JPH09157008A - Composition for forming thin (barium, strontium) titanium trioxide dielectric film and formation of the same film - Google Patents
Composition for forming thin (barium, strontium) titanium trioxide dielectric film and formation of the same filmInfo
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- JPH09157008A JPH09157008A JP7314100A JP31410095A JPH09157008A JP H09157008 A JPH09157008 A JP H09157008A JP 7314100 A JP7314100 A JP 7314100A JP 31410095 A JP31410095 A JP 31410095A JP H09157008 A JPH09157008 A JP H09157008A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は（Ｂａ，Ｓｒ）Ｔｉ
Ｏ3 誘電体薄膜形成用組成物及び（Ｂａ，Ｓｒ）ＴｉＯ
3 薄膜の形成方法に係り、特に、薄膜コンデンサ又は半
導体集積回路装置の容量絶縁膜（ＤＲＡＭ用キャパシ
タ）等として有用なＢａ1-x Ｓｒx ＴｉＯ3誘電体薄膜
を形成するための組成物及び形成方法に関する。TECHNICAL FIELD The present invention relates to (Ba, Sr) Ti
Composition for forming O 3 dielectric thin film and (Ba, Sr) TiO 3
(3 ) Composition for forming Ba 1-x Sr x TiO 3 dielectric thin film useful as a thin film capacitor or capacitive insulating film (capacitor for DRAM) of semiconductor integrated circuit device, etc. Regarding the method.
【０００２】[0002]
【従来の技術】近年、コンデンサ素子の小型化、半導体
集積回路の高集積化に伴い、これらに適用されるキャパ
シタ絶縁膜には誘電率の高い物質が求められている。こ
の高誘電率の物質としては、ペロブスカイト型の結晶構
造を持つＢａＴｉＯ3 ，ＳｒＴｉＯ3 ，（Ｂａ1-x Ｓｒ
x ）ＴｉＯ3 などのチタン酸バリウム系誘電物質が注目
されており、薄膜形成法としては、スパッタリング法、
ゾルゲル法、ＣＶＤ法などがある。具体的には、次のよ
うなものが提案されている。2. Description of the Related Art In recent years, with downsizing of capacitor elements and higher integration of semiconductor integrated circuits, a material having a high dielectric constant is required for a capacitor insulating film applied to these. Materials having a high dielectric constant include BaTiO 3 , SrTiO 3 , and (Ba 1-x Sr) having a perovskite type crystal structure.
x ) Barium titanate-based dielectric materials such as TiO 3 have been attracting attention.
There are a sol-gel method and a CVD method. Specifically, the following has been proposed.
【０００３】(i) 低級カルボン酸バリウム塩（酢酸バ
リウムが好ましい）及びチタンイソプロポキシドをエチ
レングリコールモノメチルエーテルを含む有機溶媒に溶
解し、これに水を接触させてチタン酸バリウム薄膜形成
用組成物としたもの（特開平１−１０００２４号公
報）。(I) A lower carboxylic acid barium salt (preferably barium acetate) and titanium isopropoxide are dissolved in an organic solvent containing ethylene glycol monomethyl ether and contacted with water to form a barium titanate thin film forming composition. (Japanese Patent Laid-Open No. 1-1000024).
【０００４】(ii) ＢａＣＯ3 ，ＳｒＣＯ3 及びＴｉＯ
2 の混合粉末を８００〜１０００℃で仮焼してターゲッ
トとして用い、基板温度４００〜６００℃でスパッタリ
ング法により（Ｂａ1-x Ｓｒx ）ＴｉＯ3 薄膜を成膜す
る方法。(Ii) BaCO 3 , SrCO 3 and TiO
A method of forming a (Ba 1-x Sr x ) TiO 3 thin film by a sputtering method at a substrate temperature of 400 to 600 ° C. by using the mixed powder of 2 as a target by calcination at 800 to 1000 ° C.
【０００５】なお、特開平７−１７７１３号公報には、
高誘電率で絶縁特性の良好な誘電体薄膜として、（Ｂ
ａ，Ｓｒ）ＴｉＯ3 系誘電体にＭｎ，Ｐｂ，希土類元素
を添加したものが提案されている。Incidentally, Japanese Patent Application Laid-Open No. 7-17713 discloses that
As a dielectric thin film having a high dielectric constant and good insulating properties, (B
It is proposed that Mn, Pb, and a rare earth element are added to an a, Sr) TiO 3 -based dielectric.
