JP3129175B2 - Method for manufacturing (Ba, Sr) TiO3 thin film capacitor - Google Patents
Method for manufacturing (Ba, Sr) TiO3 thin film capacitorInfo
- Publication number
- JP3129175B2 JP3129175B2 JP07307395A JP30739595A JP3129175B2 JP 3129175 B2 JP3129175 B2 JP 3129175B2 JP 07307395 A JP07307395 A JP 07307395A JP 30739595 A JP30739595 A JP 30739595A JP 3129175 B2 JP3129175 B2 JP 3129175B2
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- thin film
- tio
- film capacitor
- main component
- manufacturing
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- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
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- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は（Ｂａ，Ｓｒ）Ｔｉ
Ｏ３薄膜コンデンサの製造方法に係り、特に、半導体集
積回路等に有用な、高誘電率で高絶縁性の（Ｂａ，Ｓ
ｒ）ＴｉＯ３薄膜コンデンサの製造方法に関する。The present invention relates to (Ba, Sr) Ti
O 3 relates to a method of manufacturing a thin film capacitor, in particular, useful for a semiconductor integrated circuit or the like, a high dielectric constant high insulation (Ba, S
r) it relates to a method for producing TiO 3 thin film capacitor.
【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、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。2. Description of the Related Art In recent years, with the miniaturization of capacitor elements and the high integration of semiconductor integrated circuits, a material having a high dielectric constant is required for a capacitor insulating film.
【０００３】従来、集積回路などに用いられる薄膜コン
デンサにはＳｉＯ２，Ｓｉ３Ｎ４，Ａｌ２Ｏ３などの材
料が用いられている。これらの物質は高い絶縁性を有す
る反面、比誘電率は１０程度と小さい。Conventionally, materials such as SiO 2 , Si 3 N 4 and Al 2 O 3 have been used for thin film capacitors used for integrated circuits and the like. While these substances have high insulating properties, their relative dielectric constants are as small as about 10.
【０００４】ところで、コンデンサの静電容量は比誘電
率と表面積（電極面積）に比例し、膜厚に反比例する。
従って、薄膜コンデンサの小型化のためには膜厚の減少
には限界があるため、比誘電率の大きな誘電体物質が必
要となる。The capacitance of a capacitor is proportional to the relative permittivity and the surface area (electrode area), and is inversely proportional to the film thickness.
Accordingly, there is a limit to the reduction of the film thickness in order to reduce the size of the thin film capacitor, and a dielectric material having a large relative dielectric constant is required.
【０００５】比誘電率の大きな物質としては、従来、ペ
ロブスカイト型の結晶構造を持つＢａＴｉＯ３，ＳｒＴ
ｉＯ３，（Ｂａ１−ｘＳｒｘ）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、その薄膜形成法
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。As a substance having a large relative dielectric constant, conventionally, BaTiO 3 , SrT having a perovskite type crystal structure is used.
iO 3, (Ba 1-x Sr x) and barium titanate-based dielectric material such as TiO 3 is focused, as its thin film forming method, a sputtering method, a sol-gel method, and a CVD method. Specifically, the following has been proposed.
【０００６】(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 composition for forming a barium titanate thin film by dissolving a barium lower carboxylate (preferably barium acetate) and titanium isopropoxide in an organic solvent containing ethylene glycol monomethyl ether, and contacting water with the dissolved solution. (JP-A-1-1000024).
【０００７】(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−ｘＳｒｘ）ＴｉＯ３薄膜を成膜
する方法。(Ii) BaCO 3 , SrCO 3 and TiO
A method of calcining the mixed powder of No. 2 at 800 to 1000 ° C. and using it as a target, and forming a (Ba 1-x Sr x ) TiO 3 thin film by a sputtering method at a substrate temperature of 400 to 600 ° C.
【０００８】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。[0008] JP-A-7-17713 discloses that
As a dielectric thin film having a high dielectric constant and good insulation properties, (B
a, Sr) Mn in TiO 3 based dielectric, Pb, those obtained by adding a rare earth element has been proposed.
