JPH0499863A - Production of ferroelectric multiple oxide containing pb - Google Patents
Production of ferroelectric multiple oxide containing pbInfo
- Publication number
- JPH0499863A JPH0499863A JP21462090A JP21462090A JPH0499863A JP H0499863 A JPH0499863 A JP H0499863A JP 21462090 A JP21462090 A JP 21462090A JP 21462090 A JP21462090 A JP 21462090A JP H0499863 A JPH0499863 A JP H0499863A
- Authority
- JP
- Japan
- Prior art keywords
- ozone
- ferroelectric
- generated
- reaction chamber
- low
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 238000005240 physical vapour deposition Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000010408 film Substances 0.000 abstract description 11
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052753 mercury Inorganic materials 0.000 abstract description 8
- 239000010453 quartz Substances 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000010409 thin film Substances 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 229910020684 PbZr Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、強誘電体複合酸化物の製造方法に関する。さ
らに詳しくは、Ｐｂを含む強誘電体複合酸化物の製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a ferroelectric composite oxide. More specifically, the present invention relates to a method for manufacturing a ferroelectric composite oxide containing Pb.
〈従来の技術〉
Ｐｂを含む強誘電体複合酸化物（ＰｂＺｒ、Ｔｉ ＋−
ウ０３等）薄膜はＣＶＤ法（化学的気相成長法）あるい
は、ＰＶＤ法（物理的気相成長法）を用いることにより
形成されている。その場合、５００°Ｃ以下の低温で形
成された薄膜は、十分酸化されていないためにパイロク
ロア型結晶構造となるため、強誘電体性を示さない。強
誘電体性を示すペロブスカイト型結晶構造を得るには、
６００°Ｃ以上の基板加熱あるいは膜形成後の熱処理が
必要となる。<Prior art> Ferroelectric composite oxide containing Pb (PbZr, Ti +-
The thin film (C03, etc.) is formed by using the CVD method (chemical vapor deposition method) or the PVD method (physical vapor deposition method). In this case, the thin film formed at a low temperature of 500° C. or lower has a pyrochlore type crystal structure because it is not sufficiently oxidized, and therefore does not exhibit ferroelectric properties. To obtain a perovskite crystal structure exhibiting ferroelectric properties,
It is necessary to heat the substrate to 600° C. or higher or to perform heat treatment after film formation.
しかし、６００°Ｃ以上の熱工程では、ＴｉやＺｒに比
べＰｂの蒸気圧が非常に高いため、ＰｂＯの形態てＰｂ
が蒸発し、その結果、酸素や鉛か欠けた構造をもつ膜と
なり強誘電体性を示すペロブスカイト型結晶構造とはな
らない。このため、ＣＶＤ法ではＰｂ供給ガスの分圧を
上げ、蒸発するＰｂを補償する。一方、ＰＶＤ法では（
１）式に示すようにＰｂＺｒつＴｉ＋−８０２にあらか
じめ数十ｍｏ１％のＰ １）○を添加したターゲットを
用いることによりＰｂＯを補償する方法、また（２）式
に示すようにＰｂＯを加熱しＰｂＯ雰囲気で膜形成ある
いは形成した膜をＰｂＯ雰囲気で熱処理を行うことによ
りＰｂＯを補償する方法か用いられている。However, in thermal processes of 600°C or higher, the vapor pressure of Pb is much higher than that of Ti and Zr, so PbO is
evaporates, and as a result, the film has a structure lacking oxygen and lead, and does not have a perovskite-type crystal structure that exhibits ferroelectric properties. Therefore, in the CVD method, the partial pressure of the Pb supply gas is increased to compensate for the evaporated Pb. On the other hand, in the PVD method (
1) A method of compensating for PbO by using a target to which several tens of mo1% of P1) is added in advance to PbZrTi+-802 as shown in equation (2), and a method of heating PbO as shown in equation (2). A method of compensating for PbO by forming a film in a PbO atmosphere or heat-treating the formed film in a PbO atmosphere is used.