【０００６】[0006]
【発明が解決しようとする課題】高誘電率を有するペロ
ブスカイト構造の物質においては欠陥によるキャリアが
発生し易く、特に（Ｂａ1-x Ｓｒx ）ＴｉＯ3 系の材料
においては、比誘電率が高いほどリーク電流が大きいと
いう傾向があることから、その対策が求められている。Carriers due to defects are easily generated in a perovskite structure material having a high dielectric constant, and in particular, a (Ba 1-x Sr x ) TiO 3 -based material has a high relative dielectric constant. Since there is a tendency that the leakage current is larger, a countermeasure for it is required.
【０００７】特開平１−１０００２４号公報記載の方法
のように低級カルボン酸塩を原料に用いるゾルゲル法で
は、結晶化の際に８００℃以上もの高温焼成を必要と
し、この高温による絶縁性の劣化が避けられず、リーク
電流が大きいために実用化には至っていない。なお、こ
の絶縁性の劣化は、高温焼成による膜の急激な収縮や下
地電極の劣化などにより、薄膜内に微少なクラックやボ
イドが発生することによるものと考えられる。このゾル
ゲル法において、比較的熱分解温度の低い原料を用いて
熱処理温度をできる限り抑えて薄膜を形成する方法もあ
るが、比誘電率の低下を解消するに到っていない。In the sol-gel method using a lower carboxylate as a raw material like the method described in Japanese Patent Laid-Open No. 1-100024, a high temperature firing of 800 ° C. or higher is required for crystallization, and the insulation property deteriorates due to this high temperature. Is inevitable, and the leakage current is large, so it has not been put to practical use. It is considered that the deterioration of the insulating property is caused by the generation of minute cracks and voids in the thin film due to the rapid shrinkage of the film due to the high temperature firing and the deterioration of the base electrode. In this sol-gel method, there is also a method of forming a thin film by using a raw material having a relatively low thermal decomposition temperature and suppressing the heat treatment temperature as much as possible, but it has not been able to eliminate the decrease in the relative dielectric constant.
【０００８】スパッタリング法によるＢＳＴ薄膜の形成
でも、基板温度が６００℃以上になるとリーク特性が悪
化することが特開平３−２５７０２０号公報に示されて
いる。It is disclosed in Japanese Patent Laid-Open No. 3-257020 that leak characteristics deteriorate when the substrate temperature is 600 ° C. or higher even when the BST thin film is formed by the sputtering method.
【０００９】このように、高誘電率を有するペロブスカ
イト構造の物質においては、特に欠陥によるキャリアが
発生し易く、比誘電率が高いほどリーク電流が大きいと
いう傾向にあり、このため、従来において、高誘電率と
高絶縁性の両立は難しいとされている。As described above, in a substance having a perovskite structure having a high dielectric constant, carriers are particularly liable to be generated due to defects, and the higher the relative dielectric constant, the larger the leak current tends to be. It is said that it is difficult to achieve both a dielectric constant and high insulation.
【００１０】なお、Ｍｎ，Ｐｂ，希土類元素を添加した
特開平７−１７７１３号公報記載の誘電体薄膜では、こ
れらの元素の添加により、集積回路とした場合、半導体
（トランジスタ）の誤動作を引き起こすおそれがある。In the dielectric thin film described in Japanese Patent Laid-Open No. 7-17713, which contains Mn, Pb, and a rare earth element, the addition of these elements may cause a malfunction of a semiconductor (transistor) in an integrated circuit. There is.
【００１１】本発明は上記従来の問題点を解決し、電子
デバイスにおける様々な用途のキャパシタ材料に有効
な、高誘電率かつ高絶縁性の誘電体薄膜を形成すること
ができる（Ｂａ，Ｓｒ）ＴｉＯ3 薄膜形成用組成物及び
このような（Ｂａ，Ｓｒ）ＴｉＯ3 薄膜形成用組成物を
用いた（Ｂａ，Ｓｒ）ＴｉＯ3 薄膜の形成方法を提供す
ることを目的とする。The present invention can solve the above-mentioned conventional problems and form a dielectric thin film having a high dielectric constant and a high insulating property, which is effective as a capacitor material for various applications in electronic devices (Ba, Sr). and to provide a TiO 3 thin film-forming composition and such (Ba, Sr) TiO 3 using a thin film-forming composition (Ba, Sr) TiO 3 thin film forming method.
