JPH04183872A - 超高純度強誘電体薄膜 - Google Patents

超高純度強誘電体薄膜

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Publication number
JPH04183872A
JPH04183872A JP2310890A JP31089090A JPH04183872A JP H04183872 A JPH04183872 A JP H04183872A JP 2310890 A JP2310890 A JP 2310890A JP 31089090 A JP31089090 A JP 31089090A JP H04183872 A JPH04183872 A JP H04183872A
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Japan
Prior art keywords
thin film
lead
contg
ultra
film
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JP2310890A
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JP2891304B2 (ja
Inventor
Katsumi Ogi
勝実 小木
Nobuyuki Soyama
信幸 曽山
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority to JP2310890A priority Critical patent/JP2891304B2/ja
Priority to DE69116106T priority patent/DE69116106T2/de
Priority to EP91119082A priority patent/EP0485907B1/en
Priority to US07/791,998 priority patent/US5244742A/en
Priority to KR1019910020427A priority patent/KR100220345B1/ko
Publication of JPH04183872A publication Critical patent/JPH04183872A/ja
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。

Description

【発明の詳細な説明】 Ｃ産業上の利用分野〕 本発明は超高純度強誘電体薄膜（ＰＺＴ薄膜）に関し、
さらに詳しくは、赤外線センサー、圧電フィルター、振
動子、レーザーの変調素子、光シヤツター、キャパシタ
膜、不揮発性のメモリー等に適用される超高純度強誘電
体薄膜に関する。
〔従来技術とその課題〕
強誘電体薄膜を形成する際、良好な特性を得るためには
どのような成膜法でも最終的に熱処理を行い結晶性を」
二げることか必要である。しかし結晶性を上げていくと
、同時に結晶粒の成長が起こり粒界を通してのリーク電
流が問題となってくる。
この相反する現象のために従来は強誘電体薄膜の特性を
向」ニするうえで限界があった。
ｐｂ含含有ペロブスカイト梨型強誘電体簿膜場合も強誘
電性を上げるためには、熱処理により結晶性を上げるこ
とが必要であるが、その際、結晶粒界の成長が伴い膜中
の不純物の多くが粒界に析出してくる。この不純物領域
が粒界を通してのリーク電流を増大させる。そこでこの
不純物領域を取り除くこと↓こよってリーク電流を大幅
に減少させることが可能と考えられる。しかしながら、
薄膜の構成成分であるＰｂ、Ｌａ、　Ｔｉ、　Ｚｒ等の
高純度化が難かしく、特にＯ，ｌｐｐｍ以下にまで不純
物温度を下げることは非常に困難であった。囚に、従来
、ｐｂ含有強誘電体薄膜に関し、高純度化により特性改
善した旨の報告は見当らない。
〔課題の解決に至る知見〕
そこで本発明者等は、これら各金属成分の高純度化につ
き研究した結果、それぞれの金属成分を金属有機化合物
の形で蒸留、昇華、再結晶を繰り返し、あるいはこれら
を組み合わせることによって非常に高純度の金属成分原
料を得ることができ、これらを原料としてチタン酸鉛、
チタン酸ジルコン酸鉛あるいはランタン含有チタン酸ジ
ルコン酸鉛等のｐｂ含有強誘電体薄膜を作製したところ
、結晶化の際に不純物が粒界に析出するのを防止し、非
常に優れた特性を有する強誘電体薄膜を得ることができ
る知見を得た。
〔課題の解決手段：発明の構成〕
本発明によれば一般式 ％式％ （式中Ｘ、Ｙは０．１または１−より小さい少数）で表
わされる鉛含有強誘電体からなり、該誘電体に含まれる
不純物として、１、ｊ、Ｎａ、にの合謂含イ」址か０、
］ｐｐｍ以下、Ｕ、１’ｈの合Ｎ１含有量がＩ　Ｏｐ　
Ｐ　＋）以下であって、金属不純物の総合有量が　Ｉｐ
ＰＩＩＩ以下であることを特徴とする強誘電体薄膜が提
供される。
具体的には、チタン酸鉛（一般式においてＸ＝ｙ＝ｏ）
、チタン酸ジルコン酸鉛（一般式においてｘ＝ｏ、Ｙは
０＜Ｙ＜１＞またはランタン含有チタン酸ジルコン酸鉛
（一般式においてＸ、Ｙが０＜Ｘ、Ｙ＜１．）等が提供
される。
本発明の強誘電体薄膜は、薄膜の構成金属成分を金属有
機化合物の形で蒸留、昇華、再結晶を繰返し、あるいは
これらを組合せて精製することにより高純度化したもの