【０００９】[0009]
【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−ｘＳｒｘ）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。In a substance having a perovskite structure having a high dielectric constant, carriers due to defects are easily generated. 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 larger the leakage current is, the countermeasures are required.
【００１０】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
部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 as in the method described in Japanese Patent Application Laid-Open No. 1-1000024, high-temperature sintering of 800 ° C. or more is required during crystallization, and the insulation property is deteriorated due to this high temperature However, it has not been practically used due to the large leakage current. It is considered that the deterioration of the insulating property is caused by generation of minute cracks and voids in the thin film due to abrupt shrinkage of the film due to high-temperature baking and deterioration of the lower electrode. In this sol-gel method, there is a method of forming a thin film using a raw material having a relatively low thermal decomposition temperature while keeping the heat treatment temperature as low as possible. However, this does not solve the problem of a decrease in the relative dielectric constant.
【００１１】スパッタリング法によるＢＳＴ薄膜の形成
でも、高い比誘電率を得るためには７００℃以上の成膜
温度が必要であるが、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。Even when a BST thin film is formed by a sputtering method, a film forming temperature of 700 ° C. or more is required to obtain a high relative dielectric constant. However, when the substrate temperature is 600 ° C. or more, the leak characteristics deteriorate. This is disclosed in Japanese Unexamined Patent Publication No. 3-257020.
【００１２】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 due to defects are particularly likely to occur, and the higher the relative dielectric constant, the larger the leak current tends to be. It is considered difficult to achieve both dielectric constant and high insulation.
【００１３】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 JP-A-7-17713 to which Mn, Pb and rare earth elements are added, when these elements are added, an integrated circuit may cause a malfunction of a semiconductor (transistor). There is.
【００１４】本発明は上記従来の問題点を解決し、比誘
電率、即ち、コンデンサ容量を低下させることなく絶縁
性を向上させ、電子デバイスにおける様々な用途に有効
な（Ｂａ，Ｓｒ）ＴｉＯ３薄膜コンデンサの製造方法を
提供することを目的とする。The present invention solves the above-mentioned conventional problems, improves the dielectric constant without lowering the relative dielectric constant, ie, the capacitance of the capacitor, and is effective for various uses in electronic devices (Ba, Sr) TiO 3. and to provide a method of manufacturing a thin film capacitor.
【００１５】[0015]
【課題を解決するための手段】請求項１の（Ｂａ，Ｓ
ｒ）ＴｉＯ ３ 薄膜コンデンサの製造方法は、基板上に下
部電極、誘電体薄膜及び上部電極を順次積層形成して薄
膜コンデンサを製造する方法であって、該誘電体薄膜の
形成に当り、（Ｂａ １−ｘ Ｓｒ ｘ ）ＴｉＯ ３ （ただし、
０≦ｘ≦１．０）で表される主成分と、該主成分に対し
てＳｉとして０．１〜１０モル％のＳｉ成分とを含む有
機金属化合物溶液を、前記下部電極上に塗布、乾燥して
仮焼した後、４５０〜８００℃で焼成することにより、
（Ｂａ １−ｘ Ｓｒ ｘ ）ＴｉＯ ３ （ただし、０≦ｘ≦１．
０）で表される主成分と、該主成分に対してＳｉとして
０．１〜１０モル％のＳｉ成分とからなるペロブスカイ
ト構造を有する誘電体薄膜を形成することを特徴とす
る。According to the first aspect of the present invention, (Ba, S
r) The manufacturing method of the TiO 3 thin film capacitor is
Part electrode, dielectric thin film and upper electrode
A method for manufacturing a membrane capacitor, comprising:
Upon formation, (Ba 1-x Sr x ) TiO 3 (where
0 ≦ x ≦ 1.0) and a main component represented by
Containing 0.1 to 10 mol% of Si component as Si
Machine metal compound solution, applied on the lower electrode, dried
After calcining, by calcining at 450 to 800 ° C,
(Ba 1-x Sr x ) TiO 3 (where 0 ≦ x ≦ 1.
0) and the main component represented by Si
Perovskite comprising 0.1 to 10 mol% of Si component
A dielectric thin film having a gate structure .