【００１２】[0012]
【課題を解決するための手段】請求項１の（Ｂａ，Ｓ
ｒ）ＴｉＯ3 薄膜形成用組成物は、モル比でＢａ：Ｓ
ｒ：Ｔｉ＝（１−ｘ）：ｘ：ｙ（ただし、０≦ｘ≦１．
０，０．９≦ｙ≦１．１）の組成を有する主成分と、該
主成分に対してＳｉとして０．５〜１０モル％のＳｉ成
分とを含むことを特徴とする。[Means for Solving the Problems] (Ba, S of claim 1
r) The composition for forming a TiO 3 thin film has a molar ratio of Ba: S
r: Ti = (1-x): x: y (where 0 ≦ x ≦ 1.
It is characterized by containing a main component having a composition of 0, 0.9 ≦ y ≦ 1.1) and 0.5 to 10 mol% of Si component as Si with respect to the main component.
【００１３】モル比でＢａ：Ｓｒ：Ｔｉ＝（１−ｘ）：
ｘ：ｙ（ただし、０≦ｘ≦１．０，０．９≦ｙ≦１．
１）の組成を有する主成分と、該主成分に対してＳｉと
して０．５〜１０モル％のＳｉ成分とを配合することに
より、組成制御が容易に行えるようになり、低コストな
ゾルゲル法により、高誘電率で絶縁性の高い（Ｂａ，Ｓ
ｒ）ＴｉＯ3 誘電体薄膜を形成することが可能となる。The molar ratio of Ba: Sr: Ti = (1-x):
x: y (where 0 ≦ x ≦ 1.0, 0.9 ≦ y ≦ 1.
By blending a main component having the composition of 1) and 0.5 to 10 mol% of Si component as Si with respect to the main component, composition control can be easily performed, and a low-cost sol-gel method. Has a high dielectric constant and high insulation (Ba, S
r) It becomes possible to form a TiO 3 dielectric thin film.
【００１４】このような（Ｂａ，Ｓｒ）ＴｉＯ3 誘電体
薄膜形成用組成物は、カルボン酸バリウム、カルボン酸
ストロンチウム、チタンアルコキシド及びシリコンアル
コキシドを有機溶剤に混合することにより容易に調製す
ることができる。Such a (Ba, Sr) TiO 3 dielectric thin film forming composition can be easily prepared by mixing barium carboxylate, strontium carboxylate, titanium alkoxide and silicon alkoxide with an organic solvent. .
【００１５】本発明の（Ｂａ，Ｓｒ）ＴｉＯ3 薄膜の形
成方法は、この本発明の（Ｂａ，Ｓｒ）ＴｉＯ3 誘電体
薄膜形成用組成物をスピンコート法により基板に塗布し
た後乾燥し、次いで４５０〜８００℃で焼成することを
特徴とする。この焼成により、Ｓｉ成分はＳｉ酸化物と
なる。The method for forming a (Ba, Sr) TiO 3 thin film of the present invention is as follows. The composition for forming a (Ba, Sr) TiO 3 dielectric thin film of the present invention is applied to a substrate by spin coating and then dried. Then, it is characterized by baking at 450 to 800 ° C. By this firing, the Si component becomes Si oxide.