ＰｂＺｒ、Ｔｉ ｌ −，０３＋Ｐｂ０（数十ｍｏ１％
）→ＰｂＯ↑（ｖａｐｏｒ） ＋ＰｂＺｒ、Ｔｉ＋−，
０３＝−（１）ＰｂＺｒ、Ｔｉ＋−、０２＋Ｐｂ０（ｖ
ａｐｏｒ）↑→ＰｂＺｒＪｉ＋−ｘ ０３＝４２）上記
の方法はともに熱処理は６００°Ｃ以上の高温で行われ
るため、補償するＰｂの制御、最適化が必要である。PbZr, Ti l −,03+Pb0 (several tens of mo1%
)→PbO↑(vapor) +PbZr, Ti+-,
03=-(1) PbZr, Ti+-, 02+Pb0(v
apor)↑→PbZrJi+−x 03=42) In both of the above methods, heat treatment is performed at a high temperature of 600° C. or higher, so it is necessary to control and optimize Pb to compensate.
〈発明が解決しようとする課題〉
ところで、上述したように熱処理温度が高い場合は、Ｐ
ｂＯの状態でＰｂの再蒸発が発生し、膜の形成は不安定
となる。このため、緻密で高純度の物質の膜を形成する
ことができないという問題がある。<Problem to be solved by the invention> By the way, as mentioned above, when the heat treatment temperature is high, P
In the bO state, re-evaporation of Pb occurs and the film formation becomes unstable. For this reason, there is a problem in that a dense and highly pure substance film cannot be formed.
本発明は、以上の問題点を鑑みてなされたもので、低温
環境下においても、反応が促進され、かつ緻密で高純度
な物質の膜を安定に形成することができる製造方法を提
供することを目的とする。The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a manufacturing method capable of promoting reactions and stably forming a dense and highly pure film of a substance even in a low-temperature environment. With the goal.
く課題を解決するための手段〉
上記の目的を達成するための方法を、実施例に対応する
図面を参照しつつ説明すると、本発明の強誘電体複合酸
化物の製造方法は、ＣＶＤ法あるいは、ＰＶＤ法により
反応室１内において基板５に薄膜を形成する。反応ガス
はオゾンを導入する。Means for Solving the Problems> A method for achieving the above object will be described with reference to drawings corresponding to examples. , a thin film is formed on the substrate 5 in the reaction chamber 1 by the PVD method. Ozone is introduced as a reaction gas.
そのオゾン導入ラインは、オゾン発生器４によりオゾン
を生成し、そのオゾン発生器４より導出した合成石英チ
ューブ３を介して反応室１内にオゾンを導入する構成と
なっている。その合成石英チューブ３の周囲には、低圧
水銀ランプ２が設けられている。上述のオゾン発生器４
により発生したオゾン（０３）が合成石英チューブ３を
通過する際に、その低圧水銀ランプ２により紫外線が照
射されると、Ｏ８はラジカルＯ（’Ｄ）となり、その状
態で反応室１内に導入され、反応ガスとして使用される
。The ozone introduction line is configured to generate ozone by an ozone generator 4 and introduce the ozone into the reaction chamber 1 through a synthetic quartz tube 3 led out from the ozone generator 4. A low pressure mercury lamp 2 is provided around the synthetic quartz tube 3. Ozone generator 4 mentioned above
When the generated ozone (03) passes through the synthetic quartz tube 3 and is irradiated with ultraviolet rays by the low-pressure mercury lamp 2, O8 becomes a radical O('D) and is introduced into the reaction chamber 1 in this state. and used as a reaction gas.
く作用〉
反応ガスにオゾンを用いたので、低温環境下での膜の形
成が促進され、かつＰｂの再蒸発が抑制される。Effects> Since ozone is used as the reaction gas, film formation is promoted in a low-temperature environment, and re-evaporation of Pb is suppressed.