【００１６】請求項２の（Ｂａ，Ｓｒ）ＴｉＯ ３ 薄膜コ
ンデンサの製造方法は、基板上に下部電極、誘電体薄膜
及び上部電極を順次積層形成して薄膜コンデンサを製造
する方法において、該誘電体薄膜の形成に当り、（Ｂａ
１−ｘ Ｓｒ ｘ ）ＴｉＯ ３ （ただし、０≦ｘ≦１．０）で
表される主成分と、該主成分に対してＳｉとして０．１
〜１０モル％のＳｉ成分とを含むターゲットを用いて、
基板温度４００〜８００℃で前記下部電極上にスパッタ
リングを行うことを特徴とする。 The (Ba, Sr) TiO 3 thin film of claim 2
The method of manufacturing capacitors consists of a lower electrode and a dielectric thin film on a substrate.
And a top electrode are sequentially laminated to manufacture a thin film capacitor
In forming the dielectric thin film, (Ba)
1−x Sr x ) TiO 3 (where 0 ≦ x ≦ 1.0)
A main component represented by 0.1% as Si with respect to the main component.
Using a target containing 10 to 10 mol% of a Si component,
Sputtering on the lower electrode at a substrate temperature of 400 to 800 ° C
It is characterized by performing a ring.
【００１７】（Ｂａ１−ｘＳｒｘ）ＴｉＯ３（ただし、
０≦ｘ≦１．０）で表されるペロブスカイト構造の主成
分に対してＳｉとして０．１〜１０モル％のＳｉ成分を
添加することにより、熱処理の際の焼結性が向上し、結
果的には、比較的低い処理温度にて、高誘電率（高容
量）、高絶縁性（低リーク電流密度）で、耐圧性に優れ
る（Ｂａ，Ｓｒ）ＴｉＯ３薄膜コンデンサを形成するこ
とが可能となる。 (Ba 1-x Sr x ) TiO 3 (where,
0 ≦ x ≦ 1. By adding 0.1 to 10 mol% of Si component as Si to the main component of the perovskite structure represented by 0) , sinterability at the time of heat treatment is improved, and as a result, relatively At a low processing temperature, it is possible to form a (Ba, Sr) TiO 3 thin film capacitor having a high dielectric constant (high capacity), a high insulating property (low leakage current density), and an excellent pressure resistance .
【００１８】なお、上記請求項１の焼成により、Ｓｉ成
分はＳｉ酸化物となる。By the calcination of claim 1 , the Si component becomes a Si oxide.
【００１９】[0019]
【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.
【００２０】本発明で製造される（Ｂａ，Ｓｒ）ＴｉＯ
３薄膜コンデンサは、（Ｂａ１−ｘＳｒｘ）ＴｉＯ
３（ただし、０≦ｘ≦１．０）で表される主成分と、該
主成分に対してＳｉとして０．１〜１０モル％のＳｉ成
分とからなるペロブスカイト構造を有する誘電体薄膜を
有するものである。(Ba, Sr) TiO manufactured by the present invention
The three thin-film capacitors are made of (Ba 1-x Sr x ) TiO
3 A dielectric thin film having a perovskite structure comprising a main component represented by 0 (x ≦ 1.0) and a Si component of 0.1 to 10 mol% as Si with respect to the main component. Things.
【００２１】この誘電体薄膜において、上記主成分に対
するＳｉ成分の割合がＳｉとして０．１モル％未満で
は、Ｓｉを配合したことによる焼結性の改善効果が十分
ではなく、絶縁性が低くリーク電流が大きいものとな
る。Ｓｉ成分が上記主成分に対してＳｉとして１０モル
％を超えると絶縁性は優れるが静電容量が小さくなる。
従って、Ｓｉは上記主成分に対して０．１〜１０モル％
とする。In this dielectric thin film, if the ratio of the Si component to the above main component is less than 0.1 mol% as Si, the effect of improving the sinterability due to the incorporation of Si is not sufficient, and the insulating property is low and the leakage is low. The current becomes large. When the Si component exceeds 10 mol% as Si with respect to the above-mentioned main component, the insulating property is excellent, but the capacitance becomes small.
