JP3449617B2 - Metal oxide thin film and method for forming the same - Google Patents
Metal oxide thin film and method for forming the sameInfo
- Publication number
- JP3449617B2 JP3449617B2 JP2000291395A JP2000291395A JP3449617B2 JP 3449617 B2 JP3449617 B2 JP 3449617B2 JP 2000291395 A JP2000291395 A JP 2000291395A JP 2000291395 A JP2000291395 A JP 2000291395A JP 3449617 B2 JP3449617 B2 JP 3449617B2
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- thin film
- organic compound
- oxide thin
- compound solvent
- 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
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光学材料、光電変
換材料、電子材料、ピエゾ素子、強誘電体材料、超伝導
材料、メモリー、保護膜等に好適な金属酸化物薄膜を形
成させる方法に関する。TECHNICAL FIELD The present invention relates to a method for forming a metal oxide thin film suitable for optical materials, photoelectric conversion materials, electronic materials, piezo elements, ferroelectric materials, superconducting materials, memories, protective films and the like. .
【０００２】[0002]
【従来の技術】金属酸化物薄膜は、一般に化学的気相成
長法（以下、「ＣＶＤ法」と略記）、物理的蒸着法（以
下、「ＰＶＤ法」と略記）及びゾルゲル法により、基体
上に形成される。2. Description of the Related Art A metal oxide thin film is generally formed on a substrate by a chemical vapor deposition method (hereinafter abbreviated as "CVD method"), a physical vapor deposition method (hereinafter abbreviated as "PVD method") and a sol-gel method. Is formed.
【０００３】ＣＶＤ法やＰＶＤ法は、大面積の基体上に
金属酸化物薄膜を形成させることができず、真空系を必
要とするため高価となり、経済性の点で問題がある。The CVD method and the PVD method cannot be formed on a large-area substrate to form a metal oxide thin film, and require a vacuum system, resulting in high cost and problems in terms of economy.
【０００４】一方、ゾルゲル法は、上記欠点がなく、大
面積の基体上にも金属酸化物薄膜が形成でき、経済性に
優れており、廉価な金属酸化物薄膜の形成方法として注
目されている。On the other hand, the sol-gel method does not have the above-mentioned drawbacks, can form a metal oxide thin film on a large-area substrate, is excellent in economical efficiency, and is attracting attention as an inexpensive metal oxide thin film forming method. .
【０００５】ゾルゲル法では、一般に、金属塩をアルコ
ール溶媒で溶解させた後、酸やアルカリ触媒を添加させ
て調製した溶液を、ハケ塗りや浸漬等により、基体上に
付着させ、乾燥させた後、ついで熱処理させることによ
り、微粒子状の金属酸化物薄膜を形成させる。ゾルゲル
法で形成された金属酸化物薄膜は、微粒子状であり、金
属酸化物薄膜形成時の微粒子間の結合力が弱く、一度に
厚い金属酸化物薄膜を形成させると、クラックが発生す
るという問題点があった。In the sol-gel method, generally, a solution prepared by dissolving a metal salt in an alcohol solvent and then adding an acid or an alkali catalyst is applied onto the substrate by brush coating, dipping or the like and dried. Then, heat treatment is performed to form a fine particle metal oxide thin film. The metal oxide thin film formed by the sol-gel method is in the form of fine particles, and the bonding force between the fine particles during the formation of the metal oxide thin film is weak, and cracks occur when a thick metal oxide thin film is formed at one time. There was a point.
【０００６】特開平第１１―２２２６９０号公報には、
チタン基体及び電極活性層間に拡散混合層を形成させ
て、チタン基体上と電極活性層との密着性を向上させた
電解用電極が開示されている。Japanese Unexamined Patent Publication No. 11-222690 discloses
An electrolysis electrode is disclosed in which a diffusion mixed layer is formed between a titanium base and an electrode active layer to improve the adhesion between the titanium base and the electrode active layer.
【０００７】特開平第１１−２２２６９０号公報では、
チタン基体上に、高分子状二酸化チタン(金属酸化物オ
リゴマー―芳香族化合物溶媒錯体）含有溶液を、浸漬等
により付着させ、ついで熱処理させて形成させた二酸化
チタン超薄膜を介して、チタン基体成分と電極活性層成
分とが、分子レベルで相互に拡散した拡散混合層が形成
され、基体と電極活性層間に強固な結合が形成される。In Japanese Patent Laid-Open No. 11-222690,
A solution containing a polymer titanium dioxide (metal oxide oligomer-aromatic compound solvent complex) is deposited on a titanium substrate by dipping or the like, and then heat treated to form a titanium dioxide ultrathin film, and the titanium substrate component And the electrode active layer components are mutually diffused at the molecular level to form a diffusion mixed layer, and a strong bond is formed between the substrate and the electrode active layer.
【０００８】特開平第１１−２２２６９０号公報は、二
層以上の積層構造、特に隣接する層同士を相互に拡散、
混合させた積層構造を得るには適しているが、結晶性が
良く、均質でかつクラックを有しない薄膜が要求される
材料、例えば光学材料、光電変換材料、電子材料、ピエ
ゾ素子、強誘電体材料、超伝導材料等には不適であっ
た。Japanese Unexamined Patent Publication No. 11-222690 discloses a laminated structure of two or more layers, especially adjacent layers are mutually diffused,
Materials suitable for obtaining a mixed laminated structure, but having good crystallinity and being required to have a homogeneous and crack-free thin film, such as optical materials, photoelectric conversion materials, electronic materials, piezo elements, and ferroelectrics It was unsuitable for materials and superconducting materials.
【０００９】本発明の目的は、従来技術の上記問題点を
解決し得る、基体上に、クラックのない均質な金属酸化
物薄膜を形成させる方法及び該方法により形成される金
属酸化物薄膜を提供することである。An object of the present invention is to provide a method for forming a uniform metal oxide thin film without cracks on a substrate, which can solve the above problems of the prior art, and a metal oxide thin film formed by the method. It is to be.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、特開平第
１１−２２２６９０号公報のように、基体上に高分子状
二酸化チタン（金属酸化物オリゴマー―芳香族化合物溶
媒錯体）含有溶液を付着させた基体を、直接加熱処理さ
せると、基体成分が金属酸化物オリゴマーの金属成分に
拡散してしまうことに鑑み、生成させた金属酸化物オリ
ゴマー−有機化合物溶媒錯体含有溶液中の、均質な金属
酸化物オリゴマーの形態を可能な限り保持したまま、基
体上にほとんどクラックのない状態を保持できるか、種
々検討した結果、熱処理の前に、基体上の前記付着溶液
中の飽和有機化合物溶媒の少なくとも一部を除去させる
ことにより、上記課題が解決し得ることを見出し、本発
明に完成するに至った。DISCLOSURE OF THE INVENTION The inventors of the present invention have disclosed a solution containing a polymeric titanium dioxide (metal oxide oligomer-aromatic compound solvent complex) containing solution on a substrate as disclosed in JP-A No. 11-222690. When the adhered substrate is directly heat-treated, the substrate component diffuses into the metal component of the metal oxide oligomer, and in view of the fact that the produced metal oxide oligomer-organic compound solvent complex-containing solution is homogeneous. As a result of various studies as to whether or not the state of almost no cracks can be retained on the substrate while retaining the morphology of the metal oxide oligomer as much as possible, before the heat treatment, the saturated organic compound solvent in the deposition solution on the substrate was It was found that the above problems can be solved by removing at least a part, and the present invention has been completed.
【００１１】すなわち、本発明は、第１に、金属塩及び
飽和有機化合物溶媒を含む溶液から調製された金属酸化
物オリゴマー―飽和有機化合物溶媒錯体含有溶液を、基
体上に付着させ、ついで前記付着溶液中の飽和有機化合
物溶媒の少なくとも一部を除去させた後、さらに熱処理
させることにより、金属酸化物薄膜を形成させることを
特徴とする金属酸化物薄膜の形成方法であり、該方法に
より形成される金属酸化物薄膜である。That is, according to the present invention, firstly, a metal oxide oligomer-saturated organic compound solvent complex-containing solution prepared from a solution containing a metal salt and a saturated organic compound solvent is deposited on a substrate, and then the deposition is performed. A method for forming a metal oxide thin film, which comprises forming a metal oxide thin film by further heating after removing at least a part of the saturated organic compound solvent in the solution. Is a metal oxide thin film.
【００１２】また、本発明は、第２に、金属塩を溶解さ
せた飽和有機化合物溶媒を含む溶液に、水―アルコール
混合溶液を添加させて調製された金属酸化物オリゴマー
―飽和有機化合物溶媒錯体含有溶液を、基体上に付着さ
せ、ついで前記付着溶液中の飽和有機化合物溶媒の４０
〜８０％を除去させた後、さらに熱処理させることによ
り、金属酸化物薄膜を形成させることを特徴とする金属
酸化物薄膜の形成方法であり、該方法により形成される
金属酸化物薄膜である。Secondly, the present invention relates to a metal oxide oligomer-saturated organic compound solvent complex prepared by adding a water-alcohol mixed solution to a solution containing a saturated organic compound solvent in which a metal salt is dissolved. The containing solution is deposited on the substrate and then 40 % of the saturated organic compound solvent in the depositing solution is added.
