JPH03503277A - Method for producing thin film perovskite phase lead scandium tantalate - Google Patents
Method for producing thin film perovskite phase lead scandium tantalateInfo
- Publication number
- JPH03503277A JPH03503277A JP1511695A JP51169589A JPH03503277A JP H03503277 A JPH03503277 A JP H03503277A JP 1511695 A JP1511695 A JP 1511695A JP 51169589 A JP51169589 A JP 51169589A JP H03503277 A JPH03503277 A JP H03503277A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- scandium
- heated
- tantalum
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052706 scandium Inorganic materials 0.000 title claims description 28
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 title claims description 28
- 239000010409 thin film Substances 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 125000002524 organometallic group Chemical group 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052594 sapphire Inorganic materials 0.000 claims description 4
- 239000010980 sapphire Substances 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- -1 Tantalum alkoxides Chemical class 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 claims description 2
- CHEANNSDVJOIBS-MHZLTWQESA-N (3s)-3-cyclopropyl-3-[3-[[3-(5,5-dimethylcyclopenten-1-yl)-4-(2-fluoro-5-methoxyphenyl)phenyl]methoxy]phenyl]propanoic acid Chemical compound COC1=CC=C(F)C(C=2C(=CC(COC=3C=C(C=CC=3)[C@@H](CC(O)=O)C3CC3)=CC=2)C=2C(CCC=2)(C)C)=C1 CHEANNSDVJOIBS-MHZLTWQESA-N 0.000 claims 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims 1
- RCBQQZSYZIIPIW-UHFFFAOYSA-N 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-dioxooctanoic acid Chemical compound OC(=O)C(C)(C)C(=O)CC(=O)C(F)(F)C(F)(F)C(F)(F)F RCBQQZSYZIIPIW-UHFFFAOYSA-N 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical class [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 4
- 229910001936 tantalum oxide Inorganic materials 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 2
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/409—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or lead and B representing a refractory metal, nickel, scandium or a lanthanide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
- H10N30/076—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by vapour phase deposition
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 薄膜ペロブスカイト相鉛スカンジウムタンクレートの製造方法 本発明は薄膜ペロブスカイト（ｐｅ ｒｏｖ ｓｋ ｉ ｔｅ）相鉛スカンジウ ムタンタレートの製造方法、特に圧電装置用途の薄膜を製造する有機金属化学蒸 着（ＭＯＣＶＤ）法の改良に関する。[Detailed description of the invention] Method for producing thin film perovskite phase lead scandium tankrate The present invention is based on thin film perovskite (perovskite) phase lead scandiate. Methods for producing mutantalate, especially organometallic chemical vapors for producing thin films for piezoelectric devices. Concerning improvements in the MOCVD method.
セラミック誘導熱検出器を製作する場合、材料の薄膜片を製造する必要が多い。When making ceramic induction heat detectors, it is often necessary to fabricate thin strips of material.
従来、このためには、面倒な、時間のかかるラッピング及び切削法を適用してい た。また、薄膜セラミックの代替法として、これらセラミックの最近開発された 金属有機プリカーサ−を利用する方法が広く使用されている。これら方法では、 金属有機溶液から金属有機化学蒸着（ＭＯＣＶ Ｄ）によって薄膜を蒸着する。Traditionally, this involves applying cumbersome and time-consuming lapping and cutting methods. Ta. Also, as an alternative to thin-film ceramics, recently developed Methods utilizing metal-organic precursors are widely used. In these methods, Thin films are deposited by metal organic chemical vapor deposition (MOCVD) from metal organic solutions.
これらいずれの方法も、厚さが０１μ未満か、それ以上になるように、セラミッ ク薄膜を制御しながら蒸着する。In both of these methods, the ceramic is Controlled deposition of thin films.
これら方法は、チタン酸鉛等の物質に対して開発され、結果はよいが、鉛スカン ジウムタンクレート（ＰＳＴ）に応用できない。というのは、所要の体心立方（ ペロブスカイト）結晶構造のＰＳＴ薄膜を蒸着できないからである。These methods have been developed for materials such as lead titanate and have shown good results, but lead scans It cannot be applied to dium tank rate (PST). This is because the required body-centered cubic ( This is because a PST thin film having a perovskite (perovskite) crystal structure cannot be deposited.