Therefore, Si is 0.1 to 10 mol% based on the above main component.
And
【００２２】このような誘電体薄膜は、本発明の方法に
従って、次の又はの方法で形成することができる。 Such a dielectric thin film can be formed by the following method according to the method of the present invention.
【００２３】 ゾルゲル法：（Ｂａ１−ｘＳｒｘ）Ｔ
ｉＯ３（ただし、０≦ｘ≦１．０）で表される主成分
と、該主成分に対してＳｉとして０．１〜１０モル％の
Ｓｉ成分とを含む有機金属化合物溶液を、前記下部電極
上に塗布、乾燥して仮焼した後、４５０〜８００℃で焼
成する。Sol-gel method: (Ba 1-x Sr x ) T
An organometallic compound solution containing a main component represented by iO 3 (where 0 ≦ x ≦ 1.0) and a Si component of 0.1 to 10 mol% as Si with respect to the main component was added to the lower part. After coating on the electrode, drying and calcining, baking is performed at 450 to 800 ° C.
【００２４】 スパッタリング法：（Ｂａ１−ｘＳｒ
ｘ）ＴｉＯ３（ただし、０≦ｘ≦１．０）で表される主
成分と、該主成分に対してＳｉとして０．１〜１０モル
％のＳｉ成分とを含むターゲットを用いて、基板温度４
００〜８００℃で前記下部電極上にスパッタリングを行
う。Sputtering method: (Ba 1-x Sr
x ) using a target containing a main component represented by TiO 3 (where 0 ≦ x ≦ 1.0) and a Si component of 0.1 to 10 mol% as Si with respect to the main component, Temperature 4
Sputtering is performed on the lower electrode at 00 to 800 ° C.
【００２５】上記のゾルゲル法においては、具体的に
は、まず、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調製された有機金
属化合物の溶液を、基板上に形成された下部電極上にス
ピンコート法等により塗布する。In the sol-gel method described above, first, barium carboxylate is used as a Ba raw material,
Using strontium carboxylate as a raw material, titanium alkoxide as a Ti raw material, and silicon alkoxide as a Si raw material, so that these have a predetermined composition,
A solution of an organometallic compound prepared by mixing and dissolving in an organic solvent is applied to a lower electrode formed on a substrate by a spin coating method or the like.
【００２６】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ＣｎＨ２ｎ＋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, as an acyloxy group forming strontium carboxylate, a general formula C n H 2n + 1 COO − (however,
n is an integer of 3 to 7), specifically, n-
Butyric acid, α-methylbutyric acid, i-valeric acid, 2-ethylbutyric 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.
【００２７】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 at the time of thermal decomposition. Conversely, when n is 8 or more,
The change in weight due to evaporation of the organic components is large, and a homogeneous film without cracks cannot be formed.
【００２８】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.
【００２９】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, for example, titanium ethoxide, titanium isopropoxide, titanium butoxide, and titanium amiloxide. It is preferable to use titanium isopropoxide since the reaction rate is appropriate.
【００３０】また、シリコンアルコキシドとしては、炭
素数１〜５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、シリコンテトラブトキシド、シ
リコンテトラアミロキシドが挙げられるが、特に、適度
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。Examples of the silicon alkoxide include silicon alkoxides of linear or branched alcohols having 1 to 5 carbon atoms, for example, silicon tetramethoxide, silicon tetraethoxide, silicon tetrabutoxide, and silicon tetraamyloxide. However, it is particularly preferable to use silicon tetraethoxide because of its moderate reaction rate.
【００３１】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 materials, an ester and / or an alcohol, or a mixed solvent obtained by further mixing a carboxylic acid with the ester and / or an alcohol can be used.
【００３２】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 ester of the organic solvent 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,
-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 constituting the barium carboxylate and / or strontium carboxylate.
【００３３】本発明においては、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。In the present invention, barium carboxylate, strontium carboxylate and titanium alkoxide as thin film raw materials are added to such an organic solvent at a predetermined compositional ratio so that the total concentration in terms of oxide is 4 to 10% by weight. And a predetermined amount of silicon alkoxide is added and mixed.
