JP2931962B2 - Method for producing transition metal oxide epitaxial film - Google Patents
Method for producing transition metal oxide epitaxial filmInfo
- Publication number
- JP2931962B2 JP2931962B2 JP26335396A JP26335396A JP2931962B2 JP 2931962 B2 JP2931962 B2 JP 2931962B2 JP 26335396 A JP26335396 A JP 26335396A JP 26335396 A JP26335396 A JP 26335396A JP 2931962 B2 JP2931962 B2 JP 2931962B2
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- metal oxide
- acid
- epitaxial film
- thin film
- 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 - Lifetime
Links
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- Crystals, And After-Treatments Of Crystals (AREA)
- Compounds Of Iron (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は遷移金属酸化物エピ
タキシャル膜の製造方法に関するものである。The present invention relates to a method for producing a transition metal oxide epitaxial film.
【０００２】[0002]
【従来の技術】遷移金属酸化物エピタキシャル膜は、非
線形光学素子等の光学機能材料として使用することが可
能である。このような材料の製造方法としては、ＰＶＤ
法や、ＣＶＤ法等の気相法が知られているが、これらの
方法は生産効率の点で未だ満足し得るものではなかっ
た。2. Description of the Related Art A transition metal oxide epitaxial film can be used as an optical functional material such as a nonlinear optical element. As a method for producing such a material, PVD is used.
Methods and gas phase methods such as the CVD method are known, but these methods have not been satisfactory in terms of production efficiency.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、遷移金属酸
化物エピタキシャル膜を生産効率よく製造し得る方法を
提供することをその課題とする。An object of the present invention is to provide a method for producing a transition metal oxide epitaxial film with high production efficiency.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、単結晶基板上に形成
された少なくとも１種の有機基結合遷移金属化合物から
なる薄膜を、１０−２ａｔｍ以下の酸素分圧の条件下で
１５０〜４００℃で１０〜３６０分加熱焼成した後、５
００℃以上の温度で１０〜３６０分加熱焼成して遷移金
属酸化物の薄膜とすることを特徴とする遷移金属酸化物
エピタキシャル膜の製造方法が提供される。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, a thin film made of at least one organic group bonded transition metal compound is formed on a single crystal substrate, under the conditions of 10 -2 atm or less oxygen partial pressure at 150 to 400 ° C. 10 After heating and firing for ~ 360 minutes , 5
A method for producing a transition metal oxide epitaxial film, characterized in that it is fired at a temperature of 00 ° C. or more for 10 to 360 minutes to form a transition metal oxide thin film.
【０００５】[0005]
【発明の実施の形態】本発明の遷移金属酸化物エピタキ
シャル膜の製造方法においては、先ず、単結晶基板上に
有機基結合遷移金属化合物からなる薄膜を形成する。遷
移金属は、ｄ軌道が不完全殻の金属であり、例えば、Ｔ
ｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ等が挙げられ
る。有機基結合遷移金属化合物（以下、単に金属化合物
とも言う）は、有機溶媒に可溶性を示すものであればよ
く、このようなものには、金属の有機酸塩や錯体が包含
される。それらの具体例としては、例えば、ナフテン
酸、２−エチルヘキサン酸、カプリル酸、ステアリン
酸、ラウリン酸、酪酸、プロピオン酸、シュウ酸、クエ
ン酸、乳酸、フェノール、カテコール、安息香酸、サリ
チル酸、ＥＤＴＡ等の有機酸の金属塩や、金属アセチル
アセトナート等の金属錯体等が挙げられる。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the method for producing a transition metal oxide epitaxial film of the present invention, first, a thin film made of an organic group-bonded transition metal compound is formed on a single crystal substrate. The transition metal is a metal having an incomplete shell with d orbitals.
i, V, Cr, Mn, Fe, Co, Ni and the like. The organic group-bonded transition metal compound (hereinafter, also simply referred to as a metal compound) may be any compound that is soluble in an organic solvent, and includes a metal organic acid salt and a complex. Specific examples thereof include, for example, naphthenic acid, 2-ethylhexanoic acid, caprylic acid, stearic acid, lauric acid, butyric acid, propionic acid, oxalic acid, citric acid, lactic acid, phenol, catechol, benzoic acid, salicylic acid, EDTA And metal complexes of metal acids such as metal acetylacetonate.