を用い、これらを有機溶媒に所定の組成比となるように
溶解して被膜形成塗布液を調製し、該塗布液を基板に塗
布し、乾燥、焼成することによって得られる。
また、精製した」二記金属有機化合物から得た金属酸化
物粉末を用いスパッタリング法によっても」二記強誘電
体薄膜を得ることができる。
本発明の強誘電体薄膜の不純物は、Ｌｊ　、　Ｎａ、　
Ｋの合計含有量がＯ，ｌｐｐｍ以下、Ｕ、’ｒｈ（７）
合Ｍ１含有量が］０ｐｐｂ以下であり、かつ金属不純物
の総合有量がＩＰＩ１ｍ以ドである。
アルカリ金属は電荷移動への関与が大きく、粒界に析出
するとリーク電流を発生させ易くなるので、これらＬｉ
、　Ｎａ、にの合計含有量を０．ｌｐｐｍ以下とする。
またＵ、Ｔｈはα放射線源となり、強誘電体薄膜をＤ　
ＲＡ　Ｍのキャパシター膜として用いた場合にα線によ
るソフトエラーを生ずる原因となるので、その合ｆｌ含
有量を］０ｐｐｂ以下とする。更に第１図に示すように
、強誘電体薄膜の金属不純物総量がｌｐｐｍ以下のとき
、リーク電流密度（Ａ−ｃｍ−”）は大幅に低下するの
で、−１−記１．ｊ、　Ｎａ、　ＫおよびｔＪ、Ｔｈを
含めた金属不純物総量をｌｐｐｍ以下とする。
〔発明の効果〕
本発明の超高純度の強誘電体薄膜は、従来問題−４＝ であったリーク電流が大幅に減少し、優れた誘電特性を
示す。また膜の部位による特性変化が極めて少ない安定
な膜が得られ、エレクトロニクスの分野等において広く
用いることができる。
〔実施例および比較例〕
実施例１ 蒸留、昇華、再結晶等を繰返して不純物を取り除き精製
したＰｂ、　Ｚｒ、１°ｊ。の金属有機化合物を有機溶
媒にＰｂ：Ｚｒ：Ｔｊ＝　］　：０．５２：０．４８の
組成比となるように溶解し、”ｂＺｒｏ＋　５２　Ｔｉ
ｏＨ，１８０３換算で１（ｈｔ％濃度となるように重量
調整を行い、　ＰＺＴ被膜形成用塗布液を作製した。溶
液から得られる酸化物中の不純Ｌｊ度は、Ｎａ、に、Ｌ
、ｊのアルカリ金属はいずれも１０ｐＰｂ以下であり、
Ｕ、’ｆｈは検出限界以下であった。
この溶液をスピンツー１〜法でＰｔ基板上に塗イｌ」シ
膜厚約３０００人としたのち、７０　（１’Ｃで２時間
空気中で焼成を行った。この膜」−にＰｔ電極を形成し
電気的特性を測定したところ以下の通りであった。
実施例２ 実施例］と同様に不純物を取り除き精製したｐｂ、Ｚｒ
、　Ｔｊの金属有機化合物を有機溶媒にＰｂ　：　Ｔｊ
、＝　１　：１の組成比となるように溶解し、ＰｂＴｉ
０．換算で１０ｗｔ％濃度となるように重量調整を行い
ＰＺＴ被膜形成用塗布液を作製した。溶液から得られる
酸化物中の不純物濃度は、Ｎａ、　Ｋ　、［ｊのアルカ
リ金属はいずれも１ｏｐｐｂ以下であり、Ｕ、Ｔｈは検
出限界以下であった。この溶液をスピンコード法でｐｔ
基板上に塗布し膜厚約３０００人としたのち、７００℃
で時間空気中で焼成を行った。この膜上にｐｔ電極を形
成し電気的特性を測定したところ以下の通りであった。
実施例３ 実施例１と同様に不純物を取り除き精製したｐｂ、Ｌａ
、　Ｚｒ、　Ｔｊの金属有機化合物を有機溶媒にＰｂ　
：　Ｌａ　：Ｚｒ：１’ｊ　＝０．９１：０．０９：０
．６４：０．３４の組成比となるように溶解し、ＰｂＯ
、、□Ｌａ、　＋［１９（ＺｒＯ＋ＧＳ　ＴｉＯ＊３５
　）０　＋９’＋　７　％０３換算で１０すｔ％濃度と
なるように重量調整を行いＰＺＴ被膜形成用塗布液を作
製した。溶液から得られる酸化物中の不純物濃度は、Ｎ
ａ、に、Ｌｉのアルカリ金属はいずれも１０ｐｐｂ以下
であり、Ｕ、Ｔｈは検出限界以下であった。この溶液を
スピンコード法でｐｔ基板上に塗布し膜厚約３０００人
としたのち、７００℃で２時間空気中で焼成を行った。
この膜上にｐｔ電極を形成し電気的特性を測定したとこ
ろ以下の通りであった。
実施例４ 実施例１と同様に精製した金属有機化合物からそれぞれ
ｌ〕ｂＯ，Ｚｒｏ、’Ｎ、０゜粉末を得た。それを１）
ｂ：Ｚｒ：１’ｉ＝　］：０．５２：０．４８の組成比
となるように混合し、＝７− 焼結させてスパッタリング用ターゲットを作製した。こ
れの不純物濃度も実施例１と同様であった。
このターゲットを使いスパッタリング法によりｐｔ基板
上に膜厚約３０００人の薄膜を形成したのち、７００℃
で２時間空気中で焼成を行った。この膜上にｐｔ電極を
形成し電気的特性を測定したところ以下の通りであった
。
実施例５ 実施例１と同様に不純物を取り除き精製したＰｂ、　Ｔ
ｉの金属有機化合物を直接用い、ＣＶＯ法によりｐｂｒ
ｊ０３簿膜をｐｔ基板」二に膜厚約３０００人となるよ
うに形成したのち、７００℃で２時間空気中で焼成を行
った。因みに使用した金属有機化合物から得られる酸化
物中の不純物濃度は、Ｎａ、Ｋ　、　Ｌｉのアルカリ金
属はいずれも１０ｐｐｂ以下であり、Ｕ、Ｔｈは検出限
界以下であった。この膜上にｐｔ電極を形成し電気的特
性を測定したところ以下の通りであった。
比較例 市販のＰｂ、　Ｚｒ、　Ｔｊの金属有機化合物を使い実
施例１と同等ＰＺＴ被膜形成塗布液（Ａ液）を作製した
。
これと実施例１て作製した被膜形成液とを適量ずつ混合
し、何種類かの不純物含有量の異なる被膜形成液を作製
して、実施例１と同じＩ条件で成膜した。これらの膜に
ついて同様にしてリーク電流を測定した。この結果を図
に示す。図から明らかのように不純物含有量がｌｐｐｍ
付近でリーク電流減少の変曲点となっている。
【図面の簡単な説明】
図はチタン酸ジルコン酸鉛（ＰＺＴ）の薄膜の不純物と
リーク電流との関係を示すグラフである。