【００３４】このようにして調製された有機金属化合物
の溶液を基板の下部電極上に塗布し、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、乾燥及び仮焼成の工程を複数
回繰り返し行った後、本焼成を行う。ここで、仮焼成
は、１５０〜４００℃で行われ、本焼成は４５０〜８０
０℃で３０分〜２時間程度行われる。The solution of the organometallic compound prepared as described above is applied on the lower electrode of the substrate, and dried, pre-baked, and main-baked. If the desired film thickness cannot be obtained by one application, the steps of application, drying, and preliminary firing are repeated a plurality of times, and then main firing is performed. Here, the preliminary firing is performed at 150 to 400 ° C., and the final firing is performed at 450 to 80 ° C.
This is performed at 0 ° C. for about 30 minutes to 2 hours.
【００３５】一方、のスパッタリング法においては、
具体的には、まず、炭酸バリウム（ＢａＣＯ３）、炭酸
ストロンチウム（ＳｒＣＯ３）、二酸化チタン（ＴｉＯ
２）及び二酸化珪素（ＳｉＯ２）を所定の組成となるよ
うに混合し、８００〜１０００℃で仮焼して粉末ターゲ
ットを製造する。そして、このターゲットを用いて、基
板上に形成された下部電極上にスパッタリング法により
所望の膜厚の誘電体薄膜を形成する。このスパッタリン
グ条件は基板温度４００〜８００℃とし、スパッタガス
はＡｒ：１×１０−２〜１×１０−５Ｔｏｒｒ，Ｏ２：
１×１０−２〜１×１０−５Ｔｏｒｒで行うのが好まし
い。On the other hand, in the sputtering method,
Specifically, first, barium carbonate (BaCO 3 ), strontium carbonate (SrCO 3 ), titanium dioxide (TiO 2)
2 ) and silicon dioxide (SiO 2 ) are mixed so as to have a predetermined composition, and calcined at 800 to 1000 ° C. to produce a powder target. Then, using this target, a dielectric thin film having a desired thickness is formed on the lower electrode formed on the substrate by a sputtering method. The sputtering conditions were such that the substrate temperature was 400 to 800 ° C., and the sputtering gas was Ar: 1 × 10 −2 to 1 × 10 −5 Torr, O 2 :
It is preferably performed at 1 × 10 −2 to 1 × 10 −5 Torr.
【００３６】なお、本発明において、誘電体薄膜は膜厚
５００〜３０００Å程度とするのが好ましい。In the present invention, the dielectric thin film preferably has a thickness of about 500 to 3000 °.
【００３７】本発明において、基板としては、シリコ
ン、サファイア、石英ガラス、ジルコニア等を用いるこ
とができる。また、この基板上に形成される下部電極及
び上部電極としては、白金、金、銀、銅、クロム、アル
ミニウム、タンタル、イリジウム、ルテニウム、白金−
チタン、白金−タンタル、白金−イリジウム等が一般的
であり、これらの電極は通常の場合、スパッタリング法
により形成される。In the present invention, silicon, sapphire, quartz glass, zirconia or the like can be used as the substrate. The lower electrode and the upper electrode formed on the substrate include platinum, gold, silver, copper, chromium, aluminum, tantalum, iridium, ruthenium, platinum-
Titanium, platinum-tantalum, platinum-iridium and the like are generally used, and these electrodes are usually formed by a sputtering method.
【００３８】[0038]
【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.
【００３９】実施例１〜５ シリコン基板上に、下部電極として白金膜をスパッタリ
ング法により形成し、その上に、下記手順で誘電体薄膜
を形成した。Examples 1 to 5 On a silicon substrate, a platinum film was formed as a lower electrode by a sputtering method, and a dielectric thin film was formed thereon by the following procedure.
【００４０】即ち、まず、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（Ｂａ１−ｘＳ
ｒｘ）ＴｉＯ３において、ｘが表１に示す値となるよう
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。That is, first, barium 2-ethylhexanoate, strontium 2-ethylhexanoate and titanium isopropoxide were used and their composition ratio (Ba 1−x S
r x ) In TiO 3 , x was dissolved in an organic solvent of isoamyl acetate so that x had a value shown in Table 1 and a total concentration in terms of oxide of the composition was 7% by weight. .
