JP4329288B2 - BLT or BT ferroelectric thin film, composition for forming the same and method for forming the same - Google Patents
BLT or BT ferroelectric thin film, composition for forming the same and method for forming the same Download PDFInfo
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- JP4329288B2 JP4329288B2 JP2001263379A JP2001263379A JP4329288B2 JP 4329288 B2 JP4329288 B2 JP 4329288B2 JP 2001263379 A JP2001263379 A JP 2001263379A JP 2001263379 A JP2001263379 A JP 2001263379A JP 4329288 B2 JP4329288 B2 JP 4329288B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、電気的又は光学的性質により各種デバイスへの応用が期待されるＢＬＴ又はＢＴ強誘電体薄膜と、それを形成するための組成物及び形成方法に関する。
【０００２】
【従来の技術】
チタン酸ビスマス及びそれにランタンをドープした金属酸化物（ＢＬＴ：（ＢｉｘＬａｙ）４Ｔｉ３Ｏ１２）はその高い誘電率、優れた強誘電特性から種々のキャパシタや不揮発性メモリ等のデバイスへの応用が期待されている。これらの金属酸化物薄膜の成膜法としては、スパッタリング法、ＭＯＣＶＤ法などがあるが、比較的安価で簡便に薄膜を作製する手法として、有機金属溶液を基板に塗布するゾルゲル法がある。
【０００３】
ゾルゲル法は、原料となる各成分金属の加水分解性の化合物、その部分加水分解物及び／又はその部分重縮合物を含有する原料溶液を基板に塗布し、塗膜を乾燥させた後、例えば空気中で約４００℃に加熱して金属酸化物の膜を形成し、さらにその金属酸化物の結晶化温度以上で焼成して膜を結晶化させることにより強誘電体薄膜を成膜する方法である。
【０００４】
このゾルゲル法に似た方法として、有機金属分解（ＭＯＤ）法がある。ＭＯＤ法では、熱分解性の有機金属化合物、例えば、金属のβ−ジケトン錯体（例えば、金属アセチルアセトネート）やカルボン酸塩（例えば、酢酸塩）を含有する原料溶液を基板に塗布し、例えば空気中又は含酸素雰囲気中等で加熱して、塗膜中の溶媒の蒸発及び金属化合物の熱分解を生じさせて金属酸化物の膜を形成し、さらに結晶化温度以上で焼成して膜を結晶化させる。従って、原料化合物の種類が異なるだけで、成膜操作はゾルゲル法とほぼ同様である。
【０００５】
このようにゾルゲル法とＭＯＤ法は成膜操作が同じであるので、両者を併用した方法も可能である。即ち、原料溶液が加水分解性の金属化合物と熱分解性の金属化合物の両方を含有していてもよく、その場合には塗膜の加熱中に原料化合物の加水分解と熱分解が起こり、金属酸化物が生成する。
【０００６】
これらのゾルゲル法、ＭＯＤ法、及びこれらを併用した方法等はＣＳＤ法（Chemical
Solution Deposition）と称されている。
【０００７】
このＣＳＤ法は、安価かつ簡便で量産に適しているという利点に加えて、膜の組成制御が容易で、成膜厚みが比較的均一であるという優れた特長を有する。従って、比較的平坦な基板上に強誘電体薄膜を形成するのに有利な成膜法である。
【０００８】
なお、従来のＣＳＤ法では、原料溶液を基板に塗布して乾燥させた後仮焼し、所望の膜厚が得られるまでこの塗布、乾燥及び仮焼を繰り返し行い、最後の金属酸化物の結晶化温度以上の温度で焼成して結晶化させることにより成膜が行われている。
【０００９】
【発明が解決しようとする課題】
ＣＳＤ法による強誘電体薄膜の形成には、結晶化のために焼成を行う必要がある。
【００１０】
一方、このような強誘電体薄膜を利用したメモリにおいては、デバイスチップの小型化に伴い、加熱処理によるデバイスのトランジスタ及びその周辺回路等への悪影響が問題視されるようになってきており、金属酸化物薄膜形成時の結晶化温度を低減させることが望まれている。また、基板上のアルミニウム配線の酸化を防止するためにも、結晶化温度の低減が期待されている。
【００１１】
強誘電体メモリ以外の用途においても、成膜時の結晶化温度を低減することは、従来の結晶化温度では成膜が困難であったガラス基板等への成膜を可能とし、強誘電体や圧電体、集電体等の応用範囲の拡大を図ることが期待されることから、結晶化温度の低減が強く望まれている。
【００１２】
本発明は、ＢＬＴ又はＢＴ強誘電体薄膜を形成するに当り、５５０℃以下の低温でも結晶化を行うことが可能な金属酸化物薄膜の形成用組成物、形成方法及びこの低温結晶化方法で形成された強誘電体薄膜を提供することを目的とする。
【００１３】
【課題を解決するための手段】
本発明（請求項１）のＢＬＴ又はＢＴ強誘電体薄膜形成用組成物は、ＢＬＴ強誘電体薄膜を形成するための有機金属化合物溶液よりなる強誘電体薄膜形成用組成物において、一般式：（ＢｉｘＬａｙ）４Ｔｉ３Ｏ１２（式中、０＜ｘ＜１．３、０≦ｙ＜１）で示される複合金属化合物Ａと、Ｂｉ、Ｓｉ、Ｐｂ、Ｇｅ、Ｓｎ、Ａｌ、Ｇａ、Ｉｎ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｖ、Ｎｂ、Ｔａ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ｃｄ、Ｌｉ、Ｎａ及びＫのうちから選ばれる１種の元素から構成される金属酸化物Ｂの混合金属酸化物の薄膜を形成するための液状組成物であって、該金属酸化物を構成する各金属の熱分解性有機金属化合物、加水分解性有機金属化合物、その部分加水分解物及び／又は重縮合物が、上式で示される金属原子比を与えるような割合で有機溶剤中に溶解している溶液からなり、形成されるＢＬＴ又はＢＴ強誘電体薄膜の結晶化温度が５８０℃以下であることを特徴とするものである。
【００１４】
本発明者らは、強誘電体薄膜の結晶化温度を低下させるべく種々研究を重ねた結果、Ｂｉ、Ｓｉ、Ｐｂ、Ｇｅ、Ｓｎ、Ａｌ、Ｇａ、Ｉｎ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｖ、Ｎｂ、Ｔａ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ｃｄ、Ｌｉ、Ｎａ及びＫの群からなる１種あるいは２種以上の元素をＢＬＴ又はＢＴに添加することで、純粋なＢＬＴ又はＢＴに比べ低温で結晶化し、また膜のモフォロジーが良くなるという知見が得られた。
【００１５】
本発明の組成物は、かかる知見に基づいて創案されたものである。なお、ＢとＡとのモル比Ｂ／Ａは０＜Ｂ／Ａ＜１００が好ましい。このＢが少量混合された状態でドーパントとしてのＢの効果が現れ始めるが、Ｂの量が増えるに従い結晶化温度、更にはモフォロジーの改善効果が現れるようになる。但し、Ｂ／Ａがあまりに大きくなりすぎると、Ａ自体の特性が希釈され残留分極性Ｐｒが弱くなってくるため、用途によって最適Ｂ／Ａの量は変わる。一般的な最適範囲としては、０＜Ｂ／Ａ＜２０が好ましく、更には０．１＜Ｂ／Ａ＜２０、更には０．２＜Ｂ／Ａ＜２０、最も好ましくは０．４＜Ｂ／Ａ＜２０である。
【００１６】
本発明（請求項４）のＢＬＴ又はＢＴ強誘電体薄膜形成用組成物は、ＢＬＴ又はＢＴ強誘電体薄膜を形成するための有機金属化合物溶液よりなる強誘電体薄膜形成用組成物において、一般式：（ＢｉｘＬａｙ）４Ｔｉ３Ｏ１２（式中、０＜ｘ＜１．３、０≦ｙ＜１）で示される複合金属化合物Ａと、（Ｂｉα，Ｌａ１−α）２ＳｉＯ５ （式中、０≦α≦１）で示される複合金属酸化物Ｂの混合複合金属酸化物（ただし、ＢとＡとのモル比Ｂ／Ａは０＜Ｂ／Ａ＜５）の薄膜を形成するための液状組成物であって、該金属酸化物を構成する各金属の熱分解性有機金属化合物、加水分解性有機金属化合物、その部分加水分解物及び／又は重縮合物が、上式で示される金属原子比を与えるような割合で有機溶剤中に溶解している溶液からなることを特徴とするものである。