A method for forming a metal oxide thin film, which comprises forming a metal oxide thin film by further removing -80% and then performing heat treatment. The metal oxide thin film is formed by the method.
【００１３】本発明を、以下、詳細に説明する。The present invention will be described in detail below.
【００１４】本発明の金属酸化物薄膜の形成方法は、金
属塩及び飽和有機化合物溶媒を含む溶液から金属酸化物
オリゴマー―飽和有機化合物溶媒錯体含有溶液を調製さ
せるＡ工程、基体上に、調製された金属酸化物オリゴマ
ー―飽和有機化合物溶媒錯体含有溶液を付着させるＢ工
程、前記付着溶液中の飽和有機化合物溶媒の４０〜８０
％を除去させるＣ工程、及び基体を熱処理させて、基体
上に金属酸化物薄膜を形成させるＤ工程からなる。The method for forming a metal oxide thin film of the present invention comprises the step A of preparing a solution containing a metal oxide oligomer-saturated organic compound solvent complex from a solution containing a metal salt and a saturated organic compound solvent. Metal oxide oligomer-Step B of depositing a saturated organic compound solvent complex-containing solution, 40 to 80 of the saturated organic compound solvent in the depositing solution
%, And a step D in which the substrate is heat-treated to form a metal oxide thin film on the substrate.
【００１５】まず、金属塩及び飽和有機化合物溶媒を含
む溶液から金属酸化物オリゴマー―飽和有機化合物溶媒
錯体含有溶液を調製させるＡ工程について、以下に説明
する。First, the step A for preparing a solution containing a metal oxide oligomer-saturated organic compound solvent complex from a solution containing a metal salt and a saturated organic compound solvent will be described below.
【００１６】Ａ工程としては、１）飽和有機化合物溶媒
に、所定量の金属塩を溶解または懸濁させ、ついで所定
量の水−アルコール混合溶液を添加させた後、加水分
解、脱水縮合反応させて、金属酸化物オリゴマー―飽和
有機化合物溶媒錯体含有溶液を調製する方法、２）予め
所定量の水を加えた飽和有機化合物溶媒に、所定量の金
属塩を溶解または懸濁させた後、加熱させて、金属水酸
化物−飽和有機化合物溶媒錯体と金属塩−飽和有機化合
物溶媒錯体との含有溶液を得、ついで所定量の水−アル
コール混合溶液を加えた後、加水分解、脱水縮合反応さ
せて、金属酸化物オリゴマー−飽和有機化合物溶媒錯体
含有溶液を調製する方法、３）所定量の金属塩、アルコ
ール及び塩基性有機化合物溶媒を加熱させて形成させた
金属アルコキシド配位錯体含有溶液に、所定量の飽和有
機化合物溶媒及び水−アルコール混合溶液を加えた後、
加水分解、脱水縮合反応させて、金属酸化物オリゴマー
―飽和有機化合物溶媒錯体含有溶液を調製する方法等が
あげられる。In step A, 1) a predetermined amount of metal salt is dissolved or suspended in a saturated organic compound solvent, and then a predetermined amount of water-alcohol mixed solution is added, followed by hydrolysis and dehydration condensation reaction. Then, a method for preparing a solution containing a metal oxide oligomer-saturated organic compound solvent complex, 2) dissolving or suspending a predetermined amount of a metal salt in a saturated organic compound solvent to which a predetermined amount of water has been added in advance, and then heating. Then, a solution containing the metal hydroxide-saturated organic compound solvent complex and the metal salt-saturated organic compound solvent complex is obtained, and then a predetermined amount of water-alcohol mixed solution is added, followed by hydrolysis and dehydration condensation reaction. To prepare a solution containing a metal oxide oligomer-saturated organic compound solvent complex, 3) a metal alkoxide compound formed by heating a predetermined amount of a metal salt, alcohol and basic organic compound solvent. The complex-containing solution, saturated organic compound solvent and water at a predetermined amount - after adding an alcohol mixture,
Examples thereof include a method of preparing a solution containing a metal oxide oligomer-saturated organic compound solvent complex by carrying out hydrolysis and dehydration condensation reaction.
【００１７】作業性を考慮すると、飽和有機化合物溶媒
に、所定量の金属塩を溶解または懸濁させ、ついで所定
量の水−アルコール混合溶液を添加させた後、加水分
解、脱水縮合反応させて、金属酸化物オリゴマー―飽和
有機化合物溶媒錯体含有溶液を調製する方法が、好まし
い。Considering workability, a predetermined amount of metal salt is dissolved or suspended in a saturated organic compound solvent, and then a predetermined amount of water-alcohol mixed solution is added, followed by hydrolysis and dehydration condensation reaction. The method of preparing the metal oxide oligomer-saturated organic compound solvent complex-containing solution is preferable.
【００１８】本発明に用いられる金属塩としては、Ｍ
ｇ、Ａｌ、Ｓｉ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｍｎ、Ｆｅ、
Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｃｒ、Ｓｒ、
Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｉｎ、Ｓｎ、Ｓｂ、Ｃｓ、Ｂ
ａ、Ｔａ、Ｗ、Ｒｕ、Ｏｓ、Ｉｒ、Ｐｂ、Ｂｉ、Ｌａ、
Ｃｅ、Ｇｄ等のアルコキシド、有機酸塩、無機塩等があ
げられ、これらの少なくとも１種が用いられる。The metal salt used in the present invention is M
g, Al, Si, Ca, Sc, Ti, V, Mn, Fe,
Co, Ni, Cu, Zn, Ga, Ge, Cr, Sr,
Y, Zr, Nb, Mo, In, Sn, Sb, Cs, B
a, Ta, W, Ru, Os, Ir, Pb, Bi, La,
Examples thereof include alkoxides such as Ce and Gd, organic acid salts, and inorganic salts, and at least one of these is used.
【００１９】上記アルコキシドとしては、エトキシド、
ｎ―プロポキシド、ｉｓｏ−プロポキシド、ｎ―ブトキ
シド、ｉｓｏ−ブトキシド、ｓｅｃ−ブトキシド、ｔｅ
ｒｔ―ブトキシド等があげられ、有機酸塩としては、フ
ェノール塩、カルボン酸塩、１，３―ジケトン型塩等が
あげられ、無機塩としては、塩化物塩、硫酸塩及び硝酸
塩等があげられる。As the alkoxide, ethoxide,
n-propoxide, iso-propoxide, n-butoxide, iso-butoxide, sec-butoxide, te
Examples of the organic acid salt include phenol salt, carboxylate salt, and 1,3-diketone type salt, and examples of the inorganic salt include chloride salt, sulfate salt, nitrate salt, and the like. .
【００２０】本発明に用いられる飽和化合物溶媒として
は、脂肪族飽和炭化水素または脂環式飽和炭化水素、ハ
ロゲン化飽和炭化水素、ジアルキルエーテル類、ヘテロ
環式脂肪族飽和炭化水素及び炭素数４以上の飽和アルコ
ール等あげられ、少なくとも１種が用いられる。The saturated compound solvent used in the present invention includes aliphatic saturated hydrocarbons or alicyclic saturated hydrocarbons, halogenated saturated hydrocarbons, dialkyl ethers, heterocyclic aliphatic saturated hydrocarbons and carbon atoms of 4 or more. And the like, and at least one kind is used.
【００２１】脂肪族飽和炭化水素としては、へキサン、
ペンタン、オクタン、並びにへキサン及びペンタンの混
合物である石油エーテル等があげられ、脂環式飽和炭化
水素としては、シクロへキサン、メチルシクロへキサン
等があげられ、ハロゲン化飽和炭化水素としては、四塩
化炭素、クロロフォルム及び四フッ化炭素等があげら
れ、ジアルキルエーテル類としては、ジエチルエーテ
ル、ジブチルエーテルあげられ、、ヘテロ環式脂肪族炭
化水素としては、ジオキサン、テトラヒドロフラン、ピ
ペラジン、Ｎ―メチルピペラジンがあげられ炭素数４以
上の飽和アルコールとしては、ｎ―ブタノール、ｎ―ア
ミルアルコール、シクロへキサノール等があげられる。
さらに、上記以外の飽和有機化合物溶媒として、ジエチ
ルメルカプタン(沸点３７℃）等があげられる。As the saturated aliphatic hydrocarbon, hexane,
Examples include pentane, octane, and petroleum ether that is a mixture of hexane and pentane.Examples of alicyclic saturated hydrocarbons include cyclohexane and methylcyclohexane. Carbon chloride, chloroform, carbon tetrafluoride, and the like, dialkyl ethers include diethyl ether and dibutyl ether, and heterocyclic aliphatic hydrocarbons include dioxane, tetrahydrofuran, piperazine, and N-methylpiperazine. Examples of the saturated alcohol having 4 or more carbon atoms include n-butanol, n-amyl alcohol and cyclohexanol.
Furthermore, examples of the saturated organic compound solvent other than the above include diethyl mercaptan (boiling point 37 ° C.) and the like.
【００２２】本発明に用いられる飽和有機化合物溶媒
は、常温で液状ものが作業性の面から好ましく、また、
後工程であるＣ工程において、比較的容易に除去できる
ものが好ましい。The saturated organic compound solvent used in the present invention is preferably liquid at room temperature from the viewpoint of workability.
In the subsequent step C, those which can be removed relatively easily are preferable.
【００２３】また、本発明に用いられる飽和有機化合物
溶媒は、全量に対して２分の１未満の不飽和有機化合物
溶媒を含んでいても差支えない。The saturated organic compound solvent used in the present invention may contain less than ½ of the total amount of the unsaturated organic compound solvent.
【００２４】加水分解、脱水縮合反応において、飽和有
機化合物溶媒は、金属イオンを囲むように配置される。
上記飽和有機化合物溶媒は、疎水性が高く、水による金
属塩への攻撃を抑制し、かつ飽和有機化合物溶媒中への
水の溶解度も極めて小さいので、加水分解反応が遅くな
り、均質なネットワークを有する金属酸化物オリゴマー
を形成することができる。なお、加水分解、脱水縮合反
応は、大気中、加圧下いずれで行ってもよい。In the hydrolysis and dehydration condensation reaction, the saturated organic compound solvent is arranged so as to surround the metal ion.
The above-mentioned saturated organic compound solvent has high hydrophobicity, suppresses the attack of the metal salt by water, and since the solubility of water in the saturated organic compound solvent is also extremely small, the hydrolysis reaction is delayed and a homogeneous network is formed. A metal oxide oligomer having can be formed. The hydrolysis and dehydration condensation reaction may be performed in the atmosphere or under pressure.
【００２５】以下、飽和有機化合物溶媒に、所定量の金
属塩を溶解または懸濁させ、ついで所定量の水−アルコ
ール混合溶液を添加させた後、加水分解、脱水縮合反応
させて、金属酸化物オリゴマー―飽和有機化合物溶媒錯
体含有溶液を調製する場合について、さらに詳細に説明
する。Hereinafter, a predetermined amount of a metal salt is dissolved or suspended in a saturated organic compound solvent, and then a predetermined amount of a water-alcohol mixed solution is added, followed by hydrolysis and dehydration condensation reaction to obtain a metal oxide. The case of preparing a solution containing an oligomer-saturated organic compound solvent complex will be described in more detail.
【００２６】まず、飽和有機化合物溶媒に、金属イオン
濃度が０．０１〜３モル／Ｌとなる量の金属塩を溶解ま
たは懸濁させる。ついで、温度０〜１００℃で、金属イ
オン１モルに対して水０．１〜３モルとなる量の水濃度
０．０４６〜９．２モル／Ｌの水―アルコール混合溶液
を滴下させた後、温度０〜２００℃で１〜２４時間、加
水分解、脱水縮合反応させて、金属酸化物オリゴマー−
飽和有機化合物溶媒錯体含有溶液を形成させる。さら
に、適宜濃縮、希釈により、金属イオン濃度として０．
０１〜５モル／Ｌの金属酸化物オリゴマー−飽和有機化
合物溶媒錯体含有溶液が調製される。First, an amount of a metal salt having a metal ion concentration of 0.01 to 3 mol / L is dissolved or suspended in a saturated organic compound solvent. Then, at a temperature of 0 to 100 ° C., a water-alcohol mixed solution having a water concentration of 0.046 to 9.2 mol / L in an amount of 0.1 to 3 mol of water with respect to 1 mol of metal ion was dropped. At a temperature of 0 to 200 ° C. for 1 to 24 hours for hydrolysis and dehydration condensation reaction to obtain a metal oxide oligomer-
A solution containing a saturated organic compound solvent complex is formed. Further, by appropriately concentrating and diluting the metal ion concentration,
A solution containing 01 to 5 mol / L metal oxide oligomer-saturated organic compound solvent complex is prepared.
【００２７】金属イオン濃度が０．０１モル／Ｌ未満の
場合、金属塩間距離が大き過ぎて、金属酸化物オリゴマ
ーがうまく形成されず、また３モル／Ｌを超の場合、金
属塩間距離が小さ過ぎて、金属酸化物オリゴマーの三次
元成長が抑制できず、不都合である。When the metal ion concentration is less than 0.01 mol / L, the distance between metal salts is too large to form a metal oxide oligomer well, and when it exceeds 3 mol / L, the distance between metal salts is large. Is too small to suppress the three-dimensional growth of the metal oxide oligomer, which is inconvenient.
【００２８】水−アルコール混合溶液のアルコールとし
ては、炭素数１〜１０のアルコールから選ばれる少なく
とも１種であり、例えば、エチルアルコール、ｎ―プロ
ピルアルコール、ｉｓｏ―プロピルアルコール、ｎ―ブ
チルアルコール、ｉｓｏ―ブチルアルコール、ｔｅｒｔ
―ブチルアルコール、アミルアルコール、ヘキシルアル
コール、オクチルアルコール、ノニルアルコール、デシ
ルアルコール、グリセリン、エチレングリコール等があ
げられる。The alcohol of the water-alcohol mixed solution is at least one selected from alcohols having 1 to 10 carbon atoms, and examples thereof include ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol and iso. -Butyl alcohol, tert
-Butyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, glycerin, ethylene glycol and the like.
【００２９】水−アルコール混合溶液中のアルコール
は、水の活量を制御して、加水分解反応を抑制し、ゆっ
くりと反応させる役割を有し、また水は、加水分解の反
応速度に大きな影響を及ぼす。The alcohol in the water-alcohol mixed solution has a role of controlling the activity of water to suppress the hydrolysis reaction and causing a slow reaction, and water has a great influence on the reaction rate of hydrolysis. Exert.
【００３０】水濃度が０．０４６モル未満／Ｌの場合、
形成される金属酸化物オリゴマーの配列には乱れはない
が、加水分解反応が遅すぎて、効率が低下し、経済性が
劣り、実用的でない。また９．６モル超／Ｌの場合、加
水分解が急激に進行し、微粒子状金属水和酸化物の凝集
体が形成され、好ましくない。When the water concentration is less than 0.046 mol / L,
The arrangement of the formed metal oxide oligomer is not disturbed, but the hydrolysis reaction is too slow, the efficiency is lowered, the economical efficiency is deteriorated, and it is not practical. On the other hand, if the amount exceeds 9.6 mol / L, hydrolysis rapidly progresses, and aggregates of finely divided metal hydrated oxides are formed, which is not preferable.
【００３１】金属塩を溶解または懸濁させた飽和有機化
合物溶媒に添加される水−アルコール混合溶液は、金属
塩１モルに対して水０．１〜３モルとなる量である。水
が０．１モル未満の場合、加水分解、脱水縮合反応が遅
すぎて、効率が低下し、経済性に劣り、実用的でない。
また３モル超の場合、加水分解が急激に進行し、金属酸
化物オリゴマーの三次元成長が抑制できず、不都合であ
る。The water-alcohol mixed solution added to the saturated organic compound solvent in which the metal salt is dissolved or suspended is in an amount of 0.1 to 3 mol of water with respect to 1 mol of the metal salt. If the amount of water is less than 0.1 mol, the hydrolysis and dehydration condensation reaction are too slow, resulting in poor efficiency and poor economic efficiency, which is not practical.
On the other hand, if it exceeds 3 moles, the hydrolysis rapidly progresses and the three-dimensional growth of the metal oxide oligomer cannot be suppressed, which is inconvenient.
【００３２】水―アルコール混合溶液の添加温度が０℃
未満の場合、加水分解、脱水縮合反応が遅くなり、また
１００℃超の場合、急激な反応が部分的に起こり、形成
される金属酸化物オリゴマー−飽和有機化合物溶媒錯体
が不均質になり易く、不都合である。The addition temperature of the water-alcohol mixed solution is 0 ° C.
If it is less than 1, hydrolysis and dehydration condensation reaction become slow, and if it exceeds 100 ° C, a rapid reaction partially occurs, and the formed metal oxide oligomer-saturated organic compound solvent complex tends to be heterogeneous. It is inconvenient.
【００３３】また、加水分解、脱水縮合反応温度が０℃
未満の場合、反応が十分進行せず、また２００℃超の場
合、反応制御が困難となり、不都合である。Further, the hydrolysis and dehydration condensation reaction temperature is 0 ° C.
If it is less than 200 ° C., the reaction does not proceed sufficiently, and if it exceeds 200 ° C., it becomes difficult to control the reaction, which is inconvenient.
【００３４】調製された金属酸化物オリゴマー―飽和有
機化合物溶媒錯体含有溶液は、冷暗所に保存した場合、
１年経過後でも安定であり、経時安定性に優れている。The prepared metal oxide oligomer-saturated organic compound solvent complex-containing solution, when stored in a cool and dark place,
It is stable even after 1 year and has excellent stability over time.
【００３５】つぎに、基体上に、前のＡ工程で調製され
た金属酸化物オリゴマー―飽和有機化合物溶媒錯体含有
溶液を、付着させるＢ工程について、以下に説明する。Next, the step B for adhering the metal oxide oligomer-saturated organic compound solvent complex-containing solution prepared in the step A on the substrate will be described below.
【００３６】大気中または溶媒飽和蒸気中で、基体上
に、Ａ工程で調製された金属イオン濃度として０．０１
〜５モル／Ｌの金属酸化物オリゴマー−飽和有機化合物
溶媒錯体含有溶液を付着させる。The concentration of the metal ion prepared in the step A was 0.01 on the substrate in the atmosphere or in the solvent saturated vapor.
~ 5 mol / L metal oxide oligomer-saturated organic compound solvent complex containing solution is deposited.
【００３７】本発明に用いられる基体は、特に限定され
ず、目的や用途に応じて、材質、形状及び大きさが適宜
選択される。材質としては、例えば、シリコンウエハの
ような単結晶、多結晶、ガラス、金属、セラミックス、
高分子等があげられ、形状としては、例えば、板状、小
断片、ビーズ状球体、リング状体、筒状、繊維状及び鎖
状体等があげられる。The substrate used in the present invention is not particularly limited, and the material, shape and size are appropriately selected according to the purpose and application. As the material, for example, single crystal such as silicon wafer, polycrystal, glass, metal, ceramics,
Examples thereof include polymers and the like, and examples of the shape include a plate, a small piece, a bead-shaped sphere, a ring-shaped body, a tubular shape, a fibrous shape and a chain-shaped body.
【００３８】基体上への金属酸化物オリゴマー−飽和有
機化合物溶媒錯体含有溶液の付着は、ハケ塗り、スプレ
ー塗布，スピンコート、ディップコート等により行われ
る。The metal oxide oligomer-saturated organic compound solvent complex-containing solution is deposited on the substrate by brush coating, spray coating, spin coating, dip coating or the like.
【００３９】溶媒飽和蒸気中での付着の場合、調製され
た前記溶液中の飽和有機化合物溶媒と同一溶媒、また、
前記溶液中に含まれる飽和有記化合物溶媒以外の他の飽
和有機化合物溶媒や、脂肪族炭化水素、脂環式炭化水
素、ヘテロ原子を含む脂環式炭化水素等の不飽和有機化
合物溶媒のいずれを用いてもよい。好ましくは、疎水性
を有する溶媒である。In the case of deposition in saturated solvent vapor, the same solvent as the saturated organic compound solvent in the solution prepared above,
Any of saturated organic compound solvents other than the saturated noteworthy compound solvent contained in the solution, and aliphatic hydrocarbons, alicyclic hydrocarbons, unsaturated organic compound solvents such as alicyclic hydrocarbons containing a hetero atom May be used. A solvent having hydrophobicity is preferable.
【００４０】本発明では、Ｂ工程での１回の付着操作に
より、通常、厚さ０．０１〜５μｍの金属酸化物薄膜が
形成される。この厚さは、主としてＡ工程で調製される
金属酸化物オリゴマー―飽和有機化合物溶媒錯体含有溶
液中の金属酸化物オリゴマーの濃度と塗布量に依存す
る。また、必要に応じ、複数回の付着操作により、より
厚い金属酸化物薄膜を形成させてもよい。In the present invention, a metal oxide thin film having a thickness of 0.01 to 5 μm is usually formed by one deposition operation in the step B. This thickness mainly depends on the concentration and the coating amount of the metal oxide oligomer in the solution containing the metal oxide oligomer-saturated organic compound solvent complex prepared in the step A. Further, if necessary, a thicker metal oxide thin film may be formed by a plurality of deposition operations.
【００４１】つぎに、基体上に付着させた金属酸化物オ
リゴマー−飽和有機溶媒錯体含有溶液中の飽和有機化合
物溶媒の４０〜８０％を除去させるＣ工程について、以
下に説明する。Next, the C step for removing 40 to 80% of the saturated organic compound solvent in the solution containing the metal oxide oligomer-saturated organic solvent complex deposited on the substrate will be described below.
【００４２】前のＢ工程により、金属酸化物オリゴマー
−飽和有機溶媒錯体含有溶液を付着させた基体に、基体
成分と金属酸化物オリゴマー間の拡散、混合を実質的に
生じさせない手段を用いて、上記付着溶液中の飽和有機
化合物溶媒の４０〜８０％を除去させ、ついで、必要に
応じて乾燥させる。Using the means which does not substantially cause the diffusion and mixing between the substrate component and the metal oxide oligomer on the substrate to which the solution containing the metal oxide oligomer-saturated organic solvent complex is attached by the step B, 40-80% of the saturated organic compound solvent in the deposition solution is removed and then dried if necessary.
【００４３】飽和有機化合物溶媒の除去は、１）不活性
ガス中または減圧下で、基体金属と金属酸化物オリゴマ
ー間の拡散、混合を生じさせない温度で、基体を加熱さ
せる、２）減圧下で、基体を加熱なしに保持させる、
３）溶媒飽和蒸気中、密閉容器中の基体に、赤外線ラン
プ等により赤外線及び／または紫外線ランプにより紫外
線を間接照射させる、４）基体に、赤外線ランプ等によ
り赤外線及び／または紫外線ランプにより紫外線を直接
照射させる等、基体成分と金属酸化物オリゴマー間の拡
散、混合を実質的に生じさせない手段であればよい。Removal of the saturated organic compound solvent is carried out by 1) heating the substrate in an inert gas or under reduced pressure at a temperature at which diffusion and mixing between the substrate metal and the metal oxide oligomer do not occur, and 2) under reduced pressure. , Holding the substrate without heating,
3) Indirectly irradiate the substrate in a closed container in a solvent-saturated vapor with ultraviolet rays by an infrared lamp and / or an ultraviolet lamp. 4) Directly irradiate the substrate with infrared rays and / or an ultraviolet lamp by an infrared lamp. Any means such as irradiation may be used as long as it does not substantially cause diffusion or mixing between the substrate component and the metal oxide oligomer.
【００４４】上記Ｃ工程で除去される飽和有機化合物溶
媒は、２０％以上であり、好ましくは、４０〜８０％で
ある。The saturated organic compound solvent removed in the step C is 20% or more, preferably 40 to 80%.
【００４５】つぎに、基体上に付着させた金属酸化物オ
リゴマー−飽和有機溶媒錯体含有溶液中の飽和有機化合
物溶媒の４０〜８０％を除去させた基体を、熱処理させ
るＤ工程について、以下に説明する。Next, the step D of heat treating the substrate from which 40 to 80% of the saturated organic compound solvent in the solution containing the metal oxide oligomer-saturated organic solvent complex deposited on the substrate has been removed will be described below. To do.
【００４６】前のＣ工程により、基体上に付着させた金
属酸化物オリゴマー−飽和有機溶媒錯体含有溶液中の飽
和有機化合物溶媒の４０〜８０％を除去させた基体を、
電気炉等を用いて、温度１００〜１３００℃で１〜２４
時間熱処理させて、基体上に、金属酸化物のゲル状薄膜
を結合化させた金属酸化物薄膜を形成させる。The substrate from which 40 to 80% of the saturated organic compound solvent in the metal oxide oligomer-saturated organic solvent complex-containing solution deposited on the substrate by the previous Step C was removed ,
1-24 at a temperature of 100-1300 ° C using an electric furnace, etc.
Heat treatment is performed for a period of time to form a metal oxide thin film in which a gel-like thin film of metal oxide is bonded on the substrate.
【００４７】熱処理温度が１００℃未満の場合、金属酸
化物薄膜の結晶化が困難であり、また１３００℃超の場
合、目的とする結晶以外の結晶が形成される上、経済性
にも劣り、好ましくない。When the heat treatment temperature is less than 100 ° C., it is difficult to crystallize the metal oxide thin film, and when it exceeds 1300 ° C., crystals other than the intended crystal are formed and the economy is poor. Not preferable.
【００４８】本発明において、２種以上の金属からなる
複合金属酸化物薄膜を形成させる場合には、目的とする
２種以上の金属塩を出発原料とし、加熱分解、脱水縮合
反応させて調製された、２種以上の金属からなる金属酸
化物オリゴマー―飽和有機化合物溶媒錯体含有溶液を用
いる。In the present invention, when a composite metal oxide thin film composed of two or more kinds of metals is formed, it is prepared by subjecting two or more kinds of desired metal salts as a starting material to thermal decomposition and dehydration condensation reaction. Further, a solution containing a metal oxide oligomer-saturated organic compound solvent complex containing two or more metals is used.
【００４９】上記複合金属酸化物としては、ＰｂＺｒＯ
３、ＰｂＴｉＯ３、ＢａＴｉＯ３、ＳｒＴｉＯ３、Ｓｒ
ＲｕＴｉＯ３、ＹＭｎＯ３、ＣｕＦｅ２Ｏ４、ＬｉＮｂ
Ｏ３、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ３（以下、「ＰＺＴ」と略
記）、Ｉｎ４Ｓｎ３Ｏ１２、（Ｂａ，Ｓｒ）ＴｉＯ３、
ＳｒＢｉ２Ｔａ２Ｏ９、（Ｐｂ，Ｌａ）ＴｉＯ３、Ｂｉ
４Ｔｉ３Ｏ１２、（Ｌａ，Ｌｉ）ＴｉＯ３、（Ｌａ，Ｌ
ｉ）ＺｒＯ３、ＣａＢｉ２Ｔａ２Ｏ９、（Ｐｂ，Ｌａ）
（Ｚｒ，Ｔｉ）Ｏ３等があげられる。As the above-mentioned composite metal oxide, PbZrO
3 , PbTiO 3 , BaTiO 3 , SrTiO 3 , Sr
RuTiO 3 , YMnO 3 , CuFe 2 O 4 , LiNb
O 3 , Pb (Zr, Ti) O 3 (hereinafter abbreviated as “PZT”), In 4 Sn 3 O 12 , (Ba, Sr) TiO 3,
SrBi 2 Ta 2 O 9 , (Pb, La) TiO 3 , Bi
4 Ti 3 O 12 , (La, Li) TiO 3 , (La, L
i) ZrO 3 , CaBi 2 Ta 2 O 9 , (Pb, La)
Examples thereof include (Zr, Ti) O 3 .
【００５０】本発明では、基体上に付着させた金属酸化
物オリゴマー−飽和有機溶媒錯体含有溶液中の飽和有機
化合物溶媒の４０〜８０％を除去させるＣ工程により、
基体の成分と金属酸化物オリゴマー間での拡散、混合が
防止され、均質でクラック等のほとんどない金属酸化物
薄膜が形成できる。In the present invention, by the step C for removing 40 to 80% of the saturated organic compound solvent in the solution containing the metal oxide oligomer-saturated organic solvent complex deposited on the substrate,
Diffusion and mixing between the components of the substrate and the metal oxide oligomer are prevented, and a homogeneous metal oxide thin film having almost no cracks can be formed.
【００５１】本発明の金属酸化物薄膜を形成させた基体
は、光学材料、光電変換材料、電子材料、保護膜等、例
えば、コンデンサー、ピエゾ素子、ＳＡＷフィルター、
メモリー、超伝導材料等として用いられる。The substrate on which the metal oxide thin film of the present invention is formed is an optical material, a photoelectric conversion material, an electronic material, a protective film or the like, for example, a capacitor, a piezo element, a SAW filter,
Used as memory, superconducting material, etc.
【００５２】[0052]
【発明の実施の形態】発明の実施の形態を、以下、実施
例に基き説明する。なお、本発明は、実施例によりなん
ら限定されない。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below based on Examples. The present invention is not limited to the examples.
【００５３】実施例１
飽和有機化合物溶媒であるヘキサンに、チタンイオン濃
度として１モル／Ｌとなる量の、金属塩であるチタン―
ｎ―ブトキシドを溶解させ、温度０℃での攪拌下、チタ
ンイオン１モルに対して水１．６モルとなる量の、水濃
度４．０モル／Ｌの水―ブタノール混合溶液を滴下さ
せ、ついで温度０℃で１時間攪拌させた後、温度８０〜
９０℃で１０時間、加水分解、脱水縮合反応させて、チ
タン酸化物オリゴマー−ヘキサン錯体を形成させ、さら
にエバポレーターを用いて濃縮させ、ついでチタンイオ
ン濃度が１モル／Ｌとなるように希釈させて、チタン酸
化物オリゴマー−ヘキサン錯体含有溶液を調製した。Example 1 Titanium as a metal salt was added to hexane as a saturated organic compound solvent in an amount such that the titanium ion concentration was 1 mol / L.
Dissolve n-butoxide, and add under stirring at a temperature of 0 ° C., a water-butanol mixed solution having a water concentration of 4.0 mol / L in an amount of 1.6 mol of water to 1 mol of titanium ion, Then, after stirring for 1 hour at a temperature of 0 ° C., a temperature of 80-
Hydrolysis and dehydration condensation reaction are performed at 90 ° C. for 10 hours to form a titanium oxide oligomer-hexane complex, which is further concentrated using an evaporator, and then diluted so that the titanium ion concentration is 1 mol / L. A titanium oxide oligomer-hexane complex-containing solution was prepared.
【００５４】平均粒径１μｍのアルミナで研磨させたチ
タン基体を、脱脂、洗浄させた後、ヘキサン飽和蒸気
中、先に調製したチタン酸化物オリゴマー−ヘキサン錯
体含有溶液中に５分間浸漬させた後、ステッピングモー
ターを用いて、０．１５ｍｍ／秒の速度で引き上げ、チ
タン基体上に、チタン酸化物オリゴマー−ヘキサン錯体
含有溶液を付着させた。After degreasing and washing a titanium substrate polished with alumina having an average particle size of 1 μm, the titanium substrate was immersed in hexane saturated vapor for 5 minutes in the previously prepared titanium oxide oligomer-hexane complex-containing solution. Then, the stepping motor was used to pull up at a rate of 0.15 mm / sec to deposit the titanium oxide oligomer-hexane complex-containing solution on the titanium substrate.
【００５５】次に、チタン酸化物オリゴマー−ヘキサン
錯体含有溶液を付着させたチタン基体を、ガラス容器に
入れた後、チタン基体から約２０ｃｍ離したガラス容器
外の赤外線ランプを用いて、ヘキサン飽和蒸気中、１５
分間、間接照射させて、前記付着溶液中のヘキサンの約
４０％を除去させた。さらに温度１２０℃で３０分間乾
燥させた。Next, the titanium substrate to which the titanium oxide oligomer-hexane complex-containing solution was attached was placed in a glass container, and then hexane saturated vapor was used by using an infrared lamp outside the glass container and separated from the titanium substrate by about 20 cm. Medium, 15
Indirect irradiation was carried out for a minute to remove about 40% of the hexane in the deposition solution. Further, it was dried at a temperature of 120 ° C. for 30 minutes.
【００５６】ついで、電気炉中、温度５８０℃で１時間
熱処理させた後、室温まで自然放冷させて、チタン基体
上にチタン酸化物薄膜を形成させた。Next, after heat treatment in an electric furnace at a temperature of 580 ° C. for 1 hour, the mixture was naturally cooled to room temperature to form a titanium oxide thin film on the titanium substrate.
【００５７】走査型電子顕微鏡（以下、「ＳＥＭ」と略
記）を用いて測定したチタン酸化物薄膜の厚さは、約
０．６μｍであった。図１に示したＳＥＭ写真によれ
ば、均質でクラックのほとんどないチタン酸化物薄膜で
あった。The thickness of the titanium oxide thin film measured with a scanning electron microscope (hereinafter abbreviated as "SEM") was about 0.6 μm. According to the SEM photograph shown in FIG. 1, the titanium oxide thin film was homogeneous and had almost no cracks.
【００５８】実施例２
実施例１において、ヘキサンに、チタンイオン濃度とし
て０．５モル／Ｌとなる量のチタン―ｎ―ブトキシドを
溶解させ、温度５℃での攪拌下、チタンイオン１モルに
対して水０．２モルとなる量の、水濃度２．３モル／Ｌ
の水―ブタノール混合溶液を滴下させた後、温度５℃で
１時間攪拌させたこと、また、希釈により、チタンイオ
ン濃度が０．５モルのチタン酸化物オリゴマー−ヘキサ
ン錯体含有溶液を調製したこと以外は、実施例１と同様
にして、チタン基体上にチタン酸化物薄膜を形成させ
た。なお、付着溶液中のヘキサンの除去率は、約４０％
であった。Example 2 In Example 1, titanium-n-butoxide was dissolved in hexane in an amount of 0.5 mol / L as a titanium ion concentration, and 1 mol of titanium ion was added under stirring at a temperature of 5 ° C. On the other hand, water concentration of 0.2 mol, water concentration 2.3 mol / L
Water-butanol mixed solution was added dropwise, and the mixture was stirred at a temperature of 5 ° C. for 1 hour, and a titanium oxide oligomer-hexane complex-containing solution having a titanium ion concentration of 0.5 mol was prepared by dilution. A titanium oxide thin film was formed on a titanium substrate in the same manner as in Example 1 except for the above. The removal rate of hexane in the deposition solution is about 40%.
Met.
【００５９】実施例１に準じて測定したチタン酸化物薄
膜の厚さは、約０．１μｍであった。ＳＥＭ写真によれ
ば、均質でクラックのないチタン酸化物薄膜であった。The thickness of the titanium oxide thin film measured according to Example 1 was about 0.1 μm. According to the SEM photograph, the titanium oxide thin film was homogeneous and had no cracks.
【００６０】実施例３
実施例１において、チタン基体から約２０ｃｍ離したガ
ラス容器外の赤外線ランプを用いて、ヘキサン飽和蒸気
中、１５分間、間接照射させた代りに、圧力１３３ｈＰ
ａの減圧下、温度４０〜６０℃で加熱させた以外は、実
施例１と同様にして、チタン基体上にチタン酸化物薄膜
を形成させた。付着溶液中のヘキサンの除去率は、約７
０％であった。Example 3 In Example 1, an infrared lamp outside the glass container, which was separated from the titanium substrate by about 20 cm, was used. Instead of indirect irradiation in hexane saturated vapor for 15 minutes, the pressure was 133 hP.
A titanium oxide thin film was formed on a titanium substrate in the same manner as in Example 1 except that the heating was performed at a temperature of 40 to 60 ° C. under the reduced pressure of a. The removal rate of hexane in the deposition solution is about 7
It was 0%.
【００６１】実施例１に準じて測定したチタン酸化物薄
膜の厚さは、約０．６μｍであった。ＳＥＭ写真によれ
ば、均質でクラックのないチタン酸化物被膜であった。The thickness of the titanium oxide thin film measured according to Example 1 was about 0.6 μm. According to the SEM photograph, the titanium oxide film was homogeneous and had no cracks.
【００６２】実施例４
実施例１において、飽和有機化合物溶媒であるヘキサン
をシクロヘキサンに代えた以外は、実施例１と同様にし
て、チタン基体上にチタン酸化物薄膜を形成させた。Example 4 A titanium oxide thin film was formed on a titanium substrate in the same manner as in Example 1, except that cyclohexane was used in place of hexane which was a saturated organic compound solvent.
【００６３】実施例１に準じて測定したチタン酸化物薄
膜の厚さは、約０．４μｍであった。ＳＥＭ写真によれ
ば、均質でクラックのないチタン酸化物薄膜であった。The thickness of the titanium oxide thin film measured according to Example 1 was about 0.4 μm. According to the SEM photograph, the titanium oxide thin film was homogeneous and had no cracks.
【００６４】実施例５
実施例１において、飽和有機化合物溶媒であるヘキサン
をジオキサンに代えた以外は、実施例１と同様にして、
チタン基体上にチタン酸化物薄膜を形成させた。Example 5 In the same manner as in Example 1 except that hexane, which is a saturated organic compound solvent, was replaced with dioxane,
A titanium oxide thin film was formed on a titanium substrate.
【００６５】実施例１に準じて測定したチタン酸化物薄
膜の厚さは、約０．５μｍであった。ＳＥＭ写真によれ
ば、均質でクラックのないチタン酸化物薄膜であった。The thickness of the titanium oxide thin film measured according to Example 1 was about 0.5 μm. According to the SEM photograph, the titanium oxide thin film was homogeneous and had no cracks.
【００６６】実施例６
実施例１において、飽和有機化合物溶媒であるヘキサン
をテトラヒドロフランに代えた以外は、実施例１と同様
にして、チタン基体上に金属酸化物薄膜を形成させた。Example 6 A metal oxide thin film was formed on a titanium substrate in the same manner as in Example 1 except that hexane which was a saturated organic compound solvent was replaced with tetrahydrofuran.
【００６７】実施例１に準じて測定したチタン酸化物薄
膜の厚さは、約０．５μｍであった。ＳＥＭ写真によれ
ば、均質でクラックのないチタン酸化物薄膜であった。The thickness of the titanium oxide thin film measured according to Example 1 was about 0.5 μm. According to the SEM photograph, the titanium oxide thin film was homogeneous and had no cracks.
【００６８】実施例７
実施例１において、飽和有機化合物溶媒であるヘキサン
をｎ−ブタノールに代えた以外は、実施例１と同様にし
て、チタン基体上に金属酸化物薄膜を形成させた。Example 7 A metal oxide thin film was formed on a titanium substrate in the same manner as in Example 1 except that n-butanol was used instead of hexane as a saturated organic compound solvent.
【００６９】実施例１に準じて測定したチタン酸化物薄
膜の厚さは、約０．４μｍであった。ＳＥＭ写真によれ
ば、均質でクラックのないチタン酸化物薄膜であった。The thickness of the titanium oxide thin film measured according to Example 1 was about 0.4 μm. According to the SEM photograph, the titanium oxide thin film was homogeneous and had no cracks.
【００７０】実施例８
実施例１において、金属塩であるチタン―ｎ―ブトキシ
ドをジルコニウム−ｎ−ブトキシドに代えた以外は、実
施例１と同様にして、チタン基体上にジルコニウム酸化
物薄膜を形成させた。付着溶液中のヘキサンの除去率
は、約４０％であった。Example 8 A zirconium oxide thin film was formed on a titanium substrate in the same manner as in Example 1 except that the metal salt titanium-n-butoxide was replaced with zirconium-n-butoxide. Let The removal rate of hexane in the deposition solution was about 40%.
【００７１】実施例１に準じて測定したジルコニウム酸
化物薄膜の厚さは、約０．３μｍであった。ＳＥＭ写真
によれば、均質でクラックのないジルコニウム酸化物薄
膜であった。The thickness of the zirconium oxide thin film measured according to Example 1 was about 0.3 μm. According to the SEM photograph, it was a homogeneous and crack-free zirconium oxide thin film.
【００７２】実施例９
実施例１で調製されたチタン酸化物オリゴマー−ヘキサ
ン錯体含有溶液を、脱脂、洗浄させた石英ガラス基体上
に、スピンコータを用いて塗布させ、石英ガラス基体か
ら２０ｃｍ離した紫外線ランプを用いて紫外線を１時
間、直接照射させた後、ついで、石英ガラス基体から２
０ｃｍ離した赤外線ランプを用いて赤外線を３０分間、
直接照射させ、付着溶液中のヘキサンを、１００％除去
させた。さらに、大気中、電気炉を用いて、温度１００
℃で１時間熱処理させて、チタン酸化物薄膜を形成させ
た。Example 9 The solution containing the titanium oxide oligomer-hexane complex prepared in Example 1 was applied onto a degreased and washed quartz glass substrate by using a spin coater, and ultraviolet rays separated by 20 cm from the quartz glass substrate. Directly irradiate ultraviolet rays for 1 hour using a lamp, and then from the quartz glass substrate,
Infrared rays are emitted for 30 minutes using an infrared lamp at a distance of 0 cm.
Direct irradiation was carried out to remove 100% of hexane in the attachment solution. Further, in the atmosphere, using an electric furnace, a temperature of 100
It heat-processed at 1 degreeC for 1 hour, and formed the titanium oxide thin film.
【００７３】形成されたチタン酸化物薄膜を、Ｘ線回折
装置を用いて分析した。Ｘ線回折パターン図により、酸
化チタンのアナターゼの結晶であることが確認された。The formed titanium oxide thin film was analyzed using an X-ray diffractometer. It was confirmed from the X-ray diffraction pattern that the crystals were anatase crystals of titanium oxide.
【００７４】実施例１０
実施例１で調製されたチタン酸化物オリゴマー−ヘキサ
ン錯体含有溶液に、チタンイオン１モルに対して１モル
になる量の酢酸バリウムを加え、温度８０〜９０℃で８
時間、加水分解、脱水縮合反応させた後、エバポレータ
ーを用いて濃縮させ、ついでチタン酸バリウム濃度が１
モル／Ｌとなるように希釈させて、チタン酸バリウムオ
リゴマー−ヘキサン錯体含有溶液を調製した。Example 10 Barium acetate was added to the titanium oxide oligomer-hexane complex-containing solution prepared in Example 1 in an amount of 1 mol per 1 mol of titanium ion, and the mixture was heated at a temperature of 80 to 90 ° C. for 8 hours.
After hydrolyzing and dehydration-condensation reaction for a period of time, the mixture was concentrated using an evaporator, and then the barium titanate concentration was adjusted to 1
The solution was diluted to be mol / L to prepare a barium titanate oligomer-hexane complex-containing solution.
【００７５】調製されたチタン酸バリウムオリゴマー−
ヘキサン錯体含有溶液を、脱脂、洗浄させた石英ガラス
上に、スピンコータを用いて塗布させ、石英ガラス基体
から約２０cｍ離した赤外線ランプを用いて、３０分
間、直接照射して、付着溶液中のヘキサンの一部を除去
させた後、さらに温度１２０℃で３０分間乾燥させた。
さらに、大気中、電気炉を用いて、温度７００℃で１時
間、熱処理させた後、室温まで自然冷却させ、石英ガラ
ス上にチタン酸バリウム薄膜を形成させた。Barium Titanate Oligomer Prepared
The hexane complex-containing solution was applied onto degreased and washed quartz glass using a spin coater, and was directly irradiated for 30 minutes with an infrared lamp that was about 20 cm away from the quartz glass substrate to give hexane in the deposition solution. After removing a part of it, it was further dried at a temperature of 120 ° C. for 30 minutes.
Furthermore, after heat-treating at a temperature of 700 ° C. for 1 hour in the air using an electric furnace, it was naturally cooled to room temperature to form a barium titanate thin film on the quartz glass.
【００７６】図２に示したＸ線回折パターン図により、
チタン酸バリウム薄膜が形成されていることが確認され
た。From the X-ray diffraction pattern diagram shown in FIG.
It was confirmed that a barium titanate thin film was formed.
【００７７】実施例１１
チタンイオンとして０．９６モルとなる量の、実施例１
で調製されたチタン酸化物オリゴマー−ヘキサン錯体溶
液と、ジルコニウムイオンとして１．０４モルとなる量
の、実施例９で調製されたジルコニウム酸化物オリゴマ
ー−ヘキサン錯体溶液とを混合させ、温度８０〜９０℃
で４時間、加水分解、脱水縮合反応させた。ついで、
〔チタンイオン＋ジルコニウムイオン〕の１モルに対し
て１モルとなる量の酢酸鉛を加え、温度８０〜９０℃で
８時間、加水分解、脱水縮合反応させた後、エバポレー
ターで濃縮させ、さらにＰＺＴ（チタン酸ジルコン酸
鉛）濃度が１モル／Ｌとなるように希釈させて、ＰＺＴ
オリゴマー−ヘキサン錯体含有溶液を調製した。以下、
実施例１１と同様にして、石英ガラス上にＰＺＴ薄膜を
形成させた。Example 11 Example 1 was used in an amount of 0.96 mol as titanium ion.
The titanium oxide oligomer-hexane complex solution prepared in Example 1 was mixed with the zirconium oxide oligomer-hexane complex solution prepared in Example 9 in an amount of 1.04 mol of zirconium ions, and the temperature was adjusted to 80 to 90. ℃
Then, hydrolysis and dehydration condensation reaction were carried out for 4 hours. Then,
After adding lead acetate in an amount of 1 mol to 1 mol of [titanium ion + zirconium ion], the mixture is hydrolyzed and dehydration-condensed at a temperature of 80 to 90 ° C. for 8 hours, then concentrated by an evaporator, and further PZT is added. (Lead zirconate titanate) Dilute to a concentration of 1 mol / L, then add PZT
An oligomer-hexane complex-containing solution was prepared. Less than,
In the same manner as in Example 11, a PZT thin film was formed on quartz glass.
【００７８】図３に示したＸ線回折パターン図により、
ＰＺＴ薄膜が形成されていることが確認された。From the X-ray diffraction pattern diagram shown in FIG.
It was confirmed that the PZT thin film was formed.
【００７９】比較例１
Ｔ．Ｙｏｋｏ，Ｋ．Ｋａｍｉｙａｍａ ａｎｄ Ｓ．Ｓ
ａｋｋａ．ＹｏｇｙｏＫｙｏｋａｉｓｈｉ．９５，１９
８７,ｐ．１５０に準じて、ゾルゲル法による金属酸化
物薄膜を形成させた。Comparative Example 1 T. Yoko, K .; Kamiya and S.K. S
akka. YokyoKyokai. 95, 19
87, p. According to 150, a metal oxide thin film was formed by the sol-gel method.
【００８０】室温下、チタンイソプロポキシド０．１モ
ル及び脱水エタノール０．４モルを混合、攪拌させた
後、温度０℃での攪拌下、脱水エタノール０．４モル、
水０．１モル及び塩酸０．００８モルの混合溶液を滴下
させた後、室温で加水分解反応させて、チタン酸化物ゾ
ルを調製した。調製されたチタン酸化物ゾルは、冷暗所
での保存下、２ヶ月経過後に、ゾル中のチタン酸化物微
粒子が凝集し、使用不能となった。At room temperature, 0.1 mol of titanium isopropoxide and 0.4 mol of dehydrated ethanol were mixed and stirred, and then 0.4 mol of dehydrated ethanol was stirred at a temperature of 0 ° C.
After a mixed solution of 0.1 mol of water and 0.008 mol of hydrochloric acid was dropped, a hydrolysis reaction was carried out at room temperature to prepare a titanium oxide sol. The prepared titanium oxide sol was unusable due to aggregation of titanium oxide fine particles in the sol after storage for 2 months in a cool and dark place.
【００８１】実施例１と同様のチタン基体を、先に調製
した酸化物ゾル中に浸漬させた後、ステッピングモータ
ーを用いて、０．１５ｍｍ／秒の速度で引き上げ、自然
乾燥させた。ついで、大気中、電気炉を用いて、温度５
８０℃で１時間熱処理させた後、室温になるまで自然放
冷させて、チタン基体上にチタン酸化物薄膜を形成させ
た。The same titanium substrate as in Example 1 was dipped in the oxide sol prepared above, then pulled up at a rate of 0.15 mm / sec using a stepping motor and naturally dried. Then, in the atmosphere, using an electric furnace, a temperature of 5
After heat treatment at 80 ° C. for 1 hour, the mixture was naturally cooled to room temperature to form a titanium oxide thin film on the titanium substrate.
【００８２】実施例１に準じて測定したチタン酸化物薄
膜の厚さは、約０．０７μｍであった。また、図４に示
したＳＥＭ写真によれば、チタン酸化物微粒子が分散し
たゾルにより形成されるチタン酸化物薄膜に特有の細か
いクラックが散在していた。The thickness of the titanium oxide thin film measured according to Example 1 was about 0.07 μm. Further, according to the SEM photograph shown in FIG. 4, fine cracks peculiar to the titanium oxide thin film formed by the sol in which the fine particles of titanium oxide were dispersed were scattered.
【００８３】比較例２
実施例１と同様のチタン基体を、実施例９と同様にして
調整されたジルコニウム酸化物オリゴマー−ヘキサン錯
体含有溶液中に、５分間浸漬させた後、ステッピングモ
ーターを用いて、０．１５ｍｍ／秒の速度で引き上げ
た。さらに、電気炉を用いて、温度５８０℃で１時間熱
処理させた後、室温になるまで自然放冷し、ジルコニウ
ム酸化物薄膜を形成させた。Comparative Example 2 A titanium substrate similar to that of Example 1 was immersed in a zirconium oxide oligomer-hexane complex-containing solution prepared in the same manner as in Example 5 for 5 minutes, and then a stepping motor was used. , 0.15 mm / sec. Furthermore, after heat-treating at a temperature of 580 ° C. for 1 hour using an electric furnace, the mixture was naturally cooled to room temperature to form a zirconium oxide thin film.
【００８４】電子線プローブＸ線マイクロアナリシスを
用いて、チタン基体とジルコニウム酸化物薄膜の断面を
観察したところ、チタン基体のチタンとジルコニウム酸
化物薄膜の酸化ジルコニウムとが相互に拡散し、両者の
界面付近には、混合層が形成されていた。The cross section of the titanium substrate and the zirconium oxide thin film was observed by electron beam probe X-ray microanalysis. As a result, titanium of the titanium substrate and zirconium oxide of the zirconium oxide thin film diffused to each other, and the interface between the two was formed. A mixed layer was formed in the vicinity.
【００８５】本発明では、基体の熱処理前に、基体上に
付着させた金属酸化物オリゴマー−飽和有機溶媒錯体含
有溶液中の飽和有機化合物溶媒の少なくとも一部を除去
させることにより、基体の成分と金属酸化物オリゴマー
間での拡散、混合が防止され、均質でクラック等のほと
んどない金属酸化物薄膜が形成できる。In the present invention, at least a part of the saturated organic compound solvent in the metal oxide oligomer-saturated organic solvent complex-containing solution deposited on the substrate is removed before the substrate is heat-treated, so that Diffusion and mixing between metal oxide oligomers are prevented, and a homogeneous metal oxide thin film with almost no cracks can be formed.
【００８６】本発明の金属酸化物薄膜を形成させた基体
は、光学材料、光電変換材料、電子材料、保護膜等、例
えば、コンデンサー、ピエゾ素子、ＳＡＷフィルター、
メモリー、超伝導材料等として用いられる。The substrate on which the metal oxide thin film of the present invention is formed includes optical materials, photoelectric conversion materials, electronic materials, protective films, etc., such as capacitors, piezo elements, SAW filters,
Used as memory, superconducting material, etc.
【図１】実施例１で形成させたチタン酸化物薄膜のＳＥ
Ｍ写真である。FIG. 1 SE of titanium oxide thin film formed in Example 1
It is an M photograph.
【図２】実施例１０で形成させた金属酸化物薄膜のＸ線
回折パターン図である。2 is an X-ray diffraction pattern diagram of the metal oxide thin film formed in Example 10. FIG.
【図３】実施例１１で形成させた金属酸化物薄膜のＸ線
回折パターン図である。3 is an X-ray diffraction pattern diagram of the metal oxide thin film formed in Example 11. FIG.
【図４】比較例１で形成されたチタン酸化物薄膜のＳＥ
Ｍ写真である。FIG. 4 SE of titanium oxide thin film formed in Comparative Example 1
It is an M photograph.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 久保田 一浩 群馬県渋川市半田2470番地 日本カーリ ット株式会社 研究開発センター内 (72)発明者 加藤 琢朗 群馬県渋川市半田2470番地 日本カーリ ット株式会社 研究開発センター内 (72)発明者 蓮覚寺 聖一 富山県富山市粟島１丁目８番27−110号 (56)参考文献 特開 昭63−255375（ＪＰ，Ａ) 特開 昭59−195504（ＪＰ，Ａ) 特開 昭57−200209（ＪＰ，Ａ) 特開 平11−222690（ＪＰ，Ａ) 特開 平10−219462（ＪＰ，Ａ) 特開 平７−268637（ＪＰ，Ａ) 特開 平７−11497（ＪＰ，Ａ) 特開 平６−191896（ＪＰ，Ａ) 特開 平５−28834（ＪＰ，Ａ) 特開 平４−306528（ＪＰ，Ａ) 特開 平３−232975（ＪＰ，Ａ) 特開 平２−47268（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 18/12 C01G 23/00 C01G 23/04 C01G 25/00 C01G 25/02 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Kazuhiro Kubota 2470 Handa, Shibukawa City, Gunma Japan Carlit Co., Ltd. Research and Development Center (72) Inventor Takuro Kato 2470 Handa, Shibukawa City, Gunma Prefecture Japan Carlit Co., Ltd. Company Research & Development Center (72) Inventor Renkakuji Seiichi 1-8-27-110 Awashima, Toyama City, Toyama Prefecture (56) Reference JP-A-63-255375 (JP, A) JP-A-59-195504 ( JP, A) JP 57-200209 (JP, A) JP 11-222690 (JP, A) JP 10-219462 (JP, A) JP 7-268637 (JP, A) JP Japanese Patent Laid-Open No. 7-11497 (JP, A) Japanese Patent Laid-Open No. 6-191896 (JP, A) Japanese Patent Laid-Open No. 5-28834 (JP, A) Japanese Patent Laid-Open No. 4-306528 (JP, A) Japanese Patent Laid-Open No. 3-232975 (JP , A) JP-A-2-47268 (JP, ) (58) investigated the field (Int.Cl. 7, DB name) C23C 18/12 C01G 23/00 C01G 23/04 C01G 25/00 C01G 25/02
Claims (14)
液から調製された金属酸化物オリゴマー―飽和有機化合
物溶媒錯体含有溶液を、基体上に付着させ、ついで前記
付着溶液中の飽和有機化合物溶媒の４０〜８０％を除去
させた後、さらに熱処理させることにより、基体上に金
属酸化物薄膜を形成させることを特徴とする金属酸化物
薄膜の形成方法。1. A metal oxide oligomer-saturated organic compound solvent complex-containing solution prepared from a solution containing a metal salt and a saturated organic compound solvent is deposited on a substrate, and then the saturated organic compound solvent in the deposition solution is added. A method for forming a metal oxide thin film, which comprises forming a metal oxide thin film on a substrate by further performing heat treatment after removing 40 to 80% .
液から金属酸化物オリゴマー―飽和有機化合物溶媒錯体
含有溶液を調製させるＡ工程、基体上に、先に調製され
た金属酸化物オリゴマー―飽和有機化合物溶媒錯体含有
溶液を付着させるＢ工程、前記付着溶液中の飽和有機化
合物溶媒の４０〜８０％を除去させるＣ工程、及び基体
を熱処理させて、金属酸化物薄膜を形成させるＤ工程か
らなることを特徴とする金属酸化物薄膜の形成方法。2. Process A for preparing a solution containing a metal oxide oligomer-saturated organic compound solvent complex from a solution containing a metal salt and a saturated organic compound solvent, the previously prepared metal oxide oligomer-saturated organic compound on a substrate. The method comprises a step B of depositing a compound solvent complex-containing solution, a step C of removing 40 to 80% of a saturated organic compound solvent in the deposit solution, and a step D of heat treating a substrate to form a metal oxide thin film. And a method for forming a metal oxide thin film.
と金属酸化物オリゴマー間の拡散、混合を生じさせない
温度で、基体を加熱させることにより行われることを特
徴とする請求項１または請求項２に記載の金属酸化物薄
膜の形成方法。3. The method according to claim 1, wherein the removal of the saturated organic compound solvent is carried out by heating the substrate at a temperature which does not cause diffusion or mixing between the substrate component and the metal oxide oligomer. 2. The method for forming a metal oxide thin film according to 2.
で、基体を保持させ、かつ基体成分と金属酸化物オリゴ
マー間の拡散、混合を生じさせずに行われることを特徴
とする請求項１または請求項２に記載の金属酸化物薄膜
の形成方法。4. The removal of the saturated organic compound solvent is carried out under reduced pressure while holding the substrate and without causing diffusion or mixing between the substrate component and the metal oxide oligomer. Alternatively, the method for forming the metal oxide thin film according to claim 2.
び／または紫外線を、基体に照射、かつ基体成分と金属
酸化物オリゴマー間の拡散、混合を生じさせずに行われ
ることを特徴とする請求項１または請求項２に記載の金
属酸化物薄膜の形成方法。5. The removal of the saturated organic compound solvent is carried out by irradiating the substrate with infrared rays and / or ultraviolet rays and without causing diffusion and mixing between the substrate component and the metal oxide oligomer. The method for forming a metal oxide thin film according to claim 1 or 2.
ｃ、Ｔｉ、Ｖ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、
Ｇａ、Ｇｅ、Ｃｒ、Ｓｒ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｉ
ｎ、Ｓｎ、Ｓｂ、Ｃｓ、Ｂａ、Ｔａ、Ｗ、Ｒｕ、Ｏｓ、
Ｉｒ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅ、Ｇｄのアルコキシド、
有機酸塩または無機酸塩からなる群から選ばれる少なく
とも１種である請求項１から請求項５のいずれか１項に
記載の金属酸化物薄膜の形成方法。6. The metal salt is Mg, Al, Si, Ca, S.
c, Ti, V, Mn, Fe, Co, Ni, Cu, Zn,
Ga, Ge, Cr, Sr, Y, Zr, Nb, Mo, I
n, Sn, Sb, Cs, Ba, Ta, W, Ru, Os,
Alkoxides of Ir, Pb, Bi, La, Ce, Gd,
The method for forming a metal oxide thin film according to claim 1, wherein the metal oxide thin film is at least one selected from the group consisting of organic acid salts and inorganic acid salts.
水素、脂環式飽和炭化水素、ハロゲン化飽和炭化水素、
ジアルキルエーテル類、ヘテロ環式飽和脂肪族炭化水
素、並びに炭素数４以上の飽和アルコールからなる群か
ら選ばれる少なくとも１種である請求項１から請求項６
のいずれか１項に記載の金属酸化物薄膜の形成方法。7. The saturated organic compound solvent is an aliphatic saturated hydrocarbon, an alicyclic saturated hydrocarbon, a halogenated saturated hydrocarbon,
7. At least one selected from the group consisting of dialkyl ethers, heterocyclic saturated aliphatic hydrocarbons, and saturated alcohols having 4 or more carbon atoms.
The method for forming a metal oxide thin film according to any one of 1.
ロヘキサン、石油エーテル、ジエチルエーテル、ジオキ
サン及びテトラヒドロフラン、ｎ−ブタノールからなる
群から選ばれる少なくとも１種である請求項７に記載の
金属酸化物薄膜の形成方法。8. The metal oxide thin film according to claim 7, wherein the saturated organic compound solvent is at least one selected from the group consisting of hexane, cyclohexane, petroleum ether, diethyl ether, dioxane, tetrahydrofuran and n-butanol. Forming method.
ることを特徴とする請求項１から請求項８のいずれか１
項に記載の金属酸化物薄膜の形成方法。9. The heat treatment temperature is 100 to 1300 ° C., in any one of claims 1 to 8.
Item 5. A method for forming a metal oxide thin film according to item.
物溶媒錯体含溶液が、金属塩を溶解させた飽和有機化合
物溶媒を含む溶液に、水―アルコール混合溶液を添加さ
せて調製されることを特徴とする請求項１から請求項９
のいずれか１項に記載の金属酸化物薄膜の形成方法。10. A solution containing a metal oxide oligomer-saturated organic compound solvent complex is prepared by adding a water-alcohol mixed solution to a solution containing a saturated organic compound solvent in which a metal salt is dissolved. Claims 1 to 9
The method for forming a metal oxide thin film according to any one of 1.
が、炭素数１〜１０のアルコールから選ばれる少なくと
も１種であり、かつ水濃度が、０．０４６〜９．６モル
／Ｌであることを特徴とする請求項１０に記載の金属酸
化物薄膜の形成方法。11. The alcohol of the water-alcohol mixed solution is at least one selected from alcohols having 1 to 10 carbon atoms, and the water concentration is 0.046 to 9.6 mol / L. The method for forming a metal oxide thin film according to claim 10.
度が、０．０１〜３モル／Ｌであり、かつ、水―アルコ
ール混合溶液の添加量が、金属イオン１モルに対して水
０．１〜３モルであることを特徴とする請求項１０また
は請求項１１に記載の金属酸化物薄膜の形成方法。12. The saturated organic compound solvent has a metal ion concentration of 0.01 to 3 mol / L, and the addition amount of the water-alcohol mixed solution is 0.1 mol of water to 1 mol of metal ion. The method for forming a metal oxide thin film according to claim 10 or 11, wherein the amount is -3 mol.
物溶媒含有溶液が、金属塩を溶解させた飽和有機化合物
溶媒を含む溶液に、温度０〜１００℃で水―アルコール
混合溶液を添加させ、さらに温度０〜２００℃で反応さ
せて調製されることを特徴とする請求項１０から請求項
１２のいずれか１項に記載の金属酸化物薄膜の形成方
法。13. The metal oxide oligomer-saturated organic compound solvent-containing solution is obtained by adding a water-alcohol mixed solution at a temperature of 0 to 100 ° C. to a solution containing a saturated organic compound solvent in which a metal salt is dissolved. The method for forming a metal oxide thin film according to any one of claims 10 to 12, wherein the method is prepared by reacting at 0 to 200 ° C.
項に記載の方法により形成されてなることを特徴とする
金属酸化物薄膜。14. The method according to any one of claims 1 to 13.
A metal oxide thin film formed by the method described in the item.
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| FR2882746B1 (en) * | 2005-03-01 | 2007-04-27 | Commissariat Energie Atomique | PROCESS FOR PREPARING A SOL-GEL SOLUTION AND USE THEREOF TO FORM A COATING FOR PROTECTING A METALLIC SURFACE SUBSTRATE |
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