【０００６】単結晶基板上に金属化合物薄膜を形成する
には、金属化合物の有機溶媒溶液を単結晶基板上に塗布
し、乾燥すればよい。有機溶媒としては、前記した如き
金属化合物を溶解し得るものであればよく、各種のもの
が単独又は混合物の形で使用される。このような溶媒と
しては、例えば、ヘキサン、オクタン、ベンゼン、トル
エン、テトラリン等の炭化水素類、メタノール、エタノ
ール、プロパノール、ブタノール、アミルアルコール等
のアルコール類、アセトン、メチルエチルケトン、アセ
チルアセトン等のケトン類、ジブチルエーテル等のアル
デヒド類、ギ酸、酢酸、プロピオン酸、酪酸、カプリル
酸、ラウリン酸、ステアリン酸、ナフテン酸、リノー
酸、オレイン酸、シュウ酸、クエン酸、乳酸、フェノー
ル、Ｐートルイン酸等の有機酸類、ブチルブチレート等
のエステル酸類、ジメチルアミン、アニリン等アミン
類、Ｎーメチルアセトアミド、フオルムアミド等のアミ
ド類、ジメチルスホキシド等の硫黄含有化合物、ピリジ
ン、フルフラール等の複素環物質類等を挙げることがで
きる。これらの有機溶媒は、具体的に用いる金属化合物
の種類に応じて１種又は２種以上の組合わせで適当に選
定される。金属化合物溶液中には、粘度調節剤として高
分子物質を適量加えることができる。溶液中の金属化合
物濃度は特に制約されず、その上限は金属化合物の溶解
度等によって適宜決められるが、一般的には３〜４０重
量％である。単結晶基板上に金属化合物溶液を塗布する
方法としては、従来公知の方法、例えば、浸漬法、スプ
レー法、ハケ塗り法等の各種の方法を用いることができ
る。溶液塗布後の乾燥は、減圧乾燥、加熱乾燥及びそれ
らを組合わせた方法等で実施される。基板上に形成され
る金属化合物の薄膜は、完全乾燥させる必要はなく、幾
分の溶媒を含有しても良い。基板上に形成する金属化合
物薄膜の厚さは、０．０５〜５μｍ、好ましくは０．１
〜２μｍである。In order to form a metal compound thin film on a single crystal substrate, an organic solvent solution of a metal compound may be applied on the single crystal substrate and dried. Any organic solvent may be used as long as it can dissolve the metal compound as described above, and various types thereof are used alone or in the form of a mixture. Examples of such a solvent include hydrocarbons such as hexane, octane, benzene, toluene, and tetralin; alcohols such as methanol, ethanol, propanol, butanol, and amyl alcohol; ketones such as acetone, methyl ethyl ketone, and acetylacetone; Aldehydes such as butyl ether, organic acids such as formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, lauric acid, stearic acid, naphthenic acid, linoleic acid, oleic acid, oxalic acid, citric acid, lactic acid, phenol and P-toluic acid And ester acids such as butyl butyrate, amines such as dimethylamine and aniline, amides such as N-methylacetamide and formamide, sulfur-containing compounds such as dimethyl sulfoxide, and heterocyclic substances such as pyridine and furfural. Can These organic solvents are appropriately selected in one kind or in combination of two or more kinds according to the kind of the metal compound used specifically. An appropriate amount of a polymer substance can be added as a viscosity modifier to the metal compound solution. The concentration of the metal compound in the solution is not particularly limited, and the upper limit is appropriately determined depending on the solubility of the metal compound and the like, but is generally 3 to 40% by weight. As a method of applying the metal compound solution onto the single crystal substrate, various conventionally known methods, for example, various methods such as an immersion method, a spray method, and a brush coating method can be used. Drying after application of the solution is carried out by vacuum drying, heat drying, a method combining them, or the like. The metal compound thin film formed on the substrate does not need to be completely dried and may contain some solvent. The thickness of the metal compound thin film formed on the substrate is 0.05 to 5 μm, preferably 0.1 to 5 μm.
２2 μm.
【０００７】本発明においては、前記のようにして基板
上に形成された金属化合物の薄膜を、１０−２ａｔｍ以
下の酸素分圧の条件下で１５０〜４００℃で１０〜３６
０分加熱焼成する仮焼成工程と、その仮焼成後に、５０
０℃以上の温度で１０〜３６０分加熱焼成する本焼成工
程の２段階の焼成工程を用いて焼成する。前記仮焼成工
程における酸素分圧は、１０−２ａｔｍ以下、好ましく
は１０−３〜１０−４ａｔｍであり、焼成温度は１５０
〜４００℃、好ましくは２００〜３００℃である。焼成
時間は、１０〜３６０分、好ましくは６０〜１２０分で
ある。前記酸素分圧条件は、減圧の採用やアルゴンガ
ス、窒素ガス、ヘリウムガス等の不活性ガスの採用によ
り形成することができる。この仮焼成工程の採用によ
り、後続の本焼成工程で得られる金酸化物膜のエピタキ
シャル性を著しく向上させることを可能とする。[0007] In the present invention, the metal compound thin film formed on the substrate as described above is formed to a thickness of 10 -2 atm or less.