【００１７】
本発明（請求項５）のＢＬＴ強誘電体薄膜形成用組成物は、ＢＬＴ又はＢＴ強誘電体薄膜を形成するための有機金属化合物溶液よりなる強誘電体薄膜形成用組成物において、一般式：（ＢｉｘＬａｙ）４Ｔｉ３Ｏ１２（式中、０＜ｘ＜１．３、０≦ｙ＜１）で示される複合金属化合物Ａと、（Ｂｉβ，Ｌａ１−α）２ＳｉＯ５ （式中、０≦α≦１、α＜β＜１．３α）で示される複合金属酸化物Ｂの混合複合金属酸化物（ただし、ＢとＡとのモル比Ｂ／Ａは０＜Ｂ／Ａ＜５）の薄膜を形成するための液状組成物であって、該金属酸化物を構成する各金属の熱分解性有機金属化合物、加水分解性有機金属化合物、その部分加水分解物及び／又は重縮合物が、上式で示される金属原子比を与えるような割合で有機溶剤中に溶解している溶液からなることを特徴とするものである。
【００１８】
本発明者は、上記の複合酸化物Ｂについてさらに検討を重ねたところ、（Ｂｉα，Ｌａ１−α）２ＳｉＯ５又は（Ｂｉβ，Ｌａ１−α）２ＳｉＯ５が極めて好適であることが見出された。ただし、α＜β＜１．３αである。複合酸化物としてかかるＢｉ−Ｌａ−Ｓｉ系複合酸化物を用いると、ＢＬＴ又はＢＴ強誘電体薄膜がより低温で結晶化する。
【００１９】
本発明の強誘電体薄膜の形成方法は、この強誘電体薄膜形成用組成物を耐熱性基板に塗布し、空気中、酸化雰囲気中又は含水蒸気雰囲気中で加熱する工程を１回又は所望の厚さの膜が得られるまで繰り返し、少なくとも最終工程における加熱中或いは加熱後に該膜を結晶化温度以上で焼成することを特徴とするものである。
【００２０】
本発明の強誘電体薄膜は、この方法によって形成されたものである。
【００２１】
【発明の実施の形態】
以下に本発明の実施の形態を詳細に説明する。
【００２２】
本発明で用いる有機金属化合物原料は、有機基が、複合金属化合物Ａ用のＢｉ，Ｌａ及びＴｉ並びに金属化合物Ｂ用のＢｉ、Ｓｉ、Ｐｂ、Ｇｅ、Ｓｎ、Ａｌ、Ｇａ、Ｉｎ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｖ、Ｎｂ、Ｔａ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ｃｄ、Ｌｉ、Ｎａ及びＫの各金属に酸素又は窒素原子を介して結合しているものが好適であり、例えば金属アルコキシド、金属ジオール錯体、金属トリオール錯体、金属カルボン酸塩、金属β−ジケトネート錯体、金属β−ジケトエステル錯体、金属β−イミノケト錯体、及び金属アミノ錯体よりなる群から選ばれる１種又は２種以上が例示される。特に好適な化合物は、金属アルコキシド、その部分加水分解物及び／又は有機酸塩（例えば酢酸塩）である。アルコキシドとしては、メトキシド、エトキシド、イソプロポキシド、ブトキシド、ジメトキシジイソプロポキシド等のアルコキシドが挙げられる。金属アルコキシドはそのまま使用してもよいが、分解を促進させるためにその部分加水分解物を使用してもよい。
【００２３】
本発明のＢＬＴ又はＢＴ強誘電体薄膜形成用組成物を調製するには、これらの原料有機金属化合物を、所望のＢＬＴ又はＢＴ強誘電体薄膜組成に相当する比率で適当な溶媒に溶解して、塗布に適した濃度に調製する。
【００２４】
ここで用いるＢＬＴ又はＢＴ強誘電体薄膜形成用組成物の溶媒は、原料有機金属化合物に応じて適宜決定されるが、一般的には、カルボン酸、アルコール、エステル、ケトン類（例えば、アセトン、メチルエチルケトン）、エーテル類（例えば、ジメチルエーテル、ジエチルエーテル）、シクロアルカン類（例えば、シクロヘキサン、シクロヘキサノール）、芳香族系（例えば、ベンゼン、トルエン、キシレン）、その他テトラヒドロフラン等、或いはこれらの２種以上の混合溶媒を用いることができる。
【００２５】
複合酸化物Ｂが（Ｂｉα，Ｌａ１−α）２ＳｉＯ５又は（Ｂｉβ，Ｌａ１−α）２ＳｉＯ５である場合、溶媒はモノアルコール及びジオールの混合溶媒を含むか、又はこの混合溶媒よりなることが好ましい。ジオールとしては、トリエチレングリコールが特に好ましいが、プロピレングリコールも好適である。
【００２６】
カルボン酸としては、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−エチルヘキサン酸を用いるのが好ましい。
【００２７】
また、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、２−メトキシエタノールを用いるのが好適である。
【００２８】
なお、ＢＬＴ又はＢＴ強誘電体薄膜形成用組成物の有機金属化合物溶液中の有機金属化合物の合計濃度は、金属酸化物換算量で０．１〜２０重量％程度とするのが好ましい。
【００２９】
この有機金属化合物溶液中には、必要に応じて安定化剤として、β−ジケトン類（例えば、アセチルアセトン、ヘプタフルオロブタノイルピバロイルメタン、ジピバロイルメタン、トリフルオロアセチルアセトン、ベンゾイルアセトン等）、β−ケトン酸類（例えば、アセト酢酸、プロピオニル酢酸、ベンゾイル酢酸等）、β−ケトエステル類例えばこれらのケトン酸のメチル、プロピル、ブチル等の低級アルキルエステル類、オキシ酸類（例えば、乳酸、グリコール酸、α−オキシ酪酸、サリチル酸等）、これらのオキシ酸の低級アルキルエステル類、オキシケトン類（例えば、ジアセトンアルコール、アセトイン等）、ジオール、トリオール、高級カルボン酸、アルカノールアミン類（例えば、ジェタノールアミン、トリエタノールアミン、モノエタノールアミン）、多価アミン等を、（安定化剤分子数）／（金属原子数）で０．２〜３程度添加しても良い。
【００３０】
本発明では、このようにして調製された有機金属化合物溶液を濾過処理するなどして、パーティクルを除去し、粒径０．５μｍ以上（特に０．３μｍ以上とりわけ０．２μｍ以上）のパーティクルの個数が溶液１ｍＬ当り５０個／ｍＬ以下となるようにするのが好ましい。
【００３１】
有機金属化合物溶液中の粒径０．５μｍ以上のパーティクルの個数が５０個／ｍＬを超えると、長期保存安定性が劣るものとなる。この有機金属化合物溶液中の粒径０．５μｍ以上のパーティクルの個数は少ない程好ましく、特に３０個／ｍＬ以下であることが好ましい。
【００３２】
このようなパーティクル個数となるように、調製後の有機金属化合物溶液を処理する方法としては特に制限はないが、具体的には次のような方法が挙げられる。
【００３３】
(1) 市販の０．２μｍ孔径のメンブランフィルターを使用し、シリンジで圧送する濾過法。
(2) 市販の０．０５μｍ孔径のメンブランフィルターと加圧タンクを組み合せた加圧濾過法。
(3) 上記(2)のフィルターと溶液循環槽を組み合せた循環濾過法。
【００３４】
いずれの方法においても、溶液圧送圧力により、フィルターによるパーティクル捕捉率が異なる。圧力が低いほど捕捉率が高くなることは一般的に知られており、特に、(1)，(2)について、パーティクル５０個以下の条件を実現するためには、低圧で非常にゆっくりとフィルターに通すのが好ましい。
【００３５】
このようなＢＬＴ又はＢＴ強誘電体薄膜形成用組成物により、本発明の方法に従って、ＢＬＴ又はＢＴ強誘電体薄膜を形成するには、上述の本発明のＢＬＴ又はＢＴ強誘電体薄膜形成用組成物をスピンコート、ディップコート、ＬＳＭＣＤ（Ｌｉｑｕｉｄ Ｓｏｕｒｃｅ Ｍｉｓｔｅｄ Ｃｈｅｍｉｃａｌ Ｄｅｐｏｓｉｔｉｏｎ）法等の塗布法により基板上に塗布し、乾燥（仮焼成）及び本焼成を行う。
【００３６】
使用される基板の具体例としては、基板表層部に、単結晶Ｓｉ、多結晶Ｓｉ，Ｐｔ，Ｐｔ（最上層）／Ｔｉ，Ｐｔ（最上層）／Ｔａ，Ｒｕ，ＲｕＯ２，Ｒｕ（最上層）／ＲｕＯ２，ＲｕＯ２（最上層）／Ｒｕ，Ｉｒ，ＩｒＯ２，Ｉｒ（最上層）／ＩｒＯ２，Ｐｔ（最上層）／Ｉｒ，Ｐｔ（最上層）／ＩｒＯ２，ＳｒＲｕＯ３又は（ＬａｘＳｒ１−ｘ）ＣｏＯ３等のペロブスカイト型導電性酸化物等を用いた基板が挙げられるが、これらに限定されるものではない。
【００３７】