【００１６】[0016]
【発明の実施の形態】以下に本発明を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
【００１７】本発明の（Ｂａ，Ｓｒ）ＴｉＯ3 誘電体薄
膜形成用組成物は、モル比でＢａ：Ｓｒ：Ｔｉ＝（１−
ｘ）：ｘ：ｙ（ただし、０≦ｘ≦１．０，０．９≦ｙ≦
１．１）の組成を有する主成分と、該主成分に対してＳ
ｉとして０．５〜１０モル％のＳｉ成分とを含むもので
ある。本発明において、このＳｉ成分の含有割合がＳｉ
として上記主成分に対して０．５モル％未満では、Ｓｉ
成分を添加したことによる十分な改善効果が得られず、
絶縁性が低いものとなる。Ｓｉ成分が上記主成分に対し
てＳｉとして１０モル％を超えると絶縁率が低下する。
従って、Ｓｉは上記主成分に対して０．５〜１０モル％
とする。The composition for forming a (Ba, Sr) TiO 3 dielectric thin film of the present invention has a molar ratio of Ba: Sr: Ti = (1-
x): x: y (where 0 ≦ x ≦ 1.0, 0.9 ≦ y ≦
1.1) The main component having the composition of S) and S for the main component
i contains 0.5 to 10 mol% of Si component. In the present invention, the content ratio of this Si component is Si
If less than 0.5 mol% relative to the above main component, Si is
A sufficient improvement effect due to the addition of ingredients cannot be obtained,
The insulation is low. If the Si component exceeds 10 mol% as Si with respect to the above-mentioned main component, the insulation rate decreases.
Therefore, Si is 0.5 to 10 mol% with respect to the above main component.
And
【００１８】このような本発明の（Ｂａ，Ｓｒ）ＴｉＯ
3 誘電体薄膜形成用組成物は、Ｂａ原料としてカルボン
酸バリウムを、Ｓｒ原料としてカルボン酸ストロンチウ
ムを、Ｔｉ原料としてチタンアルコキシドを、Ｓｉ原料
としてシリコンアルコキシドを各々用い、これらを所定
組成となるように、有機溶剤に混合溶解させることによ
り容易に調製することができる。Such (Ba, Sr) TiO 2 of the present invention
(3) The dielectric thin film forming composition uses barium carboxylate as a Ba raw material, strontium carboxylate as an Sr raw material, titanium alkoxide as a Ti raw material, and silicon alkoxide as a Si raw material. It can be easily prepared by mixing and dissolving it in an organic solvent.
【００１９】薄膜原料となるカルボン酸バリウム及び／
又はカルボン酸ストロンチウムを形成するアシルオキシ
基としては、一般式Ｃn Ｈ2n+1ＣＯＯ- （ただし、ｎは
３〜７の整数）で表されるもの、具体的には、ｎ−酪
酸、α−メチル酪酸、ｉ−吉草酸、２−エチル酪酸、
２，２−ジメチル酪酸、３，３−ジメチル酪酸、２，３
−ジメチル酪酸、３−メチルペンタン酸、４−メチルペ
ンタン酸、２−エチルペンタン酸、３−エチルペンタン
酸、２，２−ジメチルペンタン酸、３，３−ジメチルペ
ンタン酸、２，３−ジメチルペンタン酸、２−エチルヘ
キサン酸、３−エチルヘキサン酸から誘導されるアシル
オキシ基を用いるのが好ましい。Barium carboxylate and / or thin film raw material
Alternatively, the acyloxy group forming strontium carboxylate is represented by the general formula C n H 2n + 1 COO − (where n is an integer of 3 to 7), specifically n-butyric acid, α- Methyl butyric acid, i-valeric acid, 2-ethyl butyric acid,
2,2-dimethylbutyric acid, 3,3-dimethylbutyric acid, 2,3
-Dimethylbutyric acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, 2,2-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 2,3-dimethylpentane It is preferable to use an acyloxy group derived from an acid, 2-ethylhexanoic acid or 3-ethylhexanoic acid.
【００２０】上記一般式中、ｎが２以下であると、熱分
解時に炭酸塩を形成し易く、逆にｎが８以上であると、
有機成分の蒸発による重量変化が大きく、クラックのな
い均質な薄膜を形成し得ない。In the above general formula, when n is 2 or less, a carbonate is easily formed during thermal decomposition, and conversely, when n is 8 or more,
The weight change due to evaporation of organic components is large, and a uniform thin film without cracks cannot be formed.
【００２１】なお、カルボン酸バリウム及びカルボン酸
ストロンチウムのアシルオキシ基は、同一であっても異
なるものであっても良い。The acyloxy groups of barium carboxylate and strontium carboxylate may be the same or different.