10-36 at 150-400 ° C. under conditions of lower oxygen partial pressure
A pre-firing step of heating and firing for 0 minutes, and after the pre-firing, 50
Firing is performed using a two-stage firing step of a main firing step of heating and firing at a temperature of 0 ° C. or more for 10 to 360 minutes . The oxygen partial pressure in the calcination step is 10 −2 atm or less , preferably 10 −3 to 10 −4 atm, and the calcination temperature is 150.
To 400 ° C, preferably 200 to 300 ° C. The firing time is 10 to 360 minutes, preferably 60 to 120 minutes. The oxygen partial pressure condition can be formed by employing a reduced pressure or an inert gas such as an argon gas, a nitrogen gas, and a helium gas. By employing this preliminary firing step, it is possible to significantly improve the epitaxial property of the gold oxide film obtained in the subsequent main firing step.
【０００８】前記本焼成工程における酸素分圧は特に制
約されないが、一般的には、１０−２ａｔｍ以下、好ま
しくは１０−４〜１０−３ａｔｍである。焼成温度は５
００℃以上、好ましくは６００〜１０００℃であり、そ
の上限温度は１５００℃程度である。焼成時間は、１０
〜３６０分、好ましくは２０〜６０分である。この本焼
成工程により、単結晶基板上に形成された金属酸化物エ
ピタキシャル薄膜が得られる。この薄膜の厚さは０．０
５〜５μｍ、好ましくは０．１〜２μｍである。The oxygen partial pressure in the firing step is not particularly limited, but is generally 10 −2 atm or less , preferably 10 −4 to 10 −3 atm. Firing temperature is 5
The temperature is at least 00 ° C, preferably 600 to 1000 ° C, and the upper limit temperature is about 1500 ° C. Firing time is 10
３360 minutes, preferably 20-60 minutes. By this main firing step, a metal oxide epitaxial thin film formed on the single crystal substrate is obtained. The thickness of this thin film is 0.0
It is 5-5 μm, preferably 0.1-2 μm.
【０００９】本発明で用いる単結晶基板としては、Ａｌ
2Ｏ3、ＳｒＴｉＯ3、ＬａＡｌＯ3、ＭｇＯ等が用いられ
る。本発明で用いる単結晶基板は、その格子定数がその
上に形成される金属酸化物の格子定数とほぼ一致するも
の、通常、金属酸化物の格子定数の不一致の割合が２％
以内のものを用いるのが好ましく、このような単結晶基
板の採用により、高エピタキシャル性の金属酸化物を得
ることができる。本発明における遷移金属酸化物には、
Ｆｅ2Ｏ3、ＮｉＯ、ＴｉＯ2、Ｃｏ3Ｏ4、Ｆｅ3Ｏ4、Ｃ
ｒ2Ｏ3、ＭｎＯ2等が包含される。The single crystal substrate used in the present invention is Al
2 O 3 , SrTiO 3 , LaAlO 3 , MgO and the like are used. The single crystal substrate used in the present invention has a lattice constant substantially equal to the lattice constant of the metal oxide formed thereon, and usually has a mismatch rate of 2% of the lattice constant of the metal oxide.
It is preferable to use a single crystal substrate. By employing such a single crystal substrate, a highly epitaxial metal oxide can be obtained. In the transition metal oxide in the present invention,
Fe 2 O 3 , NiO, TiO 2 , Co 3 O 4 , Fe 3 O 4 , C
r 2 O 3 , MnO 2 and the like are included.
【００１０】[0010]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。 実施例１ ２−エチルヘキサン酸鉄溶液（溶媒：ミネラルスピリッ
ト）をサファイヤ単結晶（012）面上に塗布し、Ar気流
中280℃で１h仮焼後、Ar中600℃で2h熱処理を行ない、
膜厚約0.1μm酸化鉄膜を作製した。この作製した膜につ
いてＸ線回折（２θ−θscan）の結果、単結晶基板と同
じ指数を持つα−Fe2O3のピークのみが見られ、高い配
向性が認められた。更に（104）反射に対する極点図形
では、基板と同一の方位関係を持ったスポットが観察さ
れた。これらのことから、面内配向したエピタキシャル
α−Fe2O3膜が生成していることが示された。この時の
β-スキャンの半値幅は約３゜であった。Next, the present invention will be described in more detail with reference to examples. Example 1 An iron 2-ethylhexanoate solution (solvent: mineral spirit) was applied on a sapphire single crystal (012) surface, calcined at 280 ° C. for 1 hour in an Ar gas stream, and heat-treated at 600 ° C. for 2 hours in Ar.