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。
【００３８】
ここで、仮焼成は、溶媒を除去すると共に有機金属化合物を熱分解又は加水分解して複合酸化物に転化させるために行うことから、空気中、酸化雰囲気中、又は含水蒸気雰囲気中で行う。空気中での加熱でも、加水分解に必要な水分は空気中の湿気により十分に確保される。この加熱は、溶媒の除去のための低温加熱と、有機金属化合物の分解のための高温加熱の２段階で実施しても良い。
【００３９】
本焼成は、仮焼成で得られた薄膜を結晶化温度以上の温度で焼成して結晶化させるための工程であり、これによりＢＬＴ又はＢＴ強誘電体薄膜が得られる。この結晶化工程の焼成雰囲気はＯ２、Ｎ２、Ａｒ、Ｎ２Ｏ又はＨ２等あるいはこれらの混合ガス等が好適である。
【００４０】
一般に、仮焼成は、１５０〜３５０℃で行われ、本焼成は５３０〜５９０℃で行われる。本発明では、本焼成温度が低くても薄膜を結晶化させることができる。
【００４１】
【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。
【００４２】
なお、以下の実施例及び比較例において、有機金属化合物原料としては、次のものを用いた。
Ｂｉ化合物： Ｂｉエトキシド
Ｌａ化合物： ランタン２−メトキシエトキシド
Ｔｉ化合物： チタンテトライソプロポキシド
Ｓｉ化合物： Ｓｉテトラエトキシド
Ｇｅ化合物： Ｇｅテトラエトキシド
Ｓｎ化合物： Ｓｎテトラｎ−ブトキシド
Ａｌ化合物： Ａｌトリイソプロポキシド
Ｇａ化合物： Ｇａトリエトキシド
Ｉｎ化合物： Ｉｎトリイソプロポキシド
Ｍｇ化合物： Ｍｇエトキシド
Ｃａ化合物： Ｃａエトキシド
Ｓｒ化合物： Ｓｒエトキシド
Ｂａ化合物： Ｂａエトキシド
Ｖ化合物 ： バナジルトリイソプロポキシド
Ｎｂ化合物： Ｎｂペンタエトキシド
Ｔａ化合物： Ｔａペンタエトキシド
Ｓｃ化合物： 酢酸スカンジウム
Ｙ化合物 ： Ｙイソプロポキシド
Ｚｒ化合物： Ｚｒテトラノルマルブトキシド
Ｈｆ化合物： Ｈｆラトラエトキシド
Ｃｒ化合物： Ｃｒトリイソプロポキシド
Ｍｎ化合物： Ｍｎメトキシド
Ｆｅ化合物： Ｆｅトリイソプロポキシド
Ｃｏ化合物： ２−エチルヘキサン酸Ｃｏ
Ｎｉ化合物： ２−エチルヘキサン酸Ｎｉ
Ｚｎ化合物： ２−エチルヘキサン酸Ｚｎ
Ｃｄ化合物： ２−エチルヘキサン酸Ｃｄ
Ｌｉ化合物： Ｌｉエトキシド
Ｎａ化合物： Ｎａエトキシド
Ｋ化合物 ： Ｋエトキシド
【００４３】
実験Ｎｏ．１〜２４１
有機溶媒として十分に脱水処理した２−メトキシエタノールを使用し、これに各金属化合物を溶解させ、溶液安定化のためアセチルアセトンを金属アルコキシドに対して２倍モル加えて加熱還流反応させ、表１〜９に示す組成で、有機金属化合物の合計濃度が金属酸化物換算濃度で約１０重量％の薄膜形成用溶液を調製した。
【００４４】
各々の溶液を用いて、下記方法によりＣＳＤ法による薄膜の形成を行った。
【００４５】
即ち、各々の溶液をスピンコート法により２０００ｒｐｍで３０秒間の条件で６インチシリコン基板上に塗布した。
【００４６】
次いで、ホットプレートを用い、２００℃で１０分間加熱して仮焼成を行った。この塗布、仮焼成の工程を２回繰り返した後、種々の温度の酸素雰囲気中で１分間ＲＴＡ（急速加熱処理装置）で焼成して膜厚２０００Åの強誘電体薄膜を形成し、結晶化温度を調べた。また、成膜された膜についてＳＥＭによりモフォロジーを観察した。結果を表１〜９に示す。なお、表１〜９において○はモフォロジーが良いことを示し、△はやや良いことを示し、×は良くないことを示す。
【００４７】
また、これらのＮｏ．１〜２４１において、最終焼成温度を一律に５５０℃としたこと以外は同一条件で強誘電体薄膜を形成し、各強誘電体薄膜の印加電圧３Ｖにおける残留分極Ｐｒを調べ、結果を表１〜９に示した。
【００４８】
【表１】
【表２】
【表３】
【表４】
【表５】
【表６】
【表７】
【表８】
【表９】
表１〜９の通り、Ｂ組成無しのＮｏ．１（比較例）に対し、Ｂ組成を添加したＮｏ．２〜２４１（実施例）のものはいずれも結晶化温度が低い。また、Ｎｏ．２〜２４１の通り、Ｂ／Ａを大きくすることにより、結晶化温度がより低くなる。そして、Ｂ／Ａを０．２以上とし、特に０．３とすることにより、結晶化温度は十分に低くなる。結晶化温度が５５０℃となるようにＢ成分を添加したサンプルは、いずれも５５０℃焼成物の残留分極Ｐｒが十分に大きい値となっている。
【００５８】
実験Ｎｏ．２４２〜３１３
１）ＢＬＴ溶液の合成
有機溶剤としてジエチレングリコールを使用し、これに２−エチルへキサン酸Ｂｉ、２−エチルへキサン酸Ｌａ、Ｔｉイソプロポキシドを溶解し、溶媒沸点下で還流させながら生成してくる低沸点副生成有機物を蒸留留去しつつ１０時間反応させＢＬＴの複合金属有機化合物を合成した。この後、アセチルアセトンを金属合計量に対して１倍モル加え、溶媒沸点下で１時間還流反応を行い、粘度調整のためブタノールで溶液を希釈し安定な表１０，１１のＢＬＴ組成のＢＬＴ薄膜形成剤を得た。
２）Ｂｉ−Ｓｉ溶液の合成
有機溶剤として十分に脱水したｎ−ブタノールを使用し、これに２−エチルへキサン酸ＢｉとＳｉエトキシドをモル比でＢｉ：Ｓｉ＝２：１となるように加えて溶解し、溶媒沸点下で２時間還流させＢｉ−Ｓｉの複合金属有機化合物を合成した。この後、アセチルアセトンを金属合計量に対して１倍モル加え、溶媒沸点下で１時間還流反応を行い、安定なＢｉ−Ｓｉ薄膜形成剤を得た。
３）Ｌａ−Ｓｉ溶液の合成
有機溶剤として十分に脱水したｎ−ブタノールを使用し、これに酢酸ランタン１．５水和物を溶解させ、共沸蒸留により結晶水を除去した。得られた溶液にモル比でＬａ：Ｓｉ＝２：１となるようにＳｉエトキシドを加えて溶解し、溶媒沸点下で２時間還流させＬａ−Ｓｉの複合金属有機化合物を合成した。この後、アセチルアセトンを金属合計量に対して１倍モル加え、溶媒沸点下で１時間還流反応を行い、安定なＬａ−Ｓｉ薄膜形成剤を得た。
【００５９】
上記Ｂｉ−Ｓｉ溶液とＬａ−Ｓｉ溶液を表１０，１１記載のＢ組成となるよう混合し、更にこの溶液とＢＬＴ溶液を表１０，１１に示すＢ／Ａ組成比となるよう混合し、溶媒沸点下で１時間還流反応を行い、安定なＢＬＴ−Ｂｉ−Ｌａ−Ｓｉ薄膜形成剤を得た。これら溶液を使用し、複合金属酸化物薄膜の成膜を行った。最終的な結晶化温度は４００，４５０，５００，５５０，６００℃でそれぞれ行い、組成により結晶化が何℃で起こっているかをＸＲＤで確認した。その結果を表１０，１１に示す。
【００６０】
【表１０】
【表１１】
実験Ｎｏ．３１４〜３８５
１）ＢＬＴ溶液の合成
有機溶剤としてプロピレングリコールを使用し、これに酢酸ランタンを溶解させ、共沸蒸留により結晶水を除去した。得られた溶液にＢｉエトキシド、Ｔｉイソプロポキシドを溶解し、溶媒沸点下で還流させながら生成してくる低沸点副生成有機物を蒸留留去しつつ５時間反応させＢＬＴの複合金属有機化合物を合成した。この後、アセチルアセトンを金属合計量に対して１倍モル加え、溶媒沸点下で１時間還流反応を行い、粘度調整のためイソプロパノールで溶液を希釈し安定な表１２，１３のＢＬＴ組成のＢＬＴ薄膜形成剤を得た。
２）Ｂｉ−Ｓｉ溶液の合成
有機溶剤として十分に脱水したｎ−ブタノールを使用し、これにＢｉエトキシドとＳｉエトキシドをモル比でＢｉ：Ｓｉ＝２：１となるように加えて溶解し、溶媒沸点下で２時間還流させＢｉ−Ｓｉの複合金属有機化合物を合成した。この後、アセチルアセトンを金属合計量に対して１倍モル加え、溶媒沸点下で１時間還流反応を行い、安定なＢｉ−Ｓｉ薄膜形成剤を得た。
３）Ｌａ−Ｓｉ溶液の合成
有機溶剤として十分に脱水したｎ−ブタノールを使用し、これに酢酸ランタン１．５水和物を溶解させ、共沸蒸留により結晶水を除去した。得られた溶液にモル比でＬａ：Ｓｉ＝２：１となるようにＳｉエトキシドを加えて溶解し、溶媒沸点下で２時間還流させＬａ−Ｓｉの複合金属有機化合物を合成した。この後、アセチルアセトンを金属合計量に対して１倍モル加え、溶媒沸点下で１時間還流反応を行い、安定なＬａ−Ｓｉ薄膜形成剤を得た。
【００６３】