【００４１】この溶液に更に、シリコンテトラエトキシ
ドを、（Ｂａ１−ｘＳｒｘ）ＴｉＯ３の主成分に対して
Ｓｉとして５モル％の割合で添加した後、１時間還流さ
せることによって十分に均一化させて薄膜形成用組成物
を調製した。Further, silicon tetraethoxide was further added to this solution at a ratio of 5 mol% as Si with respect to the main component of (Ba 1-x Sr x ) TiO 3 , and then refluxed for 1 hour. The composition for thin film formation was prepared by homogenization.
【００４２】この薄膜形成用組成物をスピンコート法に
より下部電極上に塗布して乾燥、３００℃で１０分間仮
焼成する塗布、乾燥及び仮焼成工程を繰り返し、最後に
６００℃で０．５時間焼成して、膜厚が２０００Åの
（Ｂａ１−ｘＳｒｘ）ＴｉＯ３誘電体薄膜を形成した。The composition for forming a thin film is applied on the lower electrode by spin coating, dried, and temporarily baked at 300 ° C. for 10 minutes. The coating, drying and calcination steps are repeated, and finally at 600 ° C. for 0.5 hour. By firing, a (Ba 1-x Sr x ) TiO 3 dielectric thin film having a thickness of 2000 ° was formed.
【００４３】この誘電体薄膜に上部電極として白金膜を
スパッタリング法で形成して薄膜コンデンサを作製し
た。On this dielectric thin film, a platinum film was formed as an upper electrode by a sputtering method to produce a thin film capacitor.
【００４４】得られた薄膜コンデンサの静電容量、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。The capacitance, leak current density and dielectric loss of the obtained thin film capacitor were measured, and the results are shown in Table 1.
【００４５】実施例６，７、比較例１，２ Ｓｉ添加量を表１に示す値（比較例１ではＳｉ添加せ
ず。）としたこと以外は実施例３と同様にして薄膜コン
デンサを作製し、得られた薄膜コンデンサの静電容量、
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。Examples 6 and 7, Comparative Examples 1 and 2 Thin film capacitors were produced in the same manner as in Example 3 except that the amount of Si added was set to the value shown in Table 1 (no Si was added in Comparative Example 1). And the obtained thin film capacitor's capacitance,
The leakage current density and the dielectric loss were measured, and the results are shown in Table 1.
【００４６】[0046]
【表１】 [Table 1]
【００４７】実施例８〜１２ シリコン基板上に、下部電極として白金膜をスパッタリ
ング法により形成し、その上に、下記手順で誘電体薄膜
を形成した。Examples 8 to 12 On a silicon substrate, a platinum film was formed as a lower electrode by a sputtering method, and a dielectric thin film was formed thereon by the following procedure.
【００４８】即ち、まず、ＢａＣＯ３，ＳｒＣＯ３及び
ＴｉＯ２を組成比（Ｂａ１−ｘＳｒｘ）ＴｉＯ３におい
て、ｘが表２に示す値となるように秤量すると共に、
（Ｂａ１−ｘＳｒｘ）ＴｉＯ３の主成分に対してＳｉが
１０モル％となるようにＳｉＯ２を秤量し、これらを混
合して９００℃で仮焼して粉末ターゲットを製造した。
このターゲットを用いて、スパッタリング法により下部
電極上に膜厚が２０００Åの（Ｂａ１−ｘＳｒｘ）Ｔｉ
Ｏ３誘電体薄膜を形成した。なお、基板温度は６００℃
とし、スパッタガスはＡｒ：１．４×１０−４Ｔｏｒ
ｒ，Ｏ２：８．０×１０−５Ｔｏｒｒとした。That is, first, BaCO 3 , SrCO 3 and TiO 2 are weighed such that x becomes a value shown in Table 2 in a composition ratio (Ba 1−x Sr x ) TiO 3 .