【００２２】一方、チタンアルコキシドとしては、炭素
数２〜５の直鎖状又は分岐状アルコールのチタンアルコ
キシド、例えば、チタンエトキシド、チタンイソプロポ
キシド、チタンブトキシド、チタンアミロキシドが挙げ
られるが、特に、適当な反応速度であることから、チタ
ンイソプロポキシドを用いるのが好ましい。On the other hand, examples of the titanium alkoxide include titanium alkoxides of linear or branched alcohols having 2 to 5 carbon atoms, such as titanium ethoxide, titanium isopropoxide, titanium butoxide and titanium amyloxide. It is preferable to use titanium isopropoxide because it has an appropriate reaction rate.
【００２３】また、シリコンアルコキシドとしては、炭
素数１〜１５の直鎖状又は分岐状アルコールのシリコン
アルコキシド、例えば、シリコンテトラメトキシド、シ
リコンテトラエトキシド、シリコンテトライソプロポキ
シド、シリコンテトラブトキシド、シリコンテトラアミ
ロキシド等が挙げられるが、特に、適当な反応速度であ
ることから、シリコンテトラエトキシドを用いるのが好
ましい。As the silicon alkoxide, a silicon alkoxide of a linear or branched alcohol having 1 to 15 carbon atoms, for example, silicon tetramethoxide, silicon tetraethoxide, silicon tetraisopropoxide, silicon tetrabutoxide, silicon. Although tetraamyloxide and the like can be mentioned, it is particularly preferable to use silicon tetraethoxide because of its suitable reaction rate.
【００２４】これらの薄膜原料を溶解させる有機溶剤と
しては、エステル及び／又はアルコール、或いは、エス
テル及び／又はアルコールに更にカルボン酸を混合した
混合溶剤を用いることができる。As the organic solvent for dissolving these thin film raw materials, an ester and / or alcohol, or a mixed solvent obtained by further mixing a carboxylic acid with the ester and / or alcohol can be used.
【００２５】有機溶剤のエステルとしては、酢酸エチ
ル、酢酸プロピル、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、
酢酸イソアミルを用いるのが好ましく、アルコールとし
ては、１−プロパノール、２−プロパノール、１−ブタ
ノール、２−ブタノール、イソ−ブチルアルコール、１
−ペンタノール、２−ペンタノール、２−メチル−２−
ペンタノール、イソ−アミルアルコールを用いるのが好
適である。また、カルボン酸としては、前記カルボン酸
バリウム及び／又はカルボン酸ストロンチウムを構成す
るアシルオキシ基を含むカルボン酸を用いるのが好まし
い。Examples of the organic solvent ester include ethyl acetate, propyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, isobutyl acetate and n-acetate.
Amyl, sec-amyl acetate, tert-amyl acetate,
It is preferable to use isoamyl acetate, and as the alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butyl alcohol, 1
-Pentanol, 2-pentanol, 2-methyl-2-
Pentanol and iso-amyl alcohol are preferably used. Further, as the carboxylic acid, it is preferable to use a carboxylic acid containing an acyloxy group that constitutes the barium carboxylate and / or the strontium carboxylate.
【００２６】本発明の（Ｂａ，Ｓｒ）ＴｉＯ3 誘電体薄
膜形成用組成物は、このような有機溶剤に対して、薄膜
原料のカルボン酸バリウム、カルボン酸ストロンチウム
及びチタンアルコキシドを、所定の組成比で、酸化物換
算の合計濃度が４〜１０重量％となるように溶解させる
と共に、所定量のシリコンアルコキシドを添加混合する
ことにより調製される。The composition for forming a (Ba, Sr) TiO 3 dielectric thin film of the present invention comprises barium carboxylate, strontium carboxylate and titanium alkoxide, which are thin film raw materials, in a predetermined composition ratio to such an organic solvent. Then, it is prepared by dissolving so that the total concentration in terms of oxide becomes 4 to 10% by weight, and adding and mixing a predetermined amount of silicon alkoxide.