上記Ｂｉ−Ｓｉ溶液とＬａ−Ｓｉ溶液を表１２，１３記載のＢ組成となるよう混合し、更にこの溶液とＢＬＴ溶液を表１２，１３に示すＢ／Ａ組成比となるよう混合し、溶媒沸点下で１時間還流反応を行い、安定なＢＬＴ−Ｂｉ−Ｌａ−Ｓｉ薄膜形成剤を得た。これら溶液を使用し、複合金属酸化物薄膜の成膜を行った。最終的な結晶化温度は４００，４５０，５００，５５０，６００℃でそれぞれ行い、組成により結晶化が何℃で起こっているかをＸＲＤで確認した。その結果を表１２，１３に示す。
【００６４】
【表１２】
【表１３】
実験Ｎｏ．３８６〜４５７
１）ＢＬＴ溶液の合成
有機溶剤としてジエチレングリコールを使用し、これに２−エチルへキサン酸Ｂｉ、２−エチルへキサン酸Ｌａ、Ｔｉイソプロポキシドを溶解し、溶媒沸点下で還流させながら生成してくる低沸点副生成有機物を蒸留留去しつつ１０時間反応させＢＬＴの複合金属有機化合物を合成した。この後、アセチルアセトンを金属合計量に対して１倍モル加え、溶媒沸点下で１時間還流反応を行い、粘度調整のためイソプロパノールで溶液を希釈し安定な表１４，１５のＢＬＴ組成のＢＬＴ薄膜形成剤を得た。
２）Ｂｉ−Ｓｉ溶液の合成
有機溶剤として十分に脱水したｎ−ブタノールを使用し、これに２−エチルへキサン酸ＢｉとＳｉエトキシドをモル比でＢｉ：Ｓｉ＝２．１：１となるように加えて溶解し、溶媒沸点下で２時間還流させＢｉ−Ｓｉの複合金属有機化合物を合成した。この後、アセチルアセトンを金属合計量に対して１倍モル加え、溶媒沸点下で１時間還流反応を行い、安定なＢｉ−Ｓｉ薄膜形成剤を得た。
３）Ｌａ−Ｓｉ溶液の合成
有機溶剤として十分に脱水したｎ−ブタノールを使用し、これに酢酸ランタン１．５水和物を溶解させ、共沸蒸留により結晶水を除去した。得られた溶液にモル比でＬａ：Ｓｉ＝２：１となるようにＳｉエトキシドを加えて溶解し、溶媒沸点下で２時間還流させＬａ−Ｓｉの複合金属有機化合物を合成した。この後、アセチルアセトンを金属合計量に対して１倍モル加え、溶媒沸点下で１時間還流反応を行い、安定なＬａ−Ｓｉ薄膜形成剤を得た。
【００６７】
上記Ｂｉ−Ｓｉ溶液とＬａ−Ｓｉ溶液を表１４，１５記載のＢ組成となるよう混合し、更にこの溶液とＢＬＴ溶液を表１４，１５に示すＢ／Ａ組成比となるよう混合し、溶媒沸点下で１時間還流反応を行い、安定なＢＬＴ−Ｂｉ−Ｌａ−Ｓｉ薄膜形成剤を得た。これら溶液を使用し、複合金属酸化物薄膜の成膜を行った。最終的な結晶化温度は４００，４５０，５００，５５０，６００℃でそれぞれ行い、組成により結晶化が何℃で起こっているかをＸＲＤで確認した。その結果を表１４，１５に示す。
【００６８】
【表１４】
【表１５】
表１０〜１５の通り、実験Ｎｏ．２４２〜４５７のものは、結晶化温度が十分に低い。
【００７１】
【発明の効果】
以上の通り、本発明によると、ＢＬＴ又はＢＴ強誘電体薄膜の結晶化温度を低下させることができる薄膜形成用組成物と、薄膜形成方法と、この方法により形成された強誘電体薄膜とが提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention is expected to be applied to various devices due to electrical or optical properties.Or BTThe present invention relates to a ferroelectric thin film, a composition for forming the same, and a forming method.
[0002]
[Prior art]
Bismuth titanate and metal oxide doped with lanthanum (BLT: (BixRay))4Ti3O12) Is expected to be applied to devices such as various capacitors and nonvolatile memories because of its high dielectric constant and excellent ferroelectric characteristics. As a method for forming these metal oxide thin films, there are a sputtering method, an MOCVD method, and the like. As a method for forming a thin film relatively inexpensively and simply, there is a sol-gel method in which an organic metal solution is applied to a substrate.
[0003]
In the sol-gel method, after a raw material solution containing a hydrolyzable compound of each component metal as a raw material, a partial hydrolyzate thereof and / or a partial polycondensate thereof is applied to a substrate and the coating film is dried, A method of forming a ferroelectric thin film by heating to about 400 ° C. in air to form a metal oxide film, and further firing the metal oxide at a crystallization temperature or higher to crystallize the film. is there.
[0004]
As a method similar to the sol-gel method, there is an organometallic decomposition (MOD) method. In the MOD method, a raw material solution containing a thermally decomposable organometallic compound, for example, a metal β-diketone complex (for example, metal acetylacetonate) or a carboxylate (for example, acetate) is applied to a substrate. Heating in air or in an oxygen-containing atmosphere causes evaporation of the solvent in the coating film and thermal decomposition of the metal compound to form a metal oxide film, which is further baked at a temperature higher than the crystallization temperature to crystallize the film. Make it. Accordingly, the film forming operation is almost the same as that of the sol-gel method, except that the raw material compounds are different.
[0005]