従来、金属有機プリカーサ−から鉛スカンジウム及び特表平３−５０３２７７ （２） タンタル酸化物を共蒸着しても、生成した鉛スカンジウムタンタレートが面心立 方相（パイロクロア−ｐｙ ｒ。Conventionally, from metal-organic precursors to lead scandium and Special Table of Contents Hei 3-503277 (2) Even if tantalum oxide is co-deposited, the produced lead scandium tantalate will not stand out. Hoso (pyrochlore-pyr.
ｃｈｌｏｒｅ）のみを呈するか、あるいは最善でも、望ましくないｆ、ｃ、ｃ、 相を高率で含有する体心立方相（ペロブスカイト）を呈する薄膜を得られるに過 ぎない。本出願人は、共願である、英国特許出願第８８０９９５５．１号に前記 問題の一つの解決法を開示している。しかし、この方法は、４つの段階からなる 。即ち、酸化スカンジウム及び酸化タンタルを共蒸着して、薄膜を形成する第１ 段階；この薄膜をアニーリングする第２段階；このアニーリングした薄膜に酸化 鉛を蒸着する第３段階：そしてこの結果得られた複層を再度アニーリングして、 ペロブスカイト相を呈する鉛スカンジウムタンタレート化合物を得る第４段階で ある。この方法は前記間コに一つの解決を与えるが、にもかかわらず時間がかか り、従って完全に満足のいくものではない。chlore) or, at best, undesirable f, c, c, It is possible to obtain a thin film exhibiting a body-centered cubic phase (perovskite) containing a high proportion of Ginai. The applicant has filed the above patent application in co-applicant UK Patent Application No. 8809955.1. Discloses one solution to the problem. However, this method consists of four steps. . That is, the first step is to co-evaporate scandium oxide and tantalum oxide to form a thin film. Step: Annealing this thin film Second step: Oxidizing this annealed thin film A third step of depositing lead: the resulting multilayer is then re-annealed and In the fourth step to obtain a lead scandium tantalate compound exhibiting a perovskite phase. be. Although this method provides a solution to the above problem, it is nevertheless time consuming. and therefore not completely satisfactory.
本発明の目的は、この問題をより直接的に解決する方法を提供することにある。The purpose of the present invention is to provide a method for solving this problem more directly.
即ち、本発明によれば、気相有機金属試薬から３種類の金属酸化物すべてを共蒸 着して、薄膜を形成し、これを１工程でアニーリングして、ペロブスカイトＰＳ Ｔを形成できることが見いだされた。条件が適当ならば、アニーリングをしなく ても、酸化物がペロブスカイト相として蒸着できる。That is, according to the present invention, all three metal oxides can be co-evaporated from a gas-phase organometallic reagent. perovskite PS, which is then annealed in one step to form a thin film. It has been found that T can be formed. If the conditions are suitable, do not annealing. However, the oxide can be deposited as a perovskite phase.
本発明は、酸素及び有機金属鉛スカンジウム及びタンタルのガス状試薬を混合室 に導入して、ガス混合物を形成し、そしてこのガス混合物を反応器に導入し、加 水分解剤を存在させた状態で該混合物を加熱基体に暴露して、該基体上に薄膜を 形成する工程からなるＲ膜ペロブスカイト相鉛スカンジウムタンタレートの製造 方法を提供するものである。The present invention combines oxygen and organometallic lead scandium and tantalum gaseous reagents into a mixing chamber. is introduced into the reactor to form a gas mixture, and the gas mixture is introduced into the reactor and processed. The mixture is exposed to a heated substrate in the presence of a water splitting agent to form a thin film on the substrate. Production of R film perovskite phase lead scandium tantalate consisting of the process of forming The present invention provides a method.
条件が適当ならば、即ちガス状試薬が化学量論量比で混合されている場合には、 ペロブスカイト相鉛スカンジウムタンクレート薄膜を直接形成できる。別な条件 では、前記工程に引き続いて、基体のアニーリングを行うことによって上記ペロ ブスカイトを形成できる。If the conditions are suitable, i.e. when the gaseous reagents are mixed in stoichiometric proportions, Perovskite phase lead scandium tankrate thin films can be directly formed. different conditions Next, following the above steps, the above perforation is achieved by annealing the substrate. Can form buskites.
なお、加水分解は、基体／ガス界面で生じる複雑な熱分解反応時に起きると考え られる。つまり、水蒸気の代わりに、例えば揮発性アルコール（即ち、低級アル コール）等の別な加水分解剤も使用することができる。It is believed that hydrolysis occurs during a complex thermal decomposition reaction that occurs at the substrate/gas interface. It will be done. This means that instead of water vapor, for example volatile alcohols (i.e. lower Other hydrolyzing agents can also be used, such as (coal).