An iron oxide film having a thickness of about 0.1 μm was prepared. As a result of X-ray diffraction (2θ-θscan) of this film, only a peak of α-Fe 2 O 3 having the same index as that of the single crystal substrate was observed, and high orientation was recognized. Further, in the pole figure for the (104) reflection, spots having the same azimuthal relationship as the substrate were observed. These facts indicate that an in-plane oriented epitaxial α-Fe 2 O 3 film was generated. At this time, the half width of the β-scan was about 3 °.
【００１１】比較例１ 実施例１と同様の方法で溶液を塗布した後、空気中400
℃で仮焼後Ar中600℃で2h熱処理を行なった膜について
同様のＸ線回折を行なった所、同様の結果を得たが、β
-スキャンの半値幅は約６〜９゜を示し、α−Fe2O3エピ
タキシャル膜の面内配向性は著しく低下していることが
認められた。Comparative Example 1 After a solution was applied in the same manner as in Example 1, the solution was
When the same X-ray diffraction was performed on the film that was calcined at 600 ° C. and then heat-treated at 600 ° C. for 2 hours in Ar, similar results were obtained.
The half width of the scan was about 6 to 9 °, indicating that the in-plane orientation of the α-Fe 2 O 3 epitaxial film was significantly reduced.
【００１２】[0012]
【発明の効果】本発明によれば、エピタキシーの高い遷
移金属酸化物薄膜を生産効率よくかつ安価に得ることが
できる。この遷移金属酸化物膜は、その高いエピタキシ
ーに基づいて、光学機能材料、例えば、非線形光学素子
等として有利に用いることができる。According to the present invention, a transition metal oxide thin film having high epitaxy can be obtained with good production efficiency and at low cost. The transition metal oxide film can be advantageously used as an optical functional material, for example, a nonlinear optical element, based on its high epitaxy.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山口 巌 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (72)発明者 金 昇源 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (72)発明者 近藤 和吉 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (58)調査した分野(Int.Cl.6，ＤＢ名) C30B 28/00 - 35/00 ──────────────────────────────────────────────────続 き Continued from the front page (72) Inventor Iwao Yamaguchi 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Materials Science and Technology (72) Inventor Kim Shogen 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Within the Institute for Materials Engineering and Technology (72) Inventor Kazuyoshi Kondo 1-1-1 Higashi, Tsukuba, Ibaraki Pref. Inside the Institute for Materials Engineering and Industrial Technology (58) Field surveyed (Int. Cl. 6 , DB name) C30B 28 / 00-35/00
Claims (1)
種の有機基結合遷移金属化合物からなる薄膜を、１０
−２ａｔｍ以下の酸素分圧の条件下で１５０〜４００℃
で１０〜３６０分加熱焼成した後、５００℃以上の温度
で１０〜３６０分加熱焼成して遷移金属酸化物の薄膜と
することを特徴とする遷移金属酸化物エピタキシャル膜
の製造方法。At least one of the first and second substrates is formed on a single crystal substrate.
A thin film composed of various organic group-bonded transition metal compounds
150 to 400 ° C under the condition of oxygen partial pressure of -2 atm or less
And baking for 10 to 360 minutes at a temperature of 500 ° C. or more for 10 to 360 minutes to form a transition metal oxide thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26335396A JP2931962B2 (en) | 1996-10-03 | 1996-10-03 | Method for producing transition metal oxide epitaxial film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26335396A JP2931962B2 (en) | 1996-10-03 | 1996-10-03 | Method for producing transition metal oxide epitaxial film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10101485A JPH10101485A (en) | 1998-04-21 |
| JP2931962B2 true JP2931962B2 (en) | 1999-08-09 |
Family
ID=17388306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26335396A Expired - Lifetime JP2931962B2 (en) | 1996-10-03 | 1996-10-03 | Method for producing transition metal oxide epitaxial film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2931962B2 (en) |
-
1996
- 1996-10-03 JP JP26335396A patent/JP2931962B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10101485A (en) | 1998-04-21 |
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