050299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61178542A Pending JPS6335772A (en) | 1986-07-29 | 1986-07-29 | Production of thin film of calcia-stabilized zirconia |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6335772A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007013181B4 (en) * | 2007-03-20 | 2017-11-09 | Evonik Degussa Gmbh | Transparent, electrically conductive layer |
| JP2021014390A (en) * | 2019-07-16 | 2021-02-12 | 日本特殊陶業株式会社 | Method for producing ceramic sintered body |
-
1986
- 1986-07-29 JP JP61178542A patent/JPS6335772A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007013181B4 (en) * | 2007-03-20 | 2017-11-09 | Evonik Degussa Gmbh | Transparent, electrically conductive layer |
| JP2021014390A (en) * | 2019-07-16 | 2021-02-12 | 日本特殊陶業株式会社 | Method for producing ceramic sintered body |
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