【００２７】このような本発明の（Ｂａ，Ｓｒ）ＴｉＯ
3 誘電体薄膜形成用組成物により（Ｂａ，Ｓｒ）ＴｉＯ
3 薄膜を形成するには、スピンコート法により、Ｓｉ，
Ｐｔ／Ｔｉ／ＳｉＯ2 ／Ｓｉ，Ｐｔ／Ｔａ／ＳｉＯ2 ／
Ｓｉ，Ｐｔ／ＳｉＯ2 ／Ｓｉ，Ｒｕ／ＲｕＯ2 ／ＳｉＯ
2 ／Ｓｉ，ＲｕＯ2 ／Ｓｉ，ＲｕＯ2 ／Ｒｕ／ＳｉＯ2
／Ｓｉ，Ｉｒ／ＩｒＯ2 ／Ｓｉ，Ｐｔ／Ｉｒ／ＩｒＯ2
／Ｓｉ，Ｐｔ／ＩｒＯ2 ／Ｓｉ等の基板上に本発明の組
成物を塗布し、乾燥（仮焼成）及び本焼成を行う。な
お、１回の塗布では、所望の膜厚が得られない場合に
は、塗布、乾燥の工程を複数回繰り返し行った後、本焼
成を行う。ここで、乾燥は、１５０〜４００℃で行わ
れ、本焼成は４５０〜８００℃で３０分〜２時間程度行
われる。Such (Ba, Sr) TiO 2 of the present invention
(3) Dielectric thin film forming composition (Ba, Sr) TiO
3 To form a thin film, spin coating is used to form Si,
Pt / Ti / SiO 2 / Si, Pt / Ta / SiO 2 /
Si, Pt / SiO 2 / Si, Ru / RuO 2 / SiO
2 / Si, RuO 2 / Si, RuO 2 / Ru / SiO 2
/ Si, Ir / IrO 2 / Si, Pt / Ir / IrO 2
The composition of the present invention is applied onto a substrate such as / Si, Pt / IrO 2 / Si, and dried (preliminary firing) and main firing are performed. If a desired film thickness cannot be obtained by one application, the application and drying steps are repeated a plurality of times, and then the main firing is performed. Here, the drying is performed at 150 to 400 ° C., and the main firing is performed at 450 to 800 ° C. for about 30 minutes to 2 hours.
【００２８】[0028]
【実施例】以下に実施例及び比較例を挙げて本発明をよ
り具体的に説明するが、本発明はその要旨を超えない限
り、以下の実施例に限定されるものではない。The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist.
【００２９】実施例１〜３，比較例１〜３ 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及びチタンイソプロポキ
シドを用い、これらを組成比Ｂａ0.7 Ｓｒ0.3ＴｉＯ3
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、酢酸イソアミルの有機溶剤
中に溶解させた。Examples 1 to 3 and Comparative Examples 1 to 3 Barium 2-ethylhexanoate, strontium 2-ethylhexanoate and titanium isopropoxide were used as thin film raw materials, and these were used in a composition ratio of Ba 0.7 Sr 0.3 TiO 3.
And was dissolved in an organic solvent of isoamyl acetate so that the total concentration of oxides of the composition was 7% by weight.
【００３０】この溶液に更に、シリコンテトラエトキシ
ドを表１に示す割合で添加した後（ただし、比較例１で
はシリコンテトラエトキシド添加せず）、１時間還流さ
せることによって十分に均一化させて、本発明の薄膜形
成用組成物を調製した。Silicon tetraethoxide was further added to this solution at a ratio shown in Table 1 (however, in Comparative Example 1, silicon tetraethoxide was not added), and the mixture was refluxed for 1 hour to sufficiently homogenize the solution. A thin film-forming composition of the present invention was prepared.
【００３１】この薄膜形成用組成物をスピンコート法に
よりチタン白金基板上に塗布し、３００℃で１０分間乾
燥する塗布、乾燥工程を３回繰り返し、最後に５５０℃
で１時間焼成して、Ｂａ0.7 Ｓｒ0.3 ＴｉＯ3 薄膜を形
成した。この薄膜に金で上部電極を蒸着し、比誘電率、
リーク電流密度及び誘電損失を測定し、結果を表１に示
した。This thin film-forming composition is applied on a titanium-platinum substrate by spin coating and dried at 300 ° C. for 10 minutes. The coating and drying steps are repeated 3 times, and finally 550 ° C.