〈実施例〉 本発明の実施例を、以下、図面に基づいて説明する。<Example> Embodiments of the present invention will be described below based on the drawings.
図面は本発明実施例の構成を示す図である。本発明の強
誘電体複合酸化物の製造方法は、ＣＶＤ法あるいは、Ｐ
ＶＤ法により反応室１内において基板５上に薄膜を形成
する。この時に用いる反応ガスはオゾン（０，）である
。オゾンは、無声放電型オゾン発生器４により生成する
。生成したオゾンは０．の状態では使用されず、（３）
式に示すように、オゾン（０３）が紫外線照射されるこ
とにより生成されるＯ（’Ｄ）が使用される。The drawings are diagrams showing the configuration of an embodiment of the present invention. The method for producing the ferroelectric composite oxide of the present invention is a CVD method or a P
A thin film is formed on the substrate 5 in the reaction chamber 1 by the VD method. The reaction gas used at this time is ozone (0,). Ozone is generated by a silent discharge ozone generator 4. The ozone produced is 0. It is not used in the state of (3)
As shown in the formula, O('D) generated by irradiating ozone (03) with ultraviolet light is used.
０ｓ−０（’Ｄ）＋０２・・・（３）
紫外線の照射は、無声放電型オゾン発生器４に連通した
合成石英チューブ３中を反応室１の方向へ移動する０、
に対して行われ、合成石英チューブ３の周囲に設けられ
た低圧水銀ランプ２により行われる。低圧水銀ランプ２
は例えば、スブラジル等が用いられる。低圧水銀ランプ
２により照射される紫外線は、水銀ランプの輝線２５４
ｎｍのものが用いられる。この結果、上述したように、
０３はラジカル○（１Ｄ）となり、反応室１内に導入さ
れ、反応ガスとして使用される。0s-0('D)+02...(3) Ultraviolet irradiation is carried out in the direction of the reaction chamber 1 through the synthetic quartz tube 3 connected to the silent discharge ozone generator 4.
A low-pressure mercury lamp 2 provided around a synthetic quartz tube 3 is used. Low pressure mercury lamp 2
For example, Subrasil etc. are used. The ultraviolet light emitted by the low-pressure mercury lamp 2 is the bright line 254 of the mercury lamp.
nm is used. As a result, as mentioned above,
03 becomes a radical ◯ (1D), which is introduced into the reaction chamber 1 and used as a reaction gas.
またラジカル０は（４）式に示すオゾン（０３）の熱分
解により生成されるＯ （３Ｐ ’）を用いてもよい。Further, as the radical 0, O (3P') generated by thermal decomposition of ozone (03) shown in equation (4) may be used.
この熱分解は、無声放電型オゾン発生器４により発生し
た０３が合成石英チューブ３中を通り、反応室１へ導入
されると、反応室１内において加熱された基板の輻射熱
によりなされる。This thermal decomposition is performed by the radiant heat of the heated substrate in the reaction chamber 1 when the O3 generated by the silent discharge ozone generator 4 passes through the synthetic quartz tube 3 and is introduced into the reaction chamber 1.
０３→Ｏ（’Ｐ） ＋０２・・・（４）なお、ラジカル
Ｏ（’Ｄ）はＯＣＰ ’）より１ｅＶ以上活性化された
ものであり、０ＣＰ）に比べ、より反応を促進させる。03→O('P) +02...(4) Note that the radical O('D) is activated by 1 eV or more than OCP'), and promotes the reaction more than OCP').
以上の構成よりなる製造装置を用いれば、低圧下におい
てもラジカル０は非常に酸化力があるため、形成温度を
５００°Ｃに下げても酸化反応は促進され、安定した膜
形成が行われる。If the manufacturing apparatus having the above configuration is used, the oxidation reaction is promoted even if the formation temperature is lowered to 500° C., and stable film formation is performed because radicals 0 have a very strong oxidizing power even under low pressure.