(Ba 1-x Sr x ) SiO 2 was weighed so that the content of Si was 10 mol% with respect to the main component of TiO 3 , and these were mixed and calcined at 900 ° C. to produce a powder target.
Using this target, a (Ba 1-x Sr x ) Ti having a thickness of 2000 ° is formed on the lower electrode by a sputtering method.
An O 3 dielectric thin film was formed. The substrate temperature was 600 ° C.
And the sputtering gas is Ar: 1.4 × 10 −4 Torr
r, O 2 : 8.0 × 10 −5 Torr.
【００４９】この誘電体薄膜に上部電極として白金膜を
スパッタリング法で形成して薄膜コンデンサを作製し
た。On this dielectric thin film, a platinum film was formed as an upper electrode by a sputtering method to produce a thin film capacitor.
【００５０】得られた薄膜コンデンサの静電容量、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。The capacitance, leak current density and dielectric loss of the obtained thin film capacitor were measured, and the results are shown in Table 2.
【００５１】実施例１３，１４、比較例３，４ Ｓｉ添加量を表２に示す値（比較例３ではＳｉ添加せ
ず。）としたこと以外は実施例１０と同様にして薄膜コ
ンデンサを作製し、得られた薄膜コンデンサの静電容
量、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 13 and 14, Comparative Examples 3 and 4 Thin-film capacitors were produced in the same manner as in Example 10 except that the amount of Si added was set to the value shown in Table 2 (in Comparative Example 3, no Si was added). Then, the capacitance, leakage current density and dielectric loss of the obtained thin film capacitor were measured, and the results were shown in Table 2.
It was shown to.
【００５２】[0052]
【表２】 [Table 2]
【００５３】表１，２より明らかなように、本発明に従
って、（Ｂａ１−ｘＳｒｘ）ＴｉＯ３ペロブスカイト構
造に所定量のＳｉを配合した誘電体薄膜を形成すること
により、静電容量が大きく、しかも絶縁性に優れた薄膜
コンデンサを得ることができる。As is apparent from Tables 1 and 2, according to the present invention, by forming a dielectric thin film in which a predetermined amount of Si is blended in the (Ba 1-x Sr x ) TiO 3 perovskite structure, the capacitance can be increased. It is possible to obtain a thin film capacitor which is large and has excellent insulation properties.
【００５４】[0054]
【発明の効果】以上詳述した通り、本発明の（Ｂａ，Ｓ
ｒ）ＴｉＯ３薄膜コンデンサの製造方法によれば、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、高容量かつ高絶縁性の薄膜コンデンサが提供され
る。As described in detail above, (Ba, S) of the present invention
According to the manufacturing method of r) TiO 3 thin film capacitor, is useful as a capacitor material for various applications in electronic devices, high capacity and high insulating thin film capacitor is provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０１Ｌ 21/822 Ｈ０１Ｌ 27/04 Ｃ 21/8242 27/04 (56)参考文献 特開 平５−217425（ＪＰ，Ａ) 特開 平３−11716（ＪＰ，Ａ) 特開 平５−47213（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 27/108 C01G 23/00 C04B 35/46 H01G 4/12 397 H01G 4/33 H01L 21/822 H01L 21/8242 H01L 27/04 ────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 7 Identification code FI H01L 21/822 H01L 27/04 C 21/8242 27/04 (56) References JP-A-5-217425 (JP, A) JP-A-3-11716 (JP, A) JP-A-5-47213 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01L 27/108 C01G 23/00 C04B 35/46 H01G 4/12 397 H01G 4/33 H01L 21/822 H01L 21/8242 H01L 27/04
Claims (2)
電極を順次積層形成して薄膜コンデンサを製造する方法
であって、該誘電体薄膜の形成に当り、（Ｂａ１−ｘＳ
ｒｘ）ＴｉＯ３（ただし、０≦ｘ≦１．０）で表される
主成分と、該主成分に対してＳｉとして０．１〜１０モ
ル％のＳｉ成分とを含む有機金属化合物溶液を、前記下
部電極上に塗布、乾燥して仮焼した後、４５０〜８００
℃で焼成することにより、（Ｂａ １−ｘ Ｓｒ ｘ ）ＴｉＯ
３ （ただし、０≦ｘ≦１．０）で表される主成分と、該
主成分に対してＳｉとして０．１〜１０モル％のＳｉ成
分とからなるペロブスカイト構造を有する誘電体薄膜を
形成することを特徴とする（Ｂａ，Ｓｒ）ＴｉＯ３薄膜
コンデンサの製造方法。A method of manufacturing a thin film capacitor by sequentially forming a lower electrode, a dielectric thin film and an upper electrode on a substrate.