And baked for 1 hour to form a Ba 0.7 Sr 0.3 TiO 3 thin film. The upper electrode is vapor-deposited on this thin film with gold,
The leakage current density and the dielectric loss were measured, and the results are shown in Table 1.
【００３２】[0032]
【表１】 [Table 1]
【００３３】実施例４〜６，比較例４〜６ 薄膜原料を組成比Ｂａ0.5 Ｓｒ0.5 ＴｉＯ3 となるよう
に溶解させたこと以外は、それぞれ実施例１〜３及び比
較例１〜３と同様に行って、比誘電率、リーク電流密度
及び誘電損失を測定し、結果を表２に示した。Examples 4 to 6 and Comparative Examples 4 to 6 The same as Examples 1 to 3 and Comparative Examples 1 to 3 except that the thin film raw material was dissolved to have a composition ratio of Ba 0.5 Sr 0.5 TiO 3. Then, the relative dielectric constant, the leak current density and the dielectric loss were measured, and the results are shown in Table 2.
【００３４】[0034]
【表２】 [Table 2]
【００３５】実施例７〜９，比較例７〜９ 薄膜原料を組成比Ｂａ0.3 Ｓｒ0.7 ＴｉＯ3 となるよう
に溶解させたこと以外は、それぞれ実施例１〜３及び比
較例１〜３と同様に行って、比誘電率、リーク電流密度
及び誘電損失を測定し、結果を表３に示した。Examples 7 to 9 and Comparative Examples 7 to 9 The same as Examples 1 to 3 and Comparative Examples 1 to 3, except that the thin film raw material was dissolved to have a composition ratio of Ba 0.3 Sr 0.7 TiO 3. Then, the relative dielectric constant, the leakage current density and the dielectric loss were measured, and the results are shown in Table 3.
【００３６】[0036]
【表３】 [Table 3]
【００３７】実施例１０〜１２，比較例１０〜１２ 薄膜原料を組成比ＢａＴｉＯ3 となるように溶解させた
こと以外は、それぞれ実施例１〜３及び比較例１〜３と
同様に行って、比誘電率、リーク電流密度及び誘電損失
を測定し、結果を表４に示した。Examples 10 to 12 and Comparative Examples 10 to 12 The same procedure as in Examples 1 to 3 and Comparative Examples 1 to 3 was carried out except that the thin film raw materials were dissolved so that the composition ratio was BaTiO 3 . The relative permittivity, leak current density and dielectric loss were measured, and the results are shown in Table 4.
【００３８】[0038]
【表４】 [Table 4]
【００３９】実施例１３〜１５，比較例１３〜１５ 薄膜原料を組成比ＳｒＴｉＯ3 となるように溶解させた
こと以外は、それぞれ実施例１〜３及び比較例１〜３と
同様に行って、比誘電率、リーク電流密度及び誘電損失
を測定し、結果を表５に示した。Examples 13 to 15 and Comparative Examples 13 to 15 The same procedure as in Examples 1 to 3 and Comparative Examples 1 to 3 was carried out, except that the thin film raw materials were dissolved so that the composition ratio was SrTiO 3 . The relative permittivity, leak current density and dielectric loss were measured, and the results are shown in Table 5.
【００４０】[0040]
【表５】 [Table 5]
【００４１】表１〜５より明らかなように、本発明に従
って、所定量のＳｉを配合することにより、高誘電率で
しかも高絶縁性の（Ｂａ，Ｓｒ）ＴｉＯ3 誘電体薄膜を
得ることができる。As is clear from Tables 1 to 5, according to the present invention, by mixing a predetermined amount of Si, it is possible to obtain a (Ba, Sr) TiO 3 dielectric thin film having a high dielectric constant and a high insulating property. it can.
【００４２】[0042]
【発明の効果】以上詳述した通り、本発明の（Ｂａ，Ｓ
ｒ）ＴｉＯ3 誘電体薄膜形成用組成物及び（Ｂａ，Ｓ
ｒ）ＴｉＯ3 薄膜の形成方法によれば、安価なゾルゲル
法により、電子デバイスにおける様々な用途のキャパシ
タ材料として有用な、高誘電率かつ高絶縁性の（Ｂａ，
Ｓｒ）ＴｉＯ3 誘電体薄膜が提供される。As described above in detail, (Ba, S of the present invention
r) TiO 3 dielectric thin film forming composition and (Ba, S
r) According to the method for forming a TiO 3 thin film, a high dielectric constant and a high insulating property (Ba,
A Sr) TiO 3 dielectric thin film is provided.