Thus, since the sol-gel method and the MOD method have the same film forming operation, a method using both of them is also possible. That is, the raw material solution may contain both a hydrolyzable metal compound and a thermally decomposable metal compound. In that case, hydrolysis and thermal decomposition of the raw material compound occur during heating of the coating film, and the metal An oxide is formed.
[0006]
These sol-gel methods, MOD methods, and methods using these in combination are the CSD method (Chemical
Solution Deposition).
[0007]
In addition to the advantages of being inexpensive, simple and suitable for mass production, the CSD method has the excellent features that the film composition can be easily controlled and the film thickness is relatively uniform. Therefore, this is a film forming method advantageous for forming a ferroelectric thin film on a relatively flat substrate.
[0008]
In the conventional CSD method, the raw material solution is applied to a substrate and dried, followed by calcination, and this coating, drying and calcination are repeated until a desired film thickness is obtained. Film formation is performed by baking and crystallizing at a temperature equal to or higher than the crystallization temperature.
[0009]
[Problems to be solved by the invention]
Formation of a ferroelectric thin film by the CSD method requires firing for crystallization.
[0010]
On the other hand, in the memory using such a ferroelectric thin film, with the miniaturization of the device chip, adverse effects on the transistor of the device and its peripheral circuit due to the heat treatment are becoming a problem. It is desired to reduce the crystallization temperature when forming a metal oxide thin film. Also, a reduction in crystallization temperature is expected to prevent oxidation of aluminum wiring on the substrate.
[0011]
In applications other than ferroelectric memory, reducing the crystallization temperature during film formation enables film formation on glass substrates and the like, which were difficult to form at conventional crystallization temperatures. Reduction of the crystallization temperature is strongly desired since it is expected to expand the application range of piezoelectric materials, piezoelectric materials, current collectors, and the like.
[0012]
The present invention provides BLTOr BTComposition for forming a metal oxide thin film that can be crystallized even at a low temperature of 550 ° C. or less in forming a ferroelectric thin film, formation method, and ferroelectric thin film formed by this low temperature crystallization method The purpose is to provide.
[0013]
[Means for Solving the Problems]
BLT of the present invention (Claim 1)Or BTThe composition for forming a ferroelectric thin film is a composition for forming a ferroelectric thin film made of an organometallic compound solution for forming a BLT ferroelectric thin film.xLay)4Ti3O12(Wherein, 0 <x <1.3, 0 ≦ y <1) and the composite metal compound A and Bi, Si, Pb, Ge, Sn, Al, Ga, In, Mg, Ca, Sr, Ba 1 selected from V, Nb, Ta, Sc, Y, Ti, Zr, Hf, Cr, Mn, Fe, Co, Ni, Zn, Cd, Li, Na and KSeedComposed of elementsMoneyMixture of metal oxide BalloyA liquid composition for forming a metal oxide thin film comprising a thermally decomposable organometallic compound, a hydrolyzable organometallic compound, a partially hydrolyzed product and / or a heavy metal of each metal constituting the metal oxide. The condensate is organic in proportions that give the metal atomic ratio shown in the above formulasolventFrom the solution that is dissolved inThe crystallization temperature of the formed BLT or BT ferroelectric thin film is 580 ° C. or lower.It is characterized by that.
[0014]
As a result of various studies to reduce the crystallization temperature of the ferroelectric thin film, the present inventors have found that Bi, Si, Pb, Ge, Sn, Al, Ga, In, Mg, Ca, Sr, Ba, V NLT, Nb, Ta, Sc, Y, Ti, Zr, Hf, Cr, Mn, Fe, Co, Ni, Zn, Cd, Li, Na, and K.Or BTTo add pure BLTOr BTAs a result, it was found that crystallization occurred at a lower temperature and the film morphology was improved.
[0015]
The composition of the present invention has been created based on such knowledge. The molar ratio B / A between B and A is preferably 0 <B / A <100. The effect of B as a dopant begins to appear in a state in which a small amount of B is mixed, but as the amount of B increases, an effect of improving the crystallization temperature and further the morphology appears. However, if B / A becomes too large, the characteristics of A itself are diluted and the residual polarizability Pr becomes weak. Therefore, the optimum amount of B / A varies depending on the application. As a general optimum range, 0 <B / A <20 is preferable, further 0.1 <B / A <20, further 0.2 <B / A <20, and most preferably 0.4 <B. / A <20.
[0016]
The present invention (claims)4BLTOr BTThe composition for forming a ferroelectric thin film is BLT.Or BTIn a composition for forming a ferroelectric thin film comprising an organometallic compound solution for forming a ferroelectric thin film, a general formula: (BixLay)4Ti3O12(Wherein, composite metal compound A represented by 0 <x <1.3, 0 ≦ y <1) and (Biα, La1-α)2SiO5 (Where 0 ≦ α ≦ 1)A mixed composition of composite metal oxide B represented by the formula (wherein the molar ratio B / A B / A is 0 <B / A <5), and a liquid composition for forming a thin film: A ratio such that the thermally decomposable organometallic compound, hydrolyzable organometallic compound, partially hydrolyzed product and / or polycondensate of each metal constituting the metal oxide give a metal atomic ratio represented by the above formula OrganicsolventIt consists of the solution melt | dissolved in.
[0017]
The present invention (claims)5BLT ferroelectric thin film forming composition is BLTOr BTIn a composition for forming a ferroelectric thin film comprising an organometallic compound solution for forming a ferroelectric thin film, a general formula: (BixLay)4Ti3O12(Wherein, composite metal compound A represented by 0 <x <1.3, 0 ≦ y <1) and (Biβ, La1-α)2SiO5 (Where 0 ≦ α ≦ 1, α <β <1.3α)A mixed composite metal oxide of composite metal oxide B represented by the formula (However, the molar ratio B / A between B and A is 0 <B / A <5)A liquid composition for forming a thin film of the metal oxide comprising a thermally decomposable organometallic compound, a hydrolyzable organometallic compound, a partially hydrolyzed product and / or a polycondensate of each metal constituting the metal oxide. , Organic at a ratio giving the metal atomic ratio shown in the above formulasolventIt consists of the solution melt | dissolved in.
[0018]
The inventor conducted further studies on the composite oxide B, and found that (Biα, La1-α)2SiO5Or (Biβ, La1-α)2SiO5Has been found to be very suitable. However, α <β <1.3α. When such a Bi-La-Si composite oxide is used as the composite oxide, BLTOr BTFerroelectric thin films crystallize at lower temperatures.
[0019]
In the method for forming a ferroelectric thin film of the present invention, this ferroelectric thin film forming composition is applied to a heat resistant substrate and heated in air, in an oxidizing atmosphere or in a water-containing atmosphere once or in a desired manner. The process is repeated until a film having a thickness is obtained, and the film is fired at a temperature equal to or higher than the crystallization temperature at least during or after heating in the final step.
[0020]
The ferroelectric thin film of the present invention is formed by this method.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0022]
In the organometallic compound raw material used in the present invention, the organic group is aligned with Bi, La and Ti for the composite metal compound A.To goldBi, Si, Pb, Ge, Sn, Al, Ga, In, Mg, Ca, Sr, Ba, V, Nb, Ta, Sc, Y, Ti, Zr, Hf, Cr, Mn, Fe for the genus compound B , Co, Ni, Zn, Cd, Li, Na and K are preferably bonded to each metal via an oxygen or nitrogen atom, such as metal alkoxide, metal diol complex, metal triol complex, metal carboxylic acid. Examples thereof include one or more selected from the group consisting of a salt, a metal β-diketonate complex, a metal β-diketoester complex, a metal β-iminoketo complex, and a metal amino complex. Particularly suitable compounds are metal alkoxides, partial hydrolysates thereof and / or organic acid salts (eg acetates). Examples of the alkoxide include alkoxides such as methoxide, ethoxide, isopropoxide, butoxide, dimethoxydiisopropoxide. Although the metal alkoxide may be used as it is, a partially hydrolyzed product thereof may be used in order to promote decomposition.
[0023]
BLT of the present inventionOr BTIn order to prepare a composition for forming a ferroelectric thin film, these raw material organometallic compounds are mixed with a desired BLT.Or BTIt is dissolved in a suitable solvent at a ratio corresponding to the composition of the ferroelectric thin film, and adjusted to a concentration suitable for coating.
[0024]
BLT used hereOr BTThe solvent of the composition for forming a ferroelectric thin film is appropriately determined according to the raw material organometallic compound, but in general, carboxylic acid, alcohol, ester, ketones (for example, acetone, methyl ethyl ketone), ethers ( For example, dimethyl ether, diethyl ether), cycloalkanes (for example, cyclohexane, cyclohexanol), aromatics (for example, benzene, toluene, xylene), other tetrahydrofuran, or a mixed solvent of two or more of these may be used. it can.
[0025]
Complex oxide B is (Biα, La1-α)2SiO5Or (Biβ, La1-α)2SiO5In this case, the solvent preferably contains a mixed solvent of monoalcohol and diol or consists of this mixed solvent. As the diol, triethylene glycol is particularly preferable, but propylene glycol is also preferable.
[0026]
Specific examples of the carboxylic acid include 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-dimethylpentanoic acid, 2- It is preferable to use ethylhexanoic acid or 3-ethylhexanoic acid.
[0027]
As the ester, ethyl acetate, propyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, isobutyl acetate, n-amyl acetate, sec-amyl acetate, tert-amyl acetate, isoamyl acetate are used. As the alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butyl alcohol, 1-pentanol, 2-pentanol, 2-methyl-2-pentanol, 2-methoxy It is preferred to use ethanol.
[0028]
BLTOr BTThe total concentration of the organometallic compound in the organometallic compound solution of the composition for forming a ferroelectric thin film is preferably about 0.1 to 20% by weight in terms of metal oxide.
[0029]
In this organometallic compound solution, β-diketones (for example, acetylacetone, heptafluorobutanoylpivaloylmethane, dipivaloylmethane, trifluoroacetylacetone, benzoylacetone, etc.) are used as stabilizers as necessary. Β-ketone acids (for example, acetoacetic acid, propionylacetic acid, benzoylacetic acid, etc.), β-ketoesters, for example, lower alkyl esters of these ketone acids such as methyl, propyl, butyl, etc., oxyacids (for example, lactic acid, glycolic acid) , Α-oxybutyric acid, salicylic acid, etc.), lower alkyl esters of these oxyacids, oxyketones (eg, diacetone alcohol, acetoin, etc.), diols, triols, higher carboxylic acids, alkanolamines (eg, jetanolamine) , Triethanolamine Monoethanolamine), a multivalent amine and the like, may be added from 0.2 to 3 approximately at (stabilizer number of molecules) / (number of metal atoms).