先願である英国特許出願第８８０９９５５； １号明細書に記載したの同じ金 属有機試薬を使用することができる。即ち、酸化鉛については、任意の揮発性鉛 化合物が使用できる。好ましいのは、次式で示すような、鉛ターシャリーブトキ シド等の鉛アルコキンドあるいはβ−ジケトネートである。Earlier British Patent Application No. 8809955; Same gold as stated in Specification No. 1 Organic reagents of the genus can be used. That is, for lead oxide, any volatile lead Compounds can be used. Preferably, a lead tertiary-button metal, as shown in the following formula: These are lead alcokindes such as sido or β-diketonates.
式中、Ｒ２は好ましくは水素であるが、ハロゲン又は低級アルキルでもよい。Ｒ ｏ及びＲ”はそれぞれアルキル、アリール、アルコキシ又はフッ素化（ｆｌｕｏ ｒｅｎａｔｅｄ）アルキルから選択する。In the formula, R2 is preferably hydrogen, but may also be halogen or lower alkyl. R o and R'' are each alkyl, aryl, alkoxy or fluorinated (fluo renated) alkyl.
才た、酸化スカンジウムについては、次式のβ−ジケトネート類が使用できる。For scandium oxide, β-diketonates of the following formula can be used.
但し、Ｒ１、Ｒｏ及びＲ”は前と同じ定義である。However, R1, Ro and R'' have the same definitions as before.
また、酸化タンタルについては、メトキシドやエトキシド等のタンクルアルコキ シドが使用できる。あるいは、次式に示すようなアルコキシタンタルβ−ジケト ネートも好適である。Regarding tantalum oxide, tantalum alkoxides such as methoxide and ethoxide are also used. Can be used by Sid. Alternatively, an alkoxytantalum β-diketo as shown in the following formula Nate is also suitable.
Ｕ余白コ 但し、Ｒ，はアルキルで、Ｒ２、Ｒ″及びＲ”の定義は前述の通りである。U margin However, R is alkyl, and the definitions of R2, R'' and R'' are as described above.
本発明において好ましいプリカーサ−は次の通りである。Preferable precursors in the present invention are as follows.
（１）鉛ビス（２，２−ジメチル−６，６，７，７，８，８，８−ヘプタフルオ ロオクタン−３，５−ジオ不（２）スカンジウムトリス（２，２−ジメチル−６ ，６，７，７，８，８，８−ヘプタフルオロオクタン−３，５−ジオ不−１・、 及び （３）タンタルペンタエトキシド。(1) Lead bis(2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro) looctane-3,5-dioun(2) scandium tris(2,2-dimethyl-6 ,6,7,7,8,8,8-heptafluorooctane-3,5-dioun-1. as well as (3) Tantalum pentaethoxide.
プリカーサ−（１）及び（２）はそれぞれ鉛Ｆｏｄ及びスカンジウムＦｏｄと呼 ばれている。Precursors (1) and (2) are called lead Fod and scandium Fod, respectively. It's been revealed.
本明細書に添付した図面について説明すると、第１図は本発明によりＭＯＣＶＤ 蒸着を実施する装置特表千３−５０３２７７ （３） の該略図であり、そして 第２図及び第３図は本発明により製造したペロブスカイト相鉛スカンジウムタン クレート薄膜（アニーリングを行ったものと、行わなかったもの）についてのＸ 線回折曲線図である。To explain the drawings attached to this specification, FIG. Equipment for performing vapor deposition Special Table 13-503277 (3) , and Figures 2 and 3 show perovskite phase lead scandium tan produced according to the present invention. X for crate thin films (with and without annealing) It is a line diffraction curve diagram.
以下、各図面について本発明の実施態様を説明する。Embodiments of the present invention will be described below with reference to each drawing.
但し、以下の説明は例示のみを目的としている。However, the following description is for illustrative purposes only.