In forming the dielectric thin film, (Ba 1−x S
r x ) an organometallic compound solution containing a main component represented by TiO 3 (where 0 ≦ x ≦ 1.0) and a Si component of 0.1 to 10 mol% as Si with respect to the main component. After coating on the lower electrode, drying and calcining,
(Ba 1-x Sr x ) TiO 2
3 (where 0 ≦ x ≦ 1.0)
0.1 to 10 mol% of Si as a Si component
Dielectric thin film with perovskite structure
Forming a (Ba, Sr) TiO 3 thin film capacitor.
電極を順次積層形成して薄膜コンデンサを製造する方法
において、該誘電体薄膜の形成に当り、（Ｂａ１−ｘＳ
ｒｘ）ＴｉＯ３（ただし、０≦ｘ≦１．０）で表される
主成分と、該主成分に対してＳｉとして０．１〜１０モ
ル％のＳｉ成分とを含むターゲットを用いて、基板温度
４００〜８００℃で前記下部電極上にスパッタリングを
行うことを特徴とする（Ｂａ，Ｓｒ）ＴｉＯ３薄膜コン
デンサの製造方法。2. A method of manufacturing a thin film capacitor by sequentially laminating a lower electrode, a dielectric thin film and an upper electrode on a substrate, wherein (Ba 1−x S
r x ) Using a target containing a main component represented by TiO 3 (where 0 ≦ x ≦ 1.0) and a Si component of 0.1 to 10 mol% as Si with respect to the main component, at a substrate temperature of 400 to 800 ° C. and performing sputtering on the lower electrode (Ba, Sr) TiO 3 method of manufacturing a thin film capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07307395A JP3129175B2 (en) | 1995-11-27 | 1995-11-27 | Method for manufacturing (Ba, Sr) TiO3 thin film capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07307395A JP3129175B2 (en) | 1995-11-27 | 1995-11-27 | Method for manufacturing (Ba, Sr) TiO3 thin film capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09148538A JPH09148538A (en) | 1997-06-06 |
| JP3129175B2 true JP3129175B2 (en) | 2001-01-29 |
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ID=17968540
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|---|---|---|---|
| JP07307395A Expired - Lifetime JP3129175B2 (en) | 1995-11-27 | 1995-11-27 | Method for manufacturing (Ba, Sr) TiO3 thin film capacitor |
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| Country | Link |
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| JP (1) | JP3129175B2 (en) |
Cited By (1)
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| EP2402982A1 (en) | 2010-07-01 | 2012-01-04 | STMicroelectronics (Tours) SAS | Method for manufacturing thin film capacitor and thin film capacitor obtained by the same |
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| JP4682769B2 (en) * | 2004-09-30 | 2011-05-11 | Ｔｄｋ株式会社 | Dielectric thin film, thin film dielectric element and manufacturing method thereof |
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1995
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2402982A1 (en) | 2010-07-01 | 2012-01-04 | STMicroelectronics (Tours) SAS | Method for manufacturing thin film capacitor and thin film capacitor obtained by the same |
| US8501560B2 (en) | 2010-07-01 | 2013-08-06 | Mitusbishi Materials Corporation | Method for manufacturing thin film capacitor and thin film capacitor obtained by the same |
| US8648992B2 (en) | 2010-07-01 | 2014-02-11 | Mitsubishi Materials Corporation | Method for manufacturing thin film capacitor and thin film capacitor obtained by the same |
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| Publication number | Publication date |
|---|---|
| JPH09148538A (en) | 1997-06-06 |
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