Claims (2)

    【特許請求の範囲】
  1. （１）一般式 Ｐｂ＿１＿−＿ＸＬａ＿Ｘ（Ｚｒ＿ＹＴｉ＿１＿−＿Ｙ
    ）＿１＿−＿Ｘ＿／＿４Ｏ＿３（式中Ｘ、Ｙは０．１ま
    たは１より小さい少数）で表わされる鉛含有強誘電体か
    らなり、該誘電体に含まれる不純物として、Ｌｉ、Ｎａ
    、Ｋの合計含有量が０．１ｐｐｍ以下、Ｕ、Ｔｈの合計
    含有量が１０ｐｐｂ以下であって、金属不純物の総含有
    量が１ｐｐｍ以下であることを特徴とする強誘電体薄膜
    。
  2. （２）鉛含有強誘電体がチタン酸鉛（一般式においてＸ
    ＝Ｙ＝０）、チタン酸ジルコン酸鉛（一般式においてＸ
    ＝０、Ｙは０＜Ｙ＜１）またはランタン含有チタン酸ジ
    ルコン酸鉛（一般式においてＸ、Ｙが０＜Ｘ、Ｙ＜１）
    である請求項１記載の強誘電体薄膜。
JP2310890A 1990-11-16 1990-11-16 超高純度強誘電体薄膜 Expired - Lifetime JP2891304B2 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2310890A JP2891304B2 (ja) 1990-11-16 1990-11-16 超高純度強誘電体薄膜
DE69116106T DE69116106T2 (de) 1990-11-16 1991-11-08 Dünne ferroelektrische Schicht von höchster Reinheit
EP91119082A EP0485907B1 (en) 1990-11-16 1991-11-08 Ultrahigh-purity ferroelectric thin film
US07/791,998 US5244742A (en) 1990-11-16 1991-11-14 Ultrahigh-purity ferroelectric thin film
KR1019910020427A KR100220345B1 (ko) 1990-11-16 1991-11-16 초고순도 강유전체박막 및 그 제조방법

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2310890A JP2891304B2 (ja) 1990-11-16 1990-11-16 超高純度強誘電体薄膜

Related Child Applications (1)

Application Number Title Priority Date Filing Date
JP6860494A Division JPH0754134A (ja) 1994-04-06 1994-04-06 超高純度誘電体薄膜形成用ターゲット材

Publications (2)

Publication Number Publication Date
JPH04183872A true JPH04183872A (ja) 1992-06-30
JP2891304B2 JP2891304B2 (ja) 1999-05-17

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US (1) US5244742A (ja)
EP (1) EP0485907B1 (ja)
JP (1) JP2891304B2 (ja)
KR (1) KR100220345B1 (ja)
DE (1) DE69116106T2 (ja)

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JP2020025069A (ja) * 2018-03-19 2020-02-13 株式会社リコー 酸化物形成用塗布液、酸化物膜の製造方法、及び電界効果型トランジスタの製造方法

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JP2020025069A (ja) * 2018-03-19 2020-02-13 株式会社リコー 酸化物形成用塗布液、酸化物膜の製造方法、及び電界効果型トランジスタの製造方法

Also Published As

Publication number Publication date
JP2891304B2 (ja) 1999-05-17
KR100220345B1 (ko) 1999-09-15
EP0485907A1 (en) 1992-05-20
US5244742A (en) 1993-09-14
DE69116106D1 (de) 1996-02-15
KR920009705A (ko) 1992-06-25
DE69116106T2 (de) 1996-05-15
EP0485907B1 (en) 1996-01-03

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