第１図に示す装置は１絹６つの流量制御器１．３．５．７．９及び１１．１組４ つの加熱されたステンレスチール製のバブル発生器１３．１５．１７及び１９、 混合室２１、及び反応器２３を備えている。基体２５はヒーター２７上の反応器 ２３内部に設定する。排ガスは、低温トラップ３１、スロットルバルブ３３、前 段トラップ３５、ルーツポンプ３７及び回転ポンプ３９からなるポンプ装置２９ によって反応器２３から除去する。反応器２３には、ＵＶ／可視光窓４１及び容 量形圧力計４３を設ける。例えばアルゴン等の不活性ガスを流量制御器のひとつ 、即ち制御器１を介して直接的に、あるいはそれぞれステンレススチール製のバ ブル発生器のうちの３つの発生器１３．１５及び１７及び流量制御器のうちの３ つの制御器２．５、及び７を介して間接的に、混合室２１に導入する。これら３ つのバブル発生器１３．１５及び１７のそれぞれには有機金属鉛、スカンジウム 及びタンタルプリカーサ−を装入しておく。これらの蒸気も混合室２１に導入す る。そして、残りの流量制御器、即ち制御器１１を介して混合室２１に直接導入 する酸素と混合する。第２導入口４７に隣接して設けた第１導入口４５から反応 器２３にガスと蒸気の混合物を装入する。The apparatus shown in Figure 1 includes 1 silk 6 flow controllers 1.3.5.7.9 and 11.1 sets 4 two heated stainless steel bubble generators 13.15.17 and 19; It includes a mixing chamber 21 and a reactor 23. Substrate 25 is a reactor on heater 27 Set inside 23. Exhaust gas is sent to the cold trap 31, throttle valve 33, front Pump device 29 consisting of stage trap 35, roots pump 37 and rotary pump 39 is removed from the reactor 23 by. The reactor 23 has a UV/visible window 41 and a container. A volume type pressure gauge 43 is provided. For example, one of the flow controllers for inert gas such as argon. , i.e. directly via the controller 1 or in each case via a stainless steel bar. 3 of the bull generators 13.15 and 17 and 3 of the flow controllers It is introduced into the mixing chamber 21 indirectly via two controllers 2.5 and 7. These 3 Each of the two bubble generators 13.15 and 17 contains organometallic lead, scandium and tantalum precursor are charged. These vapors are also introduced into the mixing chamber 21. Ru. Then, it is directly introduced into the mixing chamber 21 via the remaining flow rate controller, that is, the controller 11. mix with oxygen. Reaction occurs from the first inlet 45 provided adjacent to the second inlet 47. The vessel 23 is charged with a mixture of gas and steam.
残りの加熱されたステンレススチール製バブル発生器、即ち発生器１９（水を装 入しである）から第２導入口４７を介して水蒸気を装入する。場合によっては、 不活性ガスを残りの流量制御器９及びバブル発生器１９を介して装入してもよい 。The remaining heated stainless steel bubble generator, generator 19 (filled with water) Steam is introduced through the second inlet 47 from the inlet (inlet). In some cases, Inert gas may be introduced via the remaining flow controller 9 and bubble generator 19 .
鉛スカンジウムタンタレート薄膜の蒸着は次のようにして行う。The lead scandium tantalate thin film is deposited as follows.
プリカーサ−（１）、（２）及び（３）を別々に加熱して、真空状態でバブル連 行ガス流れによって運ぶことができる温度にする。各プリカーサ−（１）、（２ ）及び（３）について好適な温度は（１）８０°Ｃ３（２）９０℃及び（３）５ ５℃で、それぞれのガス流■は１０１１０及び４５５ｃｍである。次に、蒸気を 混合室２１に移して、アルゴン（４ｓｓｃｍ）及び酸素（２３ｓｓｃｍ）と混合 した後、例えばサファイヤ、酸化マグネじ′ウノ・や窒化アルミニウム等であれ ばよい、加熱された基体２５を入れた反応器２３にガス７／蒸気混合物を送り、 好適には、６５０℃に加熱して、有機金属を熱分解１−１鉛、スカンジウム及び タンクルの酸化物膜を形成する。Precursors (1), (2) and (3) are heated separately and placed in a bubble chain under vacuum. line to a temperature that can be carried by the gas flow. Each precursor (1), (2 ) and (3), the preferred temperatures are (1) 80°C, (2) 90°C, and (3) 5 At 5°C, the respective gas flows are 10110 and 455 cm. Then steam Transfer to mixing chamber 21 and mix with argon (4sscm) and oxygen (23sscm) After that, be it sapphire, magnetic oxide, aluminum nitride, etc. The gas 7/steam mixture is then fed into the reactor 23 containing the heated substrate 25; Preferably, the organic metal is heated to 650° C. to pyrolyze 1-1 lead, scandium and Forms a tankle oxide film.