Claims (3)
ｘ）：ｘ：ｙ（ただし、０≦ｘ≦１．０，０．９≦ｙ≦
１．１）の組成を有する主成分と、該主成分に対してＳ
ｉとして０．５〜１０モル％のＳｉ成分とを含むことを
特徴とする（Ｂａ，Ｓｒ）ＴｉＯ3 誘電体薄膜形成用組
成物。1. A molar ratio of Ba: Sr: Ti = (1-
x): x: y (where 0 ≦ x ≦ 1.0, 0.9 ≦ y ≦
1.1) The main component having the composition of S) and S for the main component
A composition for forming a (Ba, Sr) TiO 3 dielectric thin film, which comprises 0.5 to 10 mol% of Si component as i.
ンチウム、チタンアルコキシド及びシリコンアルコキシ
ドを有機溶剤に混合してなることを特徴とする請求項１
に記載の（Ｂａ，Ｓｒ）ＴｉＯ3 誘電体薄膜形成用組成
物。2. A barium carboxylate, strontium carboxylate, titanium alkoxide and silicon alkoxide are mixed in an organic solvent.
The composition for forming a (Ba, Sr) TiO 3 dielectric thin film as described in 1.
ＴｉＯ3 誘電体薄膜形成用組成物を、スピンコート法に
より基板に塗布した後乾燥し、次いで４５０〜８００℃
で焼成することを特徴とする（Ｂａ，Ｓｒ）ＴｉＯ3 薄
膜の形成方法。3. The (Ba, Sr) according to claim 1 or 2.
The composition for forming a TiO 3 dielectric thin film is applied to a substrate by a spin coating method and then dried, and then 450 to 800 ° C.
A method of forming a (Ba, Sr) TiO 3 thin film, characterized by firing at
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31410095A JP3146961B2 (en) | 1995-12-01 | 1995-12-01 | Composition for forming (Ba, Sr) TiO3 dielectric thin film and method for forming (Ba, Sr) TiO3 thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31410095A JP3146961B2 (en) | 1995-12-01 | 1995-12-01 | Composition for forming (Ba, Sr) TiO3 dielectric thin film and method for forming (Ba, Sr) TiO3 thin film |
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| Publication Number | Publication Date |
|---|---|
| JPH09157008A true JPH09157008A (en) | 1997-06-17 |
| JP3146961B2 JP3146961B2 (en) | 2001-03-19 |
Family
ID=18049246
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31410095A Expired - Lifetime JP3146961B2 (en) | 1995-12-01 | 1995-12-01 | Composition for forming (Ba, Sr) TiO3 dielectric thin film and method for forming (Ba, Sr) TiO3 thin film |
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| Country | Link |
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| JP (1) | JP3146961B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001084698A1 (en) * | 2000-05-03 | 2001-11-08 | Raytheon Company | Fixed frequency regulation circuit employing a voltage variable dielectric capacitor |
| EP1758152A2 (en) | 2005-08-24 | 2007-02-28 | Tokyo Electron Limited | Capacitor and manufacturing method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2402982B1 (en) | 2010-07-01 | 2021-04-21 | Mitsubishi Materials Corporation | Method for manufacturing thin film capacitor and thin film capacitor obtained by the same |
-
1995
- 1995-12-01 JP JP31410095A patent/JP3146961B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001084698A1 (en) * | 2000-05-03 | 2001-11-08 | Raytheon Company | Fixed frequency regulation circuit employing a voltage variable dielectric capacitor |
| AU762082B2 (en) * | 2000-05-03 | 2003-06-19 | Raytheon Company | Fixed frequency regulation circuit employing a voltage variable dielectric capacitor |
| EP1758152A2 (en) | 2005-08-24 | 2007-02-28 | Tokyo Electron Limited | Capacitor and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3146961B2 (en) | 2001-03-19 |
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