[0030]
In the present invention, particles are removed by filtering the organometallic compound solution thus prepared, and the number of particles having a particle size of 0.5 μm or more (particularly 0.3 μm or more, especially 0.2 μm or more). Is preferably 50 / mL or less per mL of solution.
[0031]
When the number of particles having a particle size of 0.5 μm or more in the organometallic compound solution exceeds 50 particles / mL, long-term storage stability becomes poor. The smaller the number of particles having a particle size of 0.5 μm or more in this organometallic compound solution, the more preferable, and particularly preferably 30 particles / mL or less.
[0032]
Although there is no restriction | limiting in particular as a method of processing the organometallic compound solution after preparation so that it may become such a particle count, Specifically, the following methods are mentioned.
[0033]
(1) A filtration method in which a commercially available membrane filter having a pore size of 0.2 μm is used and pressure-fed with a syringe.
(2) A pressure filtration method combining a commercially available membrane filter with a pore size of 0.05 μm and a pressure tank.
(3) the above(2)Circulation filtration method combining a filter and a solution circulation tank.
[0034]
In any method, the particle capture rate by the filter varies depending on the solution pressure. It is generally known that the lower the pressure, the higher the capture rate,(1),(2)In order to realize the condition of 50 particles or less, it is preferable to pass the filter very slowly at a low pressure.
[0035]
BLT like thisOr BTAccording to the method of the present invention, a BLT is formed by a composition for forming a ferroelectric thin film.Or BTIn order to form a ferroelectric thin film, the BLT of the present invention described above is used.Or BTThe composition for forming a ferroelectric thin film is applied onto a substrate by a coating method such as spin coating, dip coating, or LSMCD (Liquid Source Misted Chemical Deposition), and is then dried (preliminary firing) and main firing.
[0036]
As a specific example of the substrate to be used, single-crystal Si, polycrystal Si, Pt, Pt (uppermost layer) / Ti, Pt (uppermost layer) / Ta, Ru, RuO are formed on the surface layer of the substrate.2, Ru (top layer) / RuO2, RuO2(Top layer) / Ru, Ir, IrO2, Ir (top layer) / IrO2, Pt (top layer) / Ir, Pt (top layer) / IrO2, SrRuO3Or (LaxSr1-xCoO3A substrate using a perovskite-type conductive oxide such as, but not limited to, is exemplified.
[0037]
In addition, when 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 baking is performed.
[0038]
Here, the preliminary calcination is performed in order to remove the solvent and thermally decompose or hydrolyze the organometallic compound to convert it into a composite oxide, so that it is performed in air, in an oxidizing atmosphere, or in a steam-containing atmosphere. Even in heating in the air, the moisture required for hydrolysis is sufficiently secured by the humidity in the air. This heating may be performed in two stages: low temperature heating for removing the solvent and high temperature heating for decomposing the organometallic compound.
[0039]
The main baking is a process for baking and crystallizing the thin film obtained by the preliminary baking at a temperature equal to or higher than the crystallization temperature.Or BTA ferroelectric thin film is obtained. The firing atmosphere in this crystallization process is O2, N2, Ar, N2O or H2Or a mixed gas thereof is suitable.
[0040]
Generally, pre-baking is performed at 150 to 350 ° C., and main baking is performed at 530 to 590 ° C. In the present invention, the thin film can be crystallized even if the main baking temperature is low.
[0041]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
[0042]
In the following Examples and Comparative Examples, the following were used as the organometallic compound raw materials.
Bi compound: Bi ethoxide
La compound: Lanthanum 2-methoxyethoxide
Ti compound: Titanium tetraisopropoxide
Si compound: Si tetraethoxide
Ge compound: Ge tetraethoxide
Sn compound: Sn tetra-n-butoxide
Al compound: Al triisopropoxide
Ga compound: Ga triethoxide
In compound: In triisopropoxide
Mg compound: Mg ethoxide
Ca compound: Ca ethoxide
Sr compound: Sr ethoxide
Ba compound: Ba ethoxide
V compound: vanadyl triisopropoxide
Nb compound: Nb pentaethoxide
Ta compound: Ta pentaethoxide
Sc compound: scandium acetate
Y compound: Y isopropoxide
Zr compound: Zr tetranormal butoxide
Hf compound: Hf ratraethoxide
Cr compound: Cr triisopropoxide
Mn compound: Mn methoxide
Fe compound: Fe triisopropoxide
Co compound: 2-ethylhexanoic acid Co
Ni compound: 2-ethylhexanoic acid Ni
Zn compound: 2-ethylhexanoic acid Zn
Cd compound: 2-ethylhexanoic acid Cd
Li compound: Li ethoxide
Na compound: Na ethoxide
K compound: K ethoxide
[0043]
Experiment No. 1-241
Using 2-methoxyethanol that has been sufficiently dehydrated as an organic solvent, each metal compound is dissolved therein, and acetylacetone is added to the metal alkoxide twice in order to stabilize the solution, followed by heating under reflux, A thin film forming solution having the composition shown in 9 and having a total organometallic compound concentration of about 10% by weight in terms of metal oxide was prepared.
[0044]
Using each solution, a thin film was formed by the CSD method by the following method.
[0045]
That is, each solution was applied onto a 6-inch silicon substrate by spin coating at 2000 rpm for 30 seconds.
[0046]
Subsequently, using a hot plate, it preheated by heating at 200 degreeC for 10 minutes. This coating and pre-baking process was repeated twice, followed by baking with an RTA (rapid heat treatment apparatus) for 1 minute in an oxygen atmosphere at various temperatures to form a ferroelectric thin film having a thickness of 2000 mm, and a crystallization temperature. I investigated. Further, the morphology of the formed film was observed by SEM. The results are shown in Tables 1-9. In Tables 1 to 9, ◯ indicates that the morphology is good, Δ indicates that it is slightly better, and X indicates that it is not good.
[0047]
In addition, these No. 1 to 241, a ferroelectric thin film was formed under the same conditions except that the final firing temperature was uniformly set to 550 ° C., and the residual polarization Pr at an applied voltage of 3 V of each ferroelectric thin film was examined. 9 shows.
[0048]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
[Table 9]
As Tables 1 to 9, No. 1 (comparative example), No. 1 to which the B composition was added. Any of the materials of 2 to 241 (Examples) has a low crystallization temperature. No. As shown in 2 to 241, the crystallization temperature becomes lower by increasing B / A. And by making B / A 0.2 or more, especially 0.3, the crystallization temperature becomes sufficiently low. In all the samples to which the B component was added so that the crystallization temperature was 550 ° C., the residual polarization Pr of the 550 ° C. fired product had a sufficiently large value.