有機金属蒸気を反応器に導入する導入口４５における、あるいはその付近におけ るガス流れに水蒸気を導入する場合には、酸化鉛分に富む、蒸着薄膜をアニーリ ングして、ペロブスカイト鉛スカンジウムタ゛ｌタレートにする。驚くべき結果 が得られる。というのは、ゾルゲル法によって蒸着した同様な酸化物薄膜はアニ ーリングしても全くこのような相にはならないからでる。さらに、プリカーサ− の割合を慎重に制御して、化学量論量的組成に近い鉛含量にすると、蒸着薄膜は 純粋なペロブスカイト相になり、アニーリングは必要ない。At or near the inlet 45 for introducing organometallic vapor into the reactor. When water vapor is introduced into the gas stream, the deposited thin film, which is rich in lead oxide, can be annealed. to form perovskite lead scandium talate. amazing results is obtained. This is because similar oxide thin films deposited by sol-gel methods are This is because even if you use a ring, you will not get a phase like this at all. Furthermore, the precursor By carefully controlling the proportion of lead content close to stoichiometric composition, the deposited thin film can be It becomes a pure perovskite phase and no annealing is required.
夫旌豊↓ 以下の表に、実験パラメーターをまとめる。Fu Jeongfeng ↓ The table below summarizes the experimental parameters.
表１ プリカーサ−（１） （２） （３）アルゴン流１ｔ（ｓｓｃｍ） １０ １０ ４ズユｐニサ一温度（’Ｃ） ８２ エ阻− ５４酸素流ｊｌ（ｓｓｃｍ） ２３室圧 １０００ ｍＴｏｒｒ基体７基体温度°Ｃサファイヤ／６５０°Ｃ水蒸 気流量ｃｍ”／ｈ １５蒸着酸化物、Ｐｂ、Ｓｃ、Ｔａ酸化 物 アモルファス（１）鉛Ｆｏｄ （２）スカンジウムＦａｄ （３）タンタルエトキシド 蒸気条件下で、Ｐｂ：Ｓｃ：Ｔａの元素比が３．９：１：１．３の鉛、スカンジ ウム及びタンタルを含む薄膜をアモルファス層として形成する。次に、鉛ジルコ ネートによって非接触で取り囲んだ状態で、９・００°Ｃで１０時間アニーリン グすると、ペロブスカイト構造の鉛スカンジウムタンタレート薄膜が得られる。Table 1 Precursor (1) (2) (3) Argon flow 1t (sscm) 10 10 4 82 E- 54 Oxygen flow l (sscm) 23 Chamber pressure 1000 mTorr Substrate 7 Substrate temperature °C Sapphire/650 °C Water vapor Air flow rate cm”/h 15 Vapor-deposited oxides, Pb, Sc, Ta oxidation Material Amorphous (1) Lead Fod (2) Scandium Fad (3) Tantalum ethoxide Under steam conditions, lead, scandi, with an elemental ratio of Pb:Sc:Ta of 3.9:1:1.3 A thin film containing aluminum and tantalum is formed as an amorphous layer. Next, lead zirco Annealed at 9.00°C for 10 hours while being surrounded without contact by This yields a lead scandium tantalate thin film with a perovskite structure.
（第２図）。(Figure 2).
以下の表に、別な実験パラメーターをまとめる。The table below summarizes the different experimental parameters.
ｌ プリカーサ−（］） （２） （３）アルゴン流ｆｆｉ（ｓＳｃｍ） １３ １０ ８プリカーサ一温度（’Ｃ） ７９ １０４ ６３酸素流量（ｓｓｃｍ） ２３室圧 ＩＱＱＱ ｍＴｏｒｒ基体７基体温度°Ｃ窒化アルミニウム／６５ ０’Ｃ水蒸気流量ａｍ ３／ ｈ １５芭道１１１物、ｐｂ 、鈷マ堕醇化物 ベロースＺカイト −（１）鉛Ｆｏｄ （２）スカンジウムＦｏｄ （３）タンクルエトキシド 表２に記載の条件で、鉛、スカンジウム及びタンタルを２．９６：２．３１・ｌ の元素比で含む薄膜を形成する。Ｘ線分析（第３図）したところ、このものはペ ロブスカイト構造の鉛スカンジウムタンタレートであること水の代わりに追加酸 素源としてアルコールを使用することができる。l Precursor (]) (2) (3) Argon flow ffi (sScm) 13 10 8 Precursor temperature ('C) 79 104 63 Oxygen flow rate (sscm) 23 Room pressure IQQQ mTorr Substrate 7 Substrate temperature °C Aluminum nitride/65 0’C water vapor flow rate am 3/h 15 Basmichi 111, pb , Kouma Fallen Monster Bellows Z Kite - (1) Lead Fod (2) Scandium Fod (3) Tankle ethoxide Under the conditions listed in Table 2, lead, scandium, and tantalum were mixed at 2.96:2.31·l. Form a thin film containing an elemental ratio of . X-ray analysis (Figure 3) revealed that this item was a pen. Added acid instead of water to be lead scandium tantalate with lobskite structure Alcohol can be used as a source.