〈発明の効果〉
以上説明したように、本発明によれば、反応ガスにラジ
カル０を用いたので、低温環境下においても酸化反応は
促進され、安定した膜形成が行われる。その結果、緻密
で高純度のＰｂを含む強誘電体複合酸化物を得ることが
できる。<Effects of the Invention> As explained above, according to the present invention, since zero radicals are used as the reaction gas, the oxidation reaction is promoted even in a low-temperature environment, and stable film formation is performed. As a result, a dense and highly pure ferroelectric composite oxide containing Pb can be obtained.
図面は本発明実施例で用いた装置の構成図てある。 １・・・反応室 ２・・・低圧水銀ランプ ３・・・合成石英チューブ ４・・・オゾン発生器 ５・・・基板 The drawings are diagrams showing the configuration of the apparatus used in the embodiments of the present invention. 1...Reaction chamber 2...Low pressure mercury lamp 3...Synthetic quartz tube 4...Ozone generator 5... Board
Claims (1)
いは物理的気相成長法により形成する方法であって、オ
ゾン発生手段によりオゾンを発生させ、そのオゾンの分
解により発生するラジカル酸素を反応ガスとして用いる
ことを特徴とするＰｂを含む強誘電体複合酸化物の製造
方法。A method of forming a ferroelectric composite oxide containing Pb by chemical vapor deposition or physical vapor deposition, in which ozone is generated by an ozone generating means, and radical oxygen generated by decomposition of the ozone is generated. A method for producing a ferroelectric composite oxide containing Pb, characterized in that it is used as a reactive gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2214620A JP2614353B2 (en) | 1990-08-13 | 1990-08-13 | Method for producing ferroelectric composite oxide containing Pb |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2214620A JP2614353B2 (en) | 1990-08-13 | 1990-08-13 | Method for producing ferroelectric composite oxide containing Pb |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0499863A true JPH0499863A (en) | 1992-03-31 |
| JP2614353B2 JP2614353B2 (en) | 1997-05-28 |
Family
ID=16658746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2214620A Expired - Fee Related JP2614353B2 (en) | 1990-08-13 | 1990-08-13 | Method for producing ferroelectric composite oxide containing Pb |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2614353B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014040651A (en) * | 2012-07-25 | 2014-03-06 | Ulvac Japan Ltd | Pzt film and formation method of pzt film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5678422A (en) * | 1979-11-26 | 1981-06-27 | Hoxan Corp | Preparation of electrically conductive transparent thin film |
| JPS63317670A (en) * | 1987-06-18 | 1988-12-26 | Fuji Electric Co Ltd | Production of thin oxide film |
| JPH0196368A (en) * | 1987-10-05 | 1989-04-14 | Matsushita Electric Ind Co Ltd | Manufacture of thin film of ferroelectric substance |
| JPH0238561A (en) * | 1988-07-27 | 1990-02-07 | Mitsubishi Electric Corp | Thin film-forming equipment |
-
1990
- 1990-08-13 JP JP2214620A patent/JP2614353B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5678422A (en) * | 1979-11-26 | 1981-06-27 | Hoxan Corp | Preparation of electrically conductive transparent thin film |
| JPS63317670A (en) * | 1987-06-18 | 1988-12-26 | Fuji Electric Co Ltd | Production of thin oxide film |
| JPH0196368A (en) * | 1987-10-05 | 1989-04-14 | Matsushita Electric Ind Co Ltd | Manufacture of thin film of ferroelectric substance |
| JPH0238561A (en) * | 1988-07-27 | 1990-02-07 | Mitsubishi Electric Corp | Thin film-forming equipment |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014040651A (en) * | 2012-07-25 | 2014-03-06 | Ulvac Japan Ltd | Pzt film and formation method of pzt film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2614353B2 (en) | 1997-05-28 |
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|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |