JP3446461B2 - Composition for forming Ba1-xSrxTiyO3 thin film, method for forming Ba1-xSrxTiyO3 thin film, and method for manufacturing thin-film capacitor - Google Patents

Composition for forming Ba1-xSrxTiyO3 thin film, method for forming Ba1-xSrxTiyO3 thin film, and method for manufacturing thin-film capacitor

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Publication number
JP3446461B2
JP3446461B2 JP05932696A JP5932696A JP3446461B2 JP 3446461 B2 JP3446461 B2 JP 3446461B2 JP 05932696 A JP05932696 A JP 05932696A JP 5932696 A JP5932696 A JP 5932696A JP 3446461 B2 JP3446461 B2 JP 3446461B2
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Prior art keywords
thin film
forming
composition
substrate
dielectric
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JPH0952713A (en
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恵子 遠藤
政 米澤
勝実 小木
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、薄膜コンデンサ、キャ
パシタ等に用いられるＢａ１−ｘＳｒｘＴｉｙＯ３誘電
体薄膜形成用組成物、この組成物を用いたＢａ１−ｘＳ
ｒｘＴｉｙＯ３誘電体薄膜の形成方法及び薄膜コンデン
サの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Ba 1-x Sr x Ti y O 3 dielectric thin film forming composition used for thin film capacitors and capacitors, and a Ba 1-x S composition using this composition.
The method for producing a r x Ti y O 3 forming method and the thin film capacitor of the dielectric thin film.

【０００２】[0002]

【従来の技術】Ｂａ１−ｘＳｒｘＴｉｙＯ３誘電体薄膜
は高い誘電率を有することから、近年、ＳｉＯ２，Ｓｉ
Ｎｘに代わる半導体メモリのキャパシタとして、或いは
ＩＣ信号処理用の内蔵コンデンサとして注目されている
（例えば特開平３−２５７０２０号公報）。2. Description of the Related Art Since a Ba 1-x Sr x Ti y O 3 dielectric thin film has a high dielectric constant, in recent years, SiO 2 , Si
As a capacitor for a semiconductor memory that replaces N x , or as a built-in capacitor for IC signal processing, attention has been paid (for example, Japanese Patent Laid-Open No. 3-257020).

【０００３】このような薄膜の形成法として、ゾルーゲ
ル法は、種々の置換元素、添加物によって組成の変性が
可能である、低コストであるなどの利点を有することか
ら、近年研究が進められている（例えば特開平２−２７
０３１１号公報）。As a method of forming such a thin film, the sol-gel method has the advantages that the composition can be modified by various substitutional elements and additives and that the cost is low, and therefore research has been advanced in recent years. (For example, JP-A-2-27
No. 0311).

【０００４】ゾルーゲル法は、Ｂａ，Ｓｒ，Ｔｉ原料と
しての金属塩や金属アルコキシドを有機溶媒に混合して
基板上に塗布して結晶化させる方法である。Ｂａ１−ｘ
ＳｒｘＴｉｙＯ３系薄膜の成膜において、金属塩、金属
アルコキシドは有機溶媒への溶解度が高いので、通常、
塗布液を塗布した後、室温及び１５０℃で乾燥後、５０
０〜６００℃で１時間もしくは７５０℃以上の高温で１
分仮焼する。そして、膜厚を厚くするため、この塗布、
乾燥及び仮焼の操作を繰り返し、最後に６５０℃以上の
焼成温度で焼成して結晶化させる。なお、塗布液の出発
原料としては、Ｂａ，Ｓｒ，Ｔｉのすべての原料として
金属アルコキシドを用いる方法（M.N.Kamalasanan等、
J.Appl.Phys.74(9)、0021-8979(1993)）、Ｂａ，Ｓｒの
カルボン酸塩とＴｉのアルコキシドを用いる方法などが
ある（H.K.Chae等、Mat.Res.Soc.Symp.Proc.Vol.271.(1
992)）。The sol-gel method is a method in which a metal salt or a metal alkoxide as a raw material of Ba, Sr, and Ti is mixed with an organic solvent and applied on a substrate for crystallization. Ba 1-x
Since metal salts and metal alkoxides have high solubility in organic solvents in the formation of Sr x Ti y O 3 -based thin films, they are usually
After applying the coating solution, dry it at room temperature and 150 ° C, and
1 hour at 0-600 ° C or 1 hour at high temperature over 750 ° C
Calcination for minutes. Then, in order to increase the film thickness, this coating,
The operations of drying and calcination are repeated, and finally, firing is performed at a firing temperature of 650 ° C. or higher to crystallize. As a starting material for the coating liquid, a method using metal alkoxides as all the raw materials of Ba, Sr, and Ti (MN Kamalasanan et al.
J.Appl.Phys.74 (9), 0021-8979 (1993)), a method using a carboxylic acid salt of Ba and Sr and an alkoxide of Ti, and the like (HKChae et al., Mat.Res.Soc.Symp.Proc. Vol.271. (1
992)).

【０００５】従来の薄膜コンデンサには、基板上に下部
電極と誘電体薄膜と上部電極をこの順で積層してなる３
層積層タイプのものと、比抵抗の小さい基板を下部電極
として用いその上に誘電体薄膜と上部電極を積層してな
る２層積層タイプのものとがある。A conventional thin film capacitor is formed by laminating a lower electrode, a dielectric thin film and an upper electrode in this order on a substrate.
There are a layer laminated type and a two layer laminated type in which a substrate having a small specific resistance is used as a lower electrode and a dielectric thin film and an upper electrode are laminated thereon.

【０００６】[0006]

【発明が解決しようとする課題】近年、電子回路の高密
度化、多機能化に伴い、三次元構造による基板の多層配
線化、かつその製造工程の簡略化が要求されている。In recent years, with the increase in density and multifunction of electronic circuits, there is a demand for multilayer wiring of a substrate having a three-dimensional structure and simplification of its manufacturing process.

【０００７】しかし、従来の薄膜形成工程では、重ね塗
りのために、５００〜６００℃という高温の仮焼を繰り
返す上に、結晶化のための焼成温度も高いことから、既
存の素子の劣化又は余計な酸化物の生成による特性の変
化が懸念され、このような要求を満たすことは困難であ
った。However, in the conventional thin film forming process, since the calcination at a high temperature of 500 to 600 ° C. is repeated for repeated coating and the firing temperature for crystallization is also high, deterioration or deterioration of the existing element is caused. It is difficult to meet such requirements because there is concern that the characteristics may change due to the generation of extra oxides.