［余白］ 表１ プリカーサ−（１） （２） （３）ヘリウム流１ｔ（ｓｓｃｍ） ’ ６ ４ ３プリカーサ一温度（’Ｃ） ９７ ６４ ４５酸素流量（ｓｓｃｍ） １５室圧 １０００ ｍＴｏｒｒ基体／基体温度℃ サファイヤ７６５０ °Ｃ水蒸気流ｆｆ１ｃｍ’／ｈ １５（２）スカンジウムＦ ｏｄ （３）タンクルエトキシド 蒸気条件下で、鉛、スカンジウム及びタンタル酸化物をアモルファス薄膜として 蒸着した。これを実施例１と同様にアニーリングしたところ、ペロブスカイト層 の鉛スカンジウムタンクレートが得られた。[margin] Table 1 Precursor (1) (2) (3) Helium flow 1t (sscm) ’ 6 4 3 Precursor temperature (’C) 97 64 45 Oxygen flow rate (sscm) 15 Room pressure 1000 mTorr Substrate/Substrate temperature °C Sapphire 7650 °C water vapor flow ff1cm’/h 15(2) Scandium F od (3) Tankle ethoxide Lead, scandium and tantalum oxides as amorphous thin films under steam conditions Deposited. When this was annealed in the same manner as in Example 1, a perovskite layer was formed. of lead scandium tankrate was obtained.
Ｎ へ Ｉ′Ｖ＋１ｎ） 手続補正書（方式） 平成 ３年 ４月２６日Go to N I′V+1n) Procedural amendment (formality) April 26, 1991
Claims (12)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB888825948A GB8825948D0 (en) | 1988-11-05 | 1988-11-05 | Method for production of thin film perovskite phase lead scandium tantalate |
| GB8825948.6 | 1988-11-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03503277A true JPH03503277A (en) | 1991-07-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1511695A Pending JPH03503277A (en) | 1988-11-05 | 1989-11-06 | Method for producing thin film perovskite phase lead scandium tantalate |
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| Country | Link |
|---|---|
| EP (1) | EP0396703A1 (en) |
| JP (1) | JPH03503277A (en) |
| GB (1) | GB8825948D0 (en) |
| WO (1) | WO1990005202A1 (en) |
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| GB2250029A (en) * | 1990-11-23 | 1992-05-27 | Marconi Gec Ltd | Perovskite lead scandium tantalate film |
| US5790156A (en) * | 1994-09-29 | 1998-08-04 | Tektronix, Inc. | Ferroelectric relaxor actuator for an ink-jet print head |
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| US3356527A (en) * | 1964-04-23 | 1967-12-05 | Ross W Moshier | Vapor-plating metals from fluorocarbon keto metal compounds |
| EP0055459A1 (en) * | 1980-12-29 | 1982-07-07 | Rikuun Electric co. | Process for producing oxides using chemical vapour deposition |
| GB2131611B (en) * | 1982-11-17 | 1986-11-12 | Standard Telephones Cables Ltd | Dielectric materials |
-
1988
- 1988-11-05 GB GB888825948A patent/GB8825948D0/en active Pending
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1989
- 1989-11-06 EP EP89912468A patent/EP0396703A1/en not_active Withdrawn
- 1989-11-06 WO PCT/GB1989/001321 patent/WO1990005202A1/en not_active Application Discontinuation
- 1989-11-06 JP JP1511695A patent/JPH03503277A/en active Pending
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| EP0396703A1 (en) | 1990-11-14 |
| WO1990005202A1 (en) | 1990-05-17 |
| GB8825948D0 (en) | 1988-12-14 |
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