【０００８】本発明は上記従来の問題点を解決し、比較
的低温、短時間の仮焼で重ね塗りが可能であり、また、
低温焼成が可能なＢａ１−ｘＳｒｘＴｉｙＯ３薄膜形成
用組成物を提供することを第１の目的とする。The present invention solves the above-mentioned conventional problems and enables recoating by calcination at a relatively low temperature for a short time.
A first object is to provide a composition for forming a Ba 1-x Sr x Ti y O 3 thin film that can be fired at a low temperature.

【０００９】また、本発明は、このようなＢａ１−ｘＳ
ｒｘＴｉｙＯ３薄膜形成用組成物を用いて低温焼成にて
も結晶化させることができるＢａ１−ｘＳｒｘＴｉｙＯ
３薄膜の形成方法を提供することを第２の目的とする。The present invention also provides such a Ba 1-x S
r x Ti y O 3 by using a thin film-forming composition can be crystallized even at a low temperature sintered Ba 1-x Sr x Ti y O
A second object is to provide a method for forming a 3 thin film.

【００１０】ところで、上記の通り、従来の薄膜コンデ
ンサには、基板上に下部電極と誘電体薄膜と上部電極を
この順で積層してなる３層積層タイプのものと、比抵抗
の小さい基板を下部電極として用いその上に誘電体薄膜
と上部電極を積層してなる２層積層タイプのものとがあ
る。前者の３層タイプの薄膜コンデンサにあっては、誘
電体薄膜を焼成する際に下部電極も高温にさらされるこ
とから、耐熱性に優れたＰｔなどの電極を用いる必要が
あり、このような耐熱性のある貴金属電極を用いた場合
には、基板と誘電体薄膜との密着性の問題や、貴金属電
極の微細加工が難しいといった問題点があった。By the way, as described above, conventional thin film capacitors include a three-layer laminated type in which a lower electrode, a dielectric thin film and an upper electrode are laminated in this order on a substrate, and a substrate having a small specific resistance. There is a two-layer laminated type which is used as a lower electrode and on which a dielectric thin film and an upper electrode are laminated. In the former three-layer type thin film capacitor, since the lower electrode is also exposed to high temperature when firing the dielectric thin film, it is necessary to use an electrode such as Pt having excellent heat resistance. When a noble metal electrode having a good property is used, there are problems that the adhesion between the substrate and the dielectric thin film is problematic, and that fine processing of the noble metal electrode is difficult.

【００１１】一方、後者の２層タイプの薄膜コンデンサ
では、このような貴金属下部電極は不要であるが、誘電
体薄膜の熱処理に８００〜１２００℃もの高温を必要と
するため、Ｓｉ基板と誘電体薄膜との界面にの低誘電率
のＳｉＯ２混合層（ＳｉＯ２と誘電体との混合層）がで
きてしまい、高誘電率薄膜を形成しても結果的にはコン
デンサの容量を大きくとれないという問題点があった。On the other hand, in the latter two-layer type thin film capacitor, such a noble metal lower electrode is not necessary, but the heat treatment of the dielectric thin film requires a high temperature of 800 to 1200 ° C., so that the Si substrate and the dielectric are used. A low dielectric constant SiO 2 mixed layer (mixed layer of SiO 2 and dielectric) is formed at the interface with the thin film, and even if a high dielectric constant thin film is formed, the capacitance of the capacitor cannot be increased as a result. There was a problem.

【００１２】本発明は、貴金属下部電極を用いず、Ｓｉ
基板上に直接に誘電体薄膜を形成しその上に上部電極を
設けた２層タイプの薄膜コンデンサにおいて、そのコン
デンサ容量を従来よりも著しく高めることが可能な薄膜
コンデンサの製造方法を提供することを第３の目的とす
る。The present invention does not use a noble metal lower electrode,
In a two-layer type thin film capacitor in which a dielectric thin film is directly formed on a substrate and an upper electrode is provided on the dielectric thin film, it is possible to provide a method of manufacturing a thin film capacitor capable of remarkably increasing the capacitance of the capacitor. The third purpose.

【００１３】[0013]

【課題を解決するための手段】本発明のＢａ１−ｘＳｒ
ｘＴｉｙＯ３薄膜形成用組成物は、有機バリウム化合
物、有機ストロンチウム化合物及びチタンアルコキシド
を、モル比がＢａ：Ｓｒ：Ｔｉ＝１−ｘ：ｘ：ｙ（ただ
し、０＜ｘ＜１，０．９≦ｙ≦１．１）となるように有
機溶媒中に溶解してなるＢａ１−ｘＳｒｘＴｉｙＯ３薄
膜形成用組成物において、該有機バリウム化合物及び有
機ストロンチウム化合物が、一般式ＣｎＨ２ｎ＋１ＣＯ
ＯＨ（ただし、３≦ｎ≦７）で表されるカルボン酸の金
属塩であって、かつ、下記一般式［Ｉ］の構造をとり得
るカルボン酸塩であることを特徴とする。Ba 1-x Sr of the present invention
The x Ti y O 3 thin film forming composition contains an organic barium compound, an organic strontium compound and a titanium alkoxide in a molar ratio of Ba: Sr: Ti = 1−x: x: y (where 0 < x < 1,0 In the composition for forming a Ba 1-x Sr x Ti y O 3 thin film formed by dissolving the organic barium compound and the organic strontium compound in an organic solvent so as to satisfy the following general formula: C n H 2n + 1 CO
A metal salt of a carboxylic acid represented by OH (3 ≦ n ≦ 7) and a carboxylic acid salt capable of having the structure of the following general formula [I].

【００１４】[0014]

【化２】 （上記式中、Ｒ１，Ｒ２，Ｒ３，Ｒ４，Ｒ５，Ｒ６は水
素、メチル基又はエチル基を示し、ＭはＢａ又はＳｒを
示す。）[Chemical 2] (In the above formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 represent hydrogen, a methyl group or an ethyl group, and M represents Ba or Sr.)

【００１５】本発明のＢａ１−ｘＳｒｘＴｉｙＯ３薄膜
の形成方法は、本発明のＢａ１−ｘＳｒｘＴｉｙＯ３薄
膜形成用組成物を用いてＢａ１−ｘＳｒｘＴｉｙＯ３薄
膜を形成する方法であって、該Ｂａ１−ｘＳｒｘＴｉｙ
Ｏ３薄膜形成用組成物を基板に塗布して乾燥する工程を
所望の膜厚が得られるまで繰り返し行った後、７５０℃
以下の温度で焼成して結晶化させることを特徴とする。[0015] Ba 1-x Sr x Ti y O 3 formation process of a thin film of the present invention, Ba 1-x Sr x of the present invention Ti y O 3 by using a thin film forming composition Ba 1-x Sr x Ti a method of forming a y O 3 film, the Ba 1-x Sr x Ti y
The process of applying the composition for forming an O 3 thin film to a substrate and drying it is repeated until a desired film thickness is obtained, and then 750 ° C.
It is characterized in that it is fired at the following temperature to be crystallized.

【００１６】本発明の薄膜コンデンサの製造方法は、Ｓ
ｉ基板上に誘電体薄膜を形成し、この誘電体薄膜の上に
上部電極を形成する誘電体薄膜の製造方法において、該
Ｓｉ基板上に本発明のＢａ１−ｘＳｒｘＴｉｙＯ３薄膜
形成用組成物を用いてＢａ１−ｘＳｒｘＴｉｙＯ３誘電
体薄膜を形成する方法であって、該Ｂａ１−ｘＳｒｘＴ
ｉｙＯ３薄膜形成用組成物を基板に塗布して乾燥する工
程を所望の膜厚が得られるまで繰り返し行った後、７５
０℃以下の温度で焼成して結晶化させることを特徴とす
る。なお、この焼成は、電気炉中ならば３０〜６０分行
うのが好ましく、ＲＴＡ（Ｒａｐｉｄ Ｔｈｅｒｍａｌ
Ａｎｎｅａｌ，短時間アニール）装置ならば１〜３０
分行うのが好ましい。The method of manufacturing the thin film capacitor of the present invention is performed by using S
A dielectric thin film is formed on an i substrate, and an upper electrode is formed on the dielectric thin film. A Ba 1-x Sr x Ti y O 3 thin film according to the present invention is provided on the Si substrate. a method of forming a Ba 1-x Sr x Ti y O 3 dielectric thin film using a composition for forming the Ba 1-x Sr x T
After the process of applying the composition for forming a thin film of i y O 3 on a substrate and drying it is repeated until a desired film thickness is obtained, 75
It is characterized in that it is baked at a temperature of 0 ° C. or lower to be crystallized. It should be noted that this firing is preferably carried out for 30 to 60 minutes in an electric furnace, and RTA (Rapid Thermal)
1-30 for Annealing, short time annealing equipment
It is preferable to carry out in minutes.

【００１７】[0017]

【発明の実施の形態】以下に本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

【００１８】本発明において、Ｂａ原料及びＳｒ原料と
して用いられるカルボン酸塩は、一般式ＣｎＨ２ｎ＋１
ＣＯＯＨ（ただし、３≦ｎ≦７）で表され、かつ、上記
一般式［Ｉ］の構造をとり得るカルボン酸の金属塩であ
るが、このようなカルボン酸としては、具体的には次の
ようなものが挙げられる。In the present invention, the carboxylic acid salt used as the Ba raw material and the Sr raw material has a general formula of C n H 2n + 1.
A metal salt of a carboxylic acid represented by COOH (where 3 ≦ n ≦ 7) and capable of having the structure of the above-mentioned general formula [I]. Specific examples of such a carboxylic acid include the following. Something like this.

【００１９】[0019]

【表１】 [Table 1]

【００２０】このようなカルボン酸のバリウム塩又はス
トロンチウム塩は、上記カルボン酸と炭酸バリウム（Ｂ
ａＣＯ３）又は炭酸ストロンチウム（ＳｒＣＯ３）とを
反応させることにより容易に合成することができる。Such a barium salt or strontium salt of a carboxylic acid is prepared by using the above-mentioned carboxylic acid and barium carbonate (B
It can be easily synthesized by reacting with aCO 3 ) or strontium carbonate (SrCO 3 ).

【００２１】本発明において、Ｂａ原料及びＳｒ原料と
して用いるカルボン酸塩は、下記一般反応式に示す如
く、低温にて容易に分解する。In the present invention, the carboxylic acid salts used as the Ba raw material and the Sr raw material are easily decomposed at low temperature as shown in the following general reaction formula.

【００２２】[0022]

【化３】 [Chemical 3]

【００２３】即ち、このカルボン酸塩は、水素結合の働
きで構造的に六員環をとることにより、低温にて理想的
な炭素結合の分解がなされる（Allen W.等、Mat.Res.S
ec.Symp.Proc.Vol.271(1992)）。例えば、文献（M.K.Ka
malasanan等、Apple.Phys.Lett.59(27)、0003-6951）に
おいても、酢酸塩よりも２−エチルヘキサン酸塩のほう
がより低温でかつ短時間の熱処理が可能であることが示
されている。That is, this carboxylate salt ideally decomposes carbon bonds at low temperatures by taking a structural six-membered ring by the action of hydrogen bonds (Allen W. et al., Mat. Res. S
ec.Symp.Proc.Vol.271 (1992)). For example, the literature (MKKa
Malasanan et al., Apple.Phys.Lett.59 (27), 0003-6951) also showed that 2-ethylhexanoate can be heat-treated at a lower temperature and in a shorter time than acetate. There is.

【００２４】このように、本発明で用いるカルボン酸塩
は、低温にて容易に分解されることから、塗膜形成時に
おいて、低温、短時間の熱処理で重ね塗りができ、更に
低温焼成が可能となる。As described above, the carboxylic acid salt used in the present invention is easily decomposed at a low temperature, so that it is possible to carry out overcoating by a heat treatment at a low temperature for a short time at the time of forming a coating film, and further a low temperature baking is possible. Becomes

【００２５】一方、Ｔｉ原料のチタンアルコキシドとし
ては、Ｔｉ（ＯＲ）４（ただし、Ｒは炭素数２〜５の直
鎖状又は分岐状のアルキル基）で表されるものを用いる
が、具体的には、エトキシチタン、イソプロポキシチタ
ン、ｎ−プロポキシチタン、イソブトキシチタン、ｔｅ
ｒｔ−ブトキシチタン、ｎ−アミロキシチタン等が好適
に使用される。On the other hand, as the titanium alkoxide used as the Ti raw material, one represented by Ti (OR) 4 (where R is a linear or branched alkyl group having 2 to 5 carbon atoms) is used. Include ethoxy titanium, isopropoxy titanium, n-propoxy titanium, isobutoxy titanium, te.
rt-Butoxy titanium, n-amyloxy titanium and the like are preferably used.

【００２６】本発明において、これらのＢａ原料、Ｓｒ
原料及びＴｉ原料を混合する有機溶媒としては、酢酸エ
チル、酢酸ｎ−プロピル、酢酸イソプロピル、酢酸ｎ−
ブチル、酢酸ｓｅｃ−ブチル、酢酸ｔｅｒｔ−ブチル、
酢酸イソブチル、酢酸ｎ−アミル、酢酸ｓｅｃ−アミ
ル、酢酸ｔｅｒｔ−アミル、酢酸イソアミル等の、酢酸
と炭素数２〜５のアルコールとのエステルを用いること
ができる。In the present invention, these Ba raw materials, Sr
Organic solvents for mixing the raw materials and the Ti raw materials include ethyl acetate, n-propyl acetate, isopropyl acetate, and n-acetate.
Butyl, sec-butyl acetate, tert-butyl acetate,
Esters of acetic acid and an alcohol having 2 to 5 carbon atoms such as isobutyl acetate, n-amyl acetate, sec-amyl acetate, tert-amyl acetate, and isoamyl acetate can be used.

【００２７】Ｂａ原料、Ｓｒ原料及びＴｉ原料は、これ
らの有機溶媒中に所望のＢａ１−ｘＳｒｘＴｉｙＯ３組
成となるように、また、Ｂａ１−ｘＳｒｘＴｉｙＯ３濃
度が２〜１５重量％好ましくは４〜１０重量％となるよ
うに混合される。The Ba raw material, the Sr raw material and the Ti raw material are mixed so that the desired Ba 1-x Sr x Ti y O 3 composition is obtained in these organic solvents, and the Ba 1-x Sr x Ti y O 3 concentration is set. Is 2 to 15% by weight, preferably 4 to 10% by weight.

【００２８】なお、本発明においては、バリウムとスト
ロンチウムを熱分解性に優れる六員環構造を形成するカ
ルボン酸塩で加え、また、チタンをアルコキシドで加え
るが、チタンアルコキシドの加水分解性のために、ＢＳ
Ｔ薄膜形成用組成物を基板に塗布した時にストリエーシ
ョンが発生する可能性がある。従って、必要に応じて、
β−ジケトン類、β−ケトエステル類、グリコール類、
アルコール類、高級カルボン酸類等の安定化剤を加える
のが好ましい。具体的には、アセチルアセトン、ベンゾ
イルアセトン、ジベンゾイルメタン、３−オキソブタン
酸エチル、２−メトキシエタノール、２−エトキシエタ
ノール、２−エトキシプロパノール、β−ブチレングリ
コール、２，４−アミレングリコール、又は、バリウム
及びストロンチウムのカルボン酸塩と同じカルボン酸
を、チタンアルコキシドに対して５．０倍モル量以下、
とくには０．５〜４．０倍モル量添加するのが好まし
い。In the present invention, barium and strontium are added as a carboxylic acid salt forming a six-membered ring structure having excellent thermal decomposability, and titanium is added as an alkoxide. However, because of the hydrolyzability of titanium alkoxide, , BS
Striation may occur when the T thin film forming composition is applied to the substrate. Therefore, if necessary,
β-diketones, β-ketoesters, glycols,
It is preferable to add stabilizers such as alcohols and higher carboxylic acids. Specifically, acetylacetone, benzoylacetone, dibenzoylmethane, ethyl 3-oxobutanoate, 2-methoxyethanol, 2-ethoxyethanol, 2-ethoxypropanol, β-butylene glycol, 2,4-amylene glycol, or The same carboxylic acid as the carboxylic acid salt of barium and strontium is 5.0 times or less the molar amount of titanium alkoxide,
It is particularly preferable to add 0.5 to 4.0 times the molar amount.

【００２９】このようにして得られる本発明のＢａ
１−ｘＳｒｘＴｉｙＯ３薄膜形成用組成物を用いてＢａ
１−ｘＳｒｘＴｉｙＯ３薄膜を形成するには、スピンコ
ート、ディップコート、スプレーコート等の塗布法によ
り、Ｐｔ／Ｔｉ／ＳｉＯ２／Ｓｉ，Ｐｔ／ＩｒＯ／Ｉｒ
／ＳｉＯ２／Ｓｉ，Ｐｔ／ＴｉＮ／ＳｉＯ２／Ｓｉ，Ｐ
ｔ／Ｔａ／ＳｉＯ２／Ｓｉ，Ｐｔ／Ｉｒ／ＳｉＯ２／Ｓ
ｉ等の基板上、或いは、アルミナ、窒化アルミニウム、
ジルコニア等をガラスコートしたグレース基板上に本発
明の組成物を塗布して乾燥する工程を、所望の膜厚が得
られるまで複数回繰り返し行った後、焼成する。本発明
においては、Ｂａ１−ｘＳｒｘＴｉｙＯ３薄膜形成用組
成物に易分解性の原料を用いているため、この乾燥を１
５０〜４００℃の低温で行うことができ、また、焼成に
ついても４５０〜７５０℃の低温で行うことができる。
なお、乾燥時間は通常５〜１０分程度、焼成時間は１〜
６０分程度である。当然ながら、焼成温度が高いほど、
焼成時間は短かくて済む。The Ba of the present invention thus obtained
1-x Sr x Ti y O 3 using the composition for forming a thin film of Ba
To form a 1-x Sr x Ti y O 3 thin film, Pt / Ti / SiO 2 / Si, Pt / IrO / Ir is formed by a coating method such as spin coating, dip coating, or spray coating.
/ SiO 2 / Si, Pt / TiN / SiO 2 / Si, P
t / Ta / SiO 2 / Si, Pt / Ir / SiO 2 / S
on a substrate such as i or alumina, aluminum nitride,
The step of applying the composition of the present invention onto a glass substrate coated with zirconia or the like and drying it is repeated a plurality of times until a desired film thickness is obtained, and then firing. In the present invention, since a readily decomposable raw material is used for the Ba 1-x Sr x Ti y O 3 thin film forming composition, this drying is
It can be performed at a low temperature of 50 to 400 ° C., and the firing can be performed at a low temperature of 450 to 750 ° C.
The drying time is usually about 5 to 10 minutes, and the firing time is 1 to
It takes about 60 minutes. Of course, the higher the firing temperature,
The firing time is short.

【００３０】本発明の組成物を用いて薄膜コンデンサを
製造するには、上記薄膜形成方法に従ってＳｉ基板上に
誘電体薄膜を形成する。この場合、最後の焼成温度が高
くなるほど焼成時間を短かくし、Ｓｉ基板の酸化を少な
くする。In order to manufacture a thin film capacitor using the composition of the present invention, a dielectric thin film is formed on a Si substrate according to the above thin film forming method. In this case, the higher the final firing temperature is, the shorter the firing time is and the less the oxidation of the Si substrate is.

【００３１】このように７５０℃以下の低温焼成で薄膜
を結晶化させることにより、Ｓｉ基板表面の酸化層形成
量が著しく少なくなり、ＳｉＯ２と誘電体との混合層も
きわめて薄くなる。そして、これにより、薄膜コンデン
サのキャパシタ容量が８００℃以上の高温焼成を必要と
した従来に比べ格段に高いものとなる。By crystallizing the thin film by firing at a low temperature of 750 ° C. or lower, the amount of oxide layer formed on the surface of the Si substrate is significantly reduced, and the mixed layer of SiO 2 and the dielectric is extremely thin. As a result, the capacitance of the thin-film capacitor becomes significantly higher than that of the conventional one which requires high temperature firing at 800 ° C. or higher.

【００３２】この誘電体薄膜上に電極を形成するには、
蒸着、スパッタリングなど各種の方法を採用できる。To form an electrode on this dielectric thin film,
Various methods such as vapor deposition and sputtering can be adopted.

【００３３】[0033]

【実施例】以下、本発明の実施例及び比較例について説
明する。なお、以下の実施例及び比較例において、Ｓｉ
Ｏ２の換算膜厚は次のようにして計算した。EXAMPLES Examples and comparative examples of the present invention will be described below. In the following examples and comparative examples, Si
The converted film thickness of O 2 was calculated as follows.

【００３４】ＳｉＯ２換算膜厚の計算方法 ＢＳＴ（Ｂａ１−ｘＳｒｘＴｉｙＯ３）の膜厚をｄ、誘
電率をε１、ＳｉＯ２の膜厚をｘ、誘電率をε２、電束
密度をδとする。Calculation method of SiO 2 conversion film thickness BST (Ba 1-x Sr x Ti y O 3 ) film thickness d, dielectric constant ε 1 , SiO 2 film thickness x, dielectric constant ε 2 , Let δ be the electric flux density.

【００３５】電極間に比誘電率の異なる２種の誘電体が
存在する場合When two kinds of dielectrics having different relative dielectric constants exist between electrodes

【数１】 [Equation 1]

【００３６】１対の平行平板導体の間に誘電率ε１のＢ
ＳＴ膜と、誘電率ε２のＳｉ２膜とが積層配置されてお
り、導体間の電位差Ｖは次の通りとなる。B having a permittivity ε 1 between a pair of parallel plate conductors.
The ST film and the Si 2 film having the dielectric constant ε 2 are laminated and arranged, and the potential difference V between the conductors is as follows.

【数２】 [Equation 2]

【００３７】単位面積当たりの容量をＣとすると、If the capacitance per unit area is C,

【数３】 [Equation 3]

【００３８】Ｂ０．７Ｓｒ０．３ＴｉＯ３の場合、ＢＳ
Ｔの比誘電率をε１’＝３００とし、ＳｉＯ２の比誘電
率をε２’＝４とする。ここで、誘電率ε１＝ε０×ε
１’，ε２＝ε０×ε２’であり、ε０は真空の誘電率
＝８．８５４×１０−１２である。これらのε１，ε２
の値を上記（１）式に代入し、Ｃ，ｄの値の測定値から
ｘを求める。In the case of B 0.7 Sr 0.3 TiO 3 , BS
The relative permittivity of T is ε 1 ′ = 300, and the relative permittivity of SiO 2 is ε 2 ′ = 4. Here, the dielectric constant ε 1 = ε 0 × ε
1 ′, ε 2 = ε 0 × ε 2 ′, and ε 0 is the dielectric constant of vacuum = 8.854 × 10 −12 . These ε 1 , ε 2
Is substituted into the above equation (1), and x is obtained from the measured values of C and d.

【００３９】なお、（Ｂａ０．５Ｓｒ０．５）ＴｉＯ３
の場合、ε１’＝２４０、 （Ｂａ０．３Ｓｒ０．７）ＴｉＯ３の場合、ε１’＝２
００、 ＢａＴｉＯ３の場合、ε１’＝１５０ ＳｒＴｉＯ３の場合、ε１’＝１５０ として計算を行う。Note that (Ba 0.5 Sr 0.5 ) TiO 3
Ε 1 ′ = 240 in the case of, and ε 1 ′ = 2 in the case of (Ba 0.3 Sr 0.7 ) TiO 3.
00, in the case of BaTiO 3 , ε 1 ′ = 150, and in the case of SrTiO 3 , ε 1 ′ = 150.

【００４０】[実施例１]（ｎ＝３） 薄膜原料としてｎ−酪酸バリウム、ｎ−酪酸ストロンチ
ウム、チタニウムイソプロポキシドを用い、これらを組
成比Ｂａ０．７Ｓｒ０．３ＴｉＯ３となるように、か
つ、組成物の酸化物換算の合計濃度が７重量％濃度とな
るように、有機溶剤（酢酸イソアミル。以下の実施例及
び比較例において同じ）中に混合し薄膜形成剤を調製し
た。[Example 1] (n = 3) n-barium butyrate, strontium n-butyrate, and titanium isopropoxide were used as thin film raw materials, and these had a composition ratio of Ba 0.7 Sr 0.3 TiO 3. Further, a thin film forming agent was prepared by mixing the composition with an organic solvent (isoamyl acetate; the same in the following Examples and Comparative Examples) so that the total concentration of the composition in terms of oxide was 7% by weight.

【００４１】この薄膜形成剤を比抵抗が０．０２Ω・ｃ
ｍのシリコン基板上に塗布し（スピンコート）、２００
℃で１０分間乾燥させこの工程を繰り返し、最後に電気
炉中にて５５０℃で３０分焼成を行い誘電体薄膜を形成
した。この誘電体薄膜上にＰｔ上部電極を、また誘電体
薄膜を形成していない側のシリコン基板表面に、取り出
し電極としてＰｔ電極をそれぞれスパッタリングにより
形成し、薄膜コンデンサを製造した。電気特性の測定結
果を表２に示す。This thin film forming agent has a specific resistance of 0.02 Ω · c.
m on a silicon substrate (spin coating), 200
This process was repeated after drying at 0 ° C. for 10 minutes, and finally baking was performed at 550 ° C. for 30 minutes in an electric furnace to form a dielectric thin film. A Pt upper electrode was formed on the dielectric thin film, and a Pt electrode was formed as a take-out electrode on the surface of the silicon substrate on which the dielectric thin film was not formed by sputtering to manufacture a thin film capacitor. Table 2 shows the measurement results of the electrical characteristics.

【００４２】[実施例２]（ｎ＝５） 薄膜原料として４−メチルペンタン酸バリウム、４−メ
チルペンタン酸ストロンチウム、チタニウムイソプロポ
キシドを用いたこと以外は実施例１と同様にして薄膜コ
ンデンサを製造した。電気特性の測定結果を表２に示
す。[Example 2] (n = 5) A thin film capacitor was prepared in the same manner as in Example 1 except that barium 4-methylpentanoate, strontium 4-methylpentanoate and titanium isopropoxide were used as raw materials for the thin film. Manufactured. Table 2 shows the measurement results of the electrical characteristics.

【００４３】[実施例３]（ｎ＝７） 薄膜原料として２−エチルヘキサン酸バリウム、２−エ
チルヘキサン酸ストロンチウム、チタニウムイソプロポ
キシドを用いたこと以外は実施例１と同様にして薄膜コ
ンデンサを製造した。電気特性の測定結果を表２に示
す。[Example 3] (n = 7) A thin film capacitor was prepared in the same manner as in Example 1 except that barium 2-ethylhexanoate, strontium 2-ethylhexanoate and titanium isopropoxide were used as thin film raw materials. Manufactured. Table 2 shows the measurement results of the electrical characteristics.

【００４４】[比較例１]（ｎ＝２） 薄膜原料としてプロピオン酸バリウム、プロピオン酸ス
トロンチウム、チタニウムイソプロポキシドを用いたこ
と以外は実施例１と同様にして薄膜コンデンサを製造し
た。電気特性の測定結果を表２に示す。Comparative Example 1 (n = 2) A thin film capacitor was manufactured in the same manner as in Example 1 except that barium propionate, strontium propionate, and titanium isopropoxide were used as thin film raw materials. Table 2 shows the measurement results of the electrical characteristics.

【００４５】[比較例２]（ｎ＝８） 薄膜原料としてノナン酸バリウム、ノナン酸ストロンチ
ウム、チタニウムイソプロポキシドを用い、これらを組
成比Ｂａ０．７Ｓｒ０．３ＴｉＯ３となるように、か
つ、組成物の酸化物換算の合計濃度が７重量％濃度とな
るように、有機溶剤中に混合し薄膜形成剤を調製した。[Comparative Example 2] (n = 8) Barium nonanoate, strontium nonanoate, and titanium isopropoxide were used as thin film raw materials, and these were used to have a composition ratio Ba 0.7 Sr 0.3 TiO 3 . In addition, a thin film forming agent was prepared by mixing in an organic solvent so that the total concentration of the composition in terms of oxide was 7% by weight.

【００４６】この薄膜形成剤を用いて実施例１と同様に
低抵抗シリコン基板上に塗布したところ、溶液の粘度が
高く均質な膜にはならなかった。そこで有機溶剤を更に
加え溶液濃度を３重量％濃度まで希釈して基板に塗布し
たところ均質な膜にはなったが、重ね塗りの段階で前回
の塗布膜が溶解してしまい、成膜は不可能であった。When this thin film forming agent was applied onto a low resistance silicon substrate in the same manner as in Example 1, the solution had a high viscosity and a uniform film was not formed. Therefore, when an organic solvent was further added to dilute the solution concentration to 3% by weight and applied to the substrate, a uniform film was obtained, but the previously applied film was dissolved at the stage of overcoating, and film formation was not possible. It was possible.

【００４７】[比較例３〜５] 最後の熱処理を８００℃１時間で行ったこと以外は、実
施例１〜３と同様に行って薄膜コンデンサを製造した。
電気特性の測定結果を表２に示す。Comparative Examples 3 to 5 Thin film capacitors were manufactured in the same manner as in Examples 1 to 3 except that the final heat treatment was performed at 800 ° C. for 1 hour.
Table 2 shows the measurement results of the electrical characteristics.

【００４８】[比較例６，７] 最後の熱処理を８００℃１時間で行ったこと以外は、比
較例１、２と同様に行って薄膜コンデンサを製造した。
電気特性の測定結果を表２に示す。Comparative Examples 6 and 7 Thin film capacitors were manufactured in the same manner as in Comparative Examples 1 and 2 except that the final heat treatment was performed at 800 ° C. for 1 hour.
Table 2 shows the measurement results of the electrical characteristics.

【００４９】[実施例４〜６] 最後の熱処理をＲＴＡにて、７００℃１分で行ったこと
以外は、実施例１〜３と同様に行って薄膜コンデンサを
製造した。電気特性の測定結果を表３に示す。[Examples 4 to 6] Thin film capacitors were manufactured in the same manner as in Examples 1 to 3 except that the final heat treatment was performed at RTA at 700 ° C for 1 minute. Table 3 shows the measurement results of the electrical characteristics.

【００５０】[比較例８，９] 最後の熱処理をＲＴＡにて、７００℃１分で行ったこと
以外は、比較例１〜２と同様に行って薄膜コンデンサを
製造した。電気特性の測定結果を表３に示す。Comparative Examples 8 and 9 Thin film capacitors were manufactured in the same manner as in Comparative Examples 1 and 2 except that the final heat treatment was performed at RTA at 700 ° C. for 1 minute. Table 3 shows the measurement results of the electrical characteristics.

【００５１】[実施例７〜９、比較例１０，１１] 薄膜原料を組成比Ｂａ０．５Ｓｒ０．５ＴｉＯ３となる
ように溶解させたこと以外は、実施例１〜３及び比較例
１，２と同様に行って薄膜コンデンサを製造した。電気
特性の測定結果を表４に示す。[Examples 7 to 9 and Comparative Examples 10 and 11] Examples 1 to 3 and Comparative Examples except that the thin film raw material was dissolved to have a composition ratio of Ba 0.5 Sr 0.5 TiO 3. A thin film capacitor was manufactured in the same manner as 1 and 2. Table 4 shows the measurement results of the electrical characteristics.

【００５２】[実施例１０〜１２、比較例１２，１３] 薄膜原料を組成比Ｂａ０．３Ｓｒ０．７ＴｉＯ３となる
ように溶解させたこと以外は、実施例１〜３及び比較例
１，２と同様に行って薄膜コンデンサを製造した。電気
特性の測定結果を表５に示す。 [Examples 10 to 12 and Comparative Examples 12 and 13] Examples 1 to 3 and Comparative Examples except that the thin film raw material was dissolved to have a composition ratio of Ba 0.3 Sr 0.7 TiO 3. A thin film capacitor was manufactured in the same manner as 1 and 2. Table 5 shows the measurement results of the electrical characteristics .

【００５３】[実施例１３]（ｎ＝５） ２−エチル酪酸バリウム７．１１ｇ、２−エチル酪酸ス
トロンチウム２．６４ｇを酢酸イソアミル溶媒４０ｇに
溶解させ、添加剤２，４−ペンタンジオン５．５ｇを加
えた後、イソプロポキシチタン７．８９ｇを加えて還流
した。その後、イソアミルアルコール３０ｇと酢酸イソ
アミルを添加して全体が１００ｇになるようにして、６
重量％のＢａ０．７Ｓｒ０．３ＴｉＯ３薄膜形成用組成
物を調製した。Example 13 (n = 5) 7.11 g of barium 2-ethylbutyrate and 2.64 g of strontium 2-ethylbutyrate were dissolved in 40 g of isoamyl acetate solvent, and 5.5 g of 2,4-pentanedione as an additive. After the addition of 7.89 g of isopropoxy titanium, the mixture was refluxed. Then, 30 g of isoamyl alcohol and isoamyl acetate were added to make 100 g,
A wt% Ba 0.7 Sr 0.3 TiO 3 thin film forming composition was prepared.

【００５４】この溶液を用いたこと以外は同様にして薄
膜コンデンサを製造した。電気特性の測定結果を表６に
示す。A thin film capacitor was manufactured in the same manner except that this solution was used. Table 6 shows the measurement results of the electrical characteristics.

【００５５】[実施例１４]（ｎ＝４） 薄膜原料としてα−メチル酪酸を用いたこと以外は実施
例１と同様にして薄膜コンデンサを製造した。電気特性
の測定結果を表６に示す。Example 14 (n = 4) A thin film capacitor was manufactured in the same manner as in Example 1 except that α-methylbutyric acid was used as a thin film raw material. Table 6 shows the measurement results of the electrical characteristics.

【００５６】[実施例１５]（ｎ＝６） 薄膜原料としてチメチルヘキサン酸を用いたこと以外は
実施例１と同様にして薄膜コンデンサを製造した。電気
特性の測定結果を表６に示す。[Example 15 ] (n = 6) A thin-film capacitor was manufactured in the same manner as in Example 1 except that thymethylhexanoic acid was used as a thin-film raw material. Table 6 shows the measurement results of the electrical characteristics.

【００５７】[比較例１４]（酢酸塩） 酢酸バリウム４．９１ｇと酢酸ストロンチウム０．５水
和物１．７７ｇを酢酸溶媒８０ｇに溶解し、１５０℃で
脱水を行った後、添加剤２，４−ペンタンジオン５．５
０ｇを添加し、その後、イソプロポキシチタン７．８１
ｇを加えた。更に、全体の質量が１００ｇになるように
酢酸溶媒を加えて、６重量％のＢａ０．７Ｓｒ０．３Ｔ
ｉＯ３薄膜形成用組成物を調製した。Comparative Example 14 (Acetate) Barium acetate (4.91 g) and strontium acetate hemihydrate (1.77 g) were dissolved in acetic acid solvent (80 g) and dehydrated at 150 ° C., followed by addition of additive 2, 4-pentanedione 5.5
0 g was added, followed by isopropoxy titanium 7.81
g was added. Further, an acetic acid solvent was added so that the total mass became 100 g, and 6 wt% of Ba 0.7 Sr 0.3 T was added.
A composition for forming an iO 3 thin film was prepared.

【００５８】この溶液を用いて実施例１と同様の方法で
成膜を試みたところ、重ね塗りの段階で前回の塗布膜が
溶解してしまい、成膜は不可能であった。An attempt was made to form a film by using this solution in the same manner as in Example 1, but it was impossible to form a film because the previously applied film was dissolved in the step of overcoating.

【００５９】[比較例１５]（一般式［Ｉ］の構造をとら
ないｎ−ヘプタン酸塩） ｎ−ヘプタン酸バリウム７．６１ｇ、ｎ−ヘプタン酸ス
トロンチウム２．８５ｇを酢酸イソアミル溶媒７０ｇに
溶解させ、添加剤３−オキソブタン酸エチル７．１５ｇ
を添加した後、イソプロポキシチタン７．８９ｇを加え
て還流した。更に、酢酸イソアミルで全体の質量を１０
０ｇにして、６重量％のＢａ０．７Ｓｒ０．３ＴｉＯ３
薄膜形成用組成物を調製した。[Comparative Example 15 ] (n-Heptanoate not having the structure of general formula [I]) 7.61 g of barium n-heptanoate and 2.85 g of strontium n-heptanoate were dissolved in 70 g of isoamyl acetate solvent. , Additive ethyl 3-oxobutanoate 7.15 g
Was added, and then 7.89 g of isopropoxy titanium was added and refluxed. Furthermore, the total mass is 10 with isoamyl acetate.
6% by weight of Ba 0.7 Sr 0.3 TiO 3 at 0 g
A thin film forming composition was prepared.

【００６０】この溶液を用いて実施例１と同様の方法で
成膜を試みたところ、重ね塗りの段階で前回の塗布膜が
溶解してしまい、成膜は不可能であった。An attempt was made to form a film by using this solution in the same manner as in Example 1, but it was impossible to form a film because the previously applied film was dissolved in the step of overcoating.

【００６１】[0061]

【表２】 [Table 2]

【００６２】[0062]

【表３】 [Table 3]

【００６３】[0063]

【表４】 [Table 4]

【００６４】[0064]

【表５】 [Table 5]

【００６５】[0065]

【表６】 [Table 6]

【００６６】[0066]

【発明の効果】以上詳述した通り、本発明のＢａ１−ｘ
ＳｒｘＴｉｙＯ３薄膜形成用組成物及びＢａ１−ｘＳｒ
ｘＴｉｙＯ３薄膜の形成方法によれば、従来法に比べ
て、乾燥工程及び焼成工程での低温化が図れ、所望の膜
厚の高特性Ｂａ１−ｘＳｒｘＴｉｙＯ３薄膜を容易かつ
低コストに形成することが可能とされる。本発明の薄膜
コンデンサの製造方法によると、誘電体薄膜を低温焼成
できるため、誘電体薄膜とＳｉ基板との界面に生じるＳ
ｉＯ２と誘電体との混合層が従来よりも格段に薄く、こ
のためキャパシタ容量が大きい薄膜コンデンサを製造す
ることができる。As described above in detail, the Ba 1-x of the present invention is used.
Sr x Ti y O 3 thin film forming composition and Ba 1-x Sr
According to the method of forming the x Ti y O 3 thin film, the temperature can be lowered in the drying step and the firing step as compared with the conventional method, and a high-characteristic Ba 1-x Sr x Ti y O 3 thin film having a desired film thickness can be obtained. It can be formed easily and at low cost. According to the method of manufacturing a thin film capacitor of the present invention, since the dielectric thin film can be fired at a low temperature, S produced at the interface between the dielectric thin film and the Si substrate.
Since the mixed layer of iO 2 and the dielectric is much thinner than the conventional one, a thin film capacitor having a large capacitance can be manufactured.

フロントページの続き (56)参考文献 国際公開94／010084（ＷＯ，Ａ１) Ｊｏｕｒｎａｌ ｏｆ Ｍａｔｅｒｉ ａｌｓ Ｒｅｓｅａｒｃｈ，1994年，Ｖ ｏｌ．９ Ｎｏ．４，970−979 (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 1/00 - 57/00 C04B 35/46 ＣＡ（ＳＴＮ)Front Page Continuation (56) References International Publication 94/010084 (WO, A1) Journal of Material Research, 1994, Vol. 9 No. 4,970-979 (58) Fields investigated (Int.Cl. 7 , DB name) C01G 1/00-57/00 C04B 35/46 CA (STN)

Claims (6)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 有機バリウム化合物、有機ストロンチウ
ム化合物及びチタンアルコキシドを、モル比がＢａ：Ｓ
ｒ：Ｔｉ＝１−ｘ：ｘ：ｙ（ただし、０＜ｘ＜１，０．
９≦ｙ≦１．１）となるように有機溶媒中に溶解してな
るＢａ１−ｘＳｒｘＴｉｙＯ３薄膜形成用組成物におい
て、 該有機バリウム化合物及び有機ストロンチウム化合物
が、一般式ＣｎＨ２ｎ＋１ＣＯＯＨ（ただし、３≦ｎ≦
７）で表されるカルボン酸の金属塩であって、かつ、下
記一般式［Ｉ］の構造をとり得るカルボン酸塩であるこ
とを特徴とするＢａ１−ｘＳｒｘＴｉｙＯ３薄膜形成用
組成物。 【化１】 （上記式中、Ｒ１，Ｒ２，Ｒ３，Ｒ４，Ｒ５，Ｒ６は水
素、メチル基又はエチル基を示し、ＭはＢａ又はＳｒを
示す。）1. An organic barium compound, an organic strontium compound and a titanium alkoxide are used in a molar ratio of Ba: S.
r: Ti = 1-x: x: y (where 0 < x < 1,0.
In the composition for forming a Ba 1-x Sr x Ti y O 3 thin film formed by dissolving in an organic solvent so that 9 ≦ y ≦ 1.1), the organic barium compound and the organic strontium compound have the general formula C n H 2n + 1 COOH (however, 3 ≦ n ≦
Ba 1-x Sr x Ti y O 3 thin film formation, which is a metal salt of a carboxylic acid represented by 7) and is a carboxylic acid salt capable of having the structure of the following general formula [I]. Composition. [Chemical 1] (In the above formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 represent hydrogen, a methyl group or an ethyl group, and M represents Ba or Sr.) 【請求項２】 請求項１において、チタンアルコキシド
がＴｉ（ＯＲ） ４ （ただし、Ｒは炭素数２〜５の直鎖状
又は分岐状のアルキル基）で表されることを特徴とする
Ｂａ １−ｘ Ｓｒ ｘ Ｔｉ ｙ Ｏ ３ 薄膜形成用組成物。 2. The titanium alkoxide according to claim 1.
Is Ti (OR) 4 (wherein R is a straight-chain having 2 to 5 carbon atoms )
Or a branched alkyl group).
Ba 1-x Sr x Ti y O 3 thin film-forming composition. 【請求項３】 請求項１又は２に記載のＢａ１−ｘＳｒ
ｘＴｉｙＯ３薄膜形成用組成物を用いてＢａ１−ｘＳｒ
ｘＴｉｙＯ３薄膜を形成する方法であって、該Ｂａ
１−ｘＳｒｘＴｉｙＯ３薄膜形成用組成物を基板に塗布
して乾燥する工程を所望の膜厚が得られるまで繰り返し
行った後、７５０℃以下の温度で焼成して結晶化させる
ことを特徴とするＢａ１−ｘＳｒｘＴｉｙＯ３薄膜の形
成方法。3. The Ba 1-x Sr according to claim 1 or 2.
x Ti y O 3 using the composition for forming a thin film of Ba 1-x Sr
x Ti y O 3 thin film forming method, comprising:
1-x Sr x Ti y O 3 A thin film-forming composition is applied to a substrate and dried, which is repeatedly performed until a desired film thickness is obtained, and then baked at a temperature of 750 ° C. or lower to be crystallized. A method for forming a Ba 1-x Sr x Ti y O 3 thin film, comprising: 【請求項４】 Ｓｉ基板上に誘電体薄膜を形成し、この
誘電体薄膜の上に上部電極を形成する薄膜コンデンサの
製造方法において、 該Ｓｉ基板上に請求項１又は２に記載のＢａ１−ｘＳｒ
ｘＴｉｙＯ３薄膜形成用組成物を用いてＢａ１−ｘＳｒ
ｘＴｉｙＯ３誘電体薄膜を形成する方法であって、 該Ｂａ１−ｘＳｒｘＴｉｙＯ３薄膜形成用組成物を基板
に塗布して乾燥する工程を所望の膜厚が得られるまで繰
り返し行った後、７５０℃以下の温度で焼成して結晶化
させることを特徴とする薄膜コンデンサの製造方法。4. A method of manufacturing a thin film capacitor, comprising forming a dielectric thin film on a Si substrate and forming an upper electrode on the dielectric thin film, wherein the Ba 1 according to claim 1 or 2 is formed on the Si substrate. -X Sr
x Ti y O 3 using the composition for forming a thin film of Ba 1-x Sr
A method of forming an x Ti y O 3 dielectric thin film, comprising the steps of applying the Ba 1-x Sr x Ti y O 3 thin film forming composition to a substrate and drying the composition until a desired film thickness is obtained. A method of manufacturing a thin-film capacitor, which comprises repeatedly performing firing and crystallization at a temperature of 750 ° C. or lower. 【請求項５】 請求項４において、焼成を電気炉中にて
３０〜６０分行うことを特徴とする薄膜コンデンサの製
造方法。5. The method for manufacturing a thin film capacitor according to claim 4, wherein firing is performed in an electric furnace for 30 to 60 minutes. 【請求項６】 請求項４において、焼成をＲＴＡ装置に
て１〜３０分行うことを特徴とする薄膜コンデンサの製
造方法。6. The method for manufacturing a thin film capacitor according to claim 4, wherein the firing is performed for 1 to 30 minutes with an RTA apparatus.
JP05932696A 1995-06-09 1996-03-15 Composition for forming Ba1-xSrxTiyO3 thin film, method for forming Ba1-xSrxTiyO3 thin film, and method for manufacturing thin-film capacitor Expired - Lifetime JP3446461B2 (en)

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Title
Ｊｏｕｒｎａｌ ｏｆ Ｍａｔｅｒｉａｌｓ Ｒｅｓｅａｒｃｈ，１９９４年，Ｖｏｌ．９ Ｎｏ．４，９７０−９７９

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