[0058]
Experiment No. 242-313
1) Synthesis of BLT solution
Diethylene glycol is used as the organic solvent, and 2-ethylhexanoic acid Bi, 2-ethylhexanoic acid La, and Ti isopropoxide are dissolved in this, and the low-boiling by-product organic product is produced while refluxing at the boiling point of the solvent. Was reacted by distillation for 10 hours to synthesize BLT complex metal organic compound. After that, acetylacetone is added in a molar amount of 1 times the total amount of metal, and the reaction is refluxed for 1 hour at the boiling point of the solvent. An agent was obtained.
2) Synthesis of Bi-Si solution
Use sufficiently dehydrated n-butanol as an organic solvent, and add 2-ethylhexanoic acid Bi and Si ethoxide in a molar ratio of Bi: Si = 2: 1 and dissolve it at a solvent boiling point. The mixture was refluxed for 2 hours to synthesize a Bi—Si composite metal organic compound. Thereafter, acetylacetone was added in an amount of 1-fold mol with respect to the total amount of metals, and a reflux reaction was carried out at the boiling point of the solvent for 1 hour to obtain a stable Bi-Si thin film forming agent.
3) Synthesis of La-Si solution
Sufficiently dehydrated n-butanol was used as an organic solvent, and lanthanum acetate hemihydrate was dissolved in this, and water of crystallization was removed by azeotropic distillation. Si ethoxide was added to the resulting solution so that the molar ratio of La: Si = 2: 1 was dissolved, and the mixture was refluxed at the boiling point of the solvent for 2 hours to synthesize a La—Si complex metal organic compound. Thereafter, 1 mol of acetylacetone was added to the total amount of metals, and a reflux reaction was performed for 1 hour at the boiling point of the solvent to obtain a stable La-Si thin film forming agent.
[0059]
The Bi-Si solution and the La-Si solution are mixed so as to have the B composition described in Tables 10 and 11, and this solution and the BLT solution are further mixed so that the B / A composition ratios shown in Tables 10 and 11 are obtained. A reflux reaction was performed at the boiling point for 1 hour to obtain a stable BLT-Bi-La-Si thin film forming agent. Using these solutions, a composite metal oxide thin film was formed. Final crystallization temperatures were 400, 450, 500, 550, and 600 ° C., respectively, and it was confirmed by XRD how many degrees of crystallization occurred depending on the composition. The results are shown in Tables 10 and 11.
[0060]
[Table 10]
[Table 11]
Experiment No. 314-385
1) Synthesis of BLT solution
Propylene glycol was used as an organic solvent, lanthanum acetate was dissolved in the solvent, and crystal water was removed by azeotropic distillation. Bi ethoxide and Ti isopropoxide are dissolved in the resulting solution, and a low-boiling by-product organic compound produced while refluxing at the boiling point of the solvent is distilled off for 5 hours to synthesize a composite metal organic compound of BLT. did. Thereafter, acetylacetone is added in a molar amount of 1 times the total amount of metal, and the reaction is refluxed for 1 hour at the boiling point of the solvent. An agent was obtained.
2) Synthesis of Bi-Si solution
A sufficiently dehydrated n-butanol is used as an organic solvent, and Bi ethoxide and Si ethoxide are added and dissolved in a molar ratio of Bi: Si = 2: 1. The mixture is refluxed for 2 hours at the boiling point of the solvent. A composite metal organic compound of -Si was synthesized. Thereafter, acetylacetone was added in an amount of 1-fold mol with respect to the total amount of metals, and a reflux reaction was carried out at the boiling point of the solvent for 1 hour to obtain a stable Bi-Si thin film forming agent.
3) Synthesis of La-Si solution
Sufficiently dehydrated n-butanol was used as an organic solvent, and lanthanum acetate hemihydrate was dissolved in this, and water of crystallization was removed by azeotropic distillation. Si ethoxide was added to the resulting solution so that the molar ratio of La: Si = 2: 1 was dissolved, and the mixture was refluxed at the boiling point of the solvent for 2 hours to synthesize a La—Si complex metal organic compound. Thereafter, 1 mol of acetylacetone was added to the total amount of metals, and a reflux reaction was performed for 1 hour at the boiling point of the solvent to obtain a stable La-Si thin film forming agent.
[0063]
The Bi-Si solution and the La-Si solution are mixed so as to have the B composition described in Tables 12 and 13, and this solution and the BLT solution are further mixed so that the B / A composition ratios shown in Tables 12 and 13 are obtained. A reflux reaction was performed at the boiling point for 1 hour to obtain a stable BLT-Bi-La-Si thin film forming agent. Using these solutions, a composite metal oxide thin film was formed. Final crystallization temperatures were 400, 450, 500, 550, and 600 ° C., respectively, and it was confirmed by XRD how many degrees of crystallization occurred depending on the composition. The results are shown in Tables 12 and 13.
[0064]
[Table 12]
[Table 13]
Experiment No. 386-457
1) Synthesis of BLT solution
Diethylene glycol is used as the organic solvent, and 2-ethylhexanoic acid Bi, 2-ethylhexanoic acid La, and Ti isopropoxide are dissolved in this, and the low-boiling by-product organic product is produced while refluxing at the boiling point of the solvent. Was reacted by distillation for 10 hours to synthesize BLT complex metal organic compound. Thereafter, acetylacetone is added in a molar amount of 1 times the total amount of metal, and the reaction is refluxed for 1 hour at the boiling point of the solvent. An agent was obtained.
2) Synthesis of Bi-Si solution
A sufficiently dehydrated n-butanol is used as an organic solvent, and 2-ethylhexanoic acid Bi and Si ethoxide are added and dissolved in a molar ratio of Bi: Si = 2.1: 1, and the solvent boiling point is obtained. The mixture was refluxed for 2 hours to synthesize a Bi-Si composite metal organic compound. Thereafter, acetylacetone was added in an amount of 1-fold mol with respect to the total amount of metals, and a reflux reaction was carried out at the boiling point of the solvent for 1 hour to obtain a stable Bi-Si thin film forming agent.
3) Synthesis of La-Si solution
Sufficiently dehydrated n-butanol was used as an organic solvent, and lanthanum acetate hemihydrate was dissolved in this, and water of crystallization was removed by azeotropic distillation. Si ethoxide was added to the resulting solution so that the molar ratio of La: Si = 2: 1 was dissolved, and the mixture was refluxed at the boiling point of the solvent for 2 hours to synthesize a La—Si complex metal organic compound. Thereafter, 1 mol of acetylacetone was added to the total amount of metals, and a reflux reaction was performed for 1 hour at the boiling point of the solvent to obtain a stable La-Si thin film forming agent.
[0067]
The Bi-Si solution and the La-Si solution are mixed so as to have the B composition described in Tables 14 and 15, and this solution and the BLT solution are further mixed so as to have the B / A composition ratios shown in Tables 14 and 15. A reflux reaction was performed at the boiling point for 1 hour to obtain a stable BLT-Bi-La-Si thin film forming agent. Using these solutions, a composite metal oxide thin film was formed. Final crystallization temperatures were 400, 450, 500, 550, and 600 ° C., respectively, and it was confirmed by XRD how many degrees of crystallization occurred depending on the composition. The results are shown in Tables 14 and 15.
[0068]
[Table 14]
[Table 15]
As shown in Tables 10 to 15, Experiment No. Those of 242 to 457 have a sufficiently low crystallization temperature.
[0071]
【The invention's effect】
As described above, according to the present invention, BLTOr BTCan lower the crystallization temperature of ferroelectric thin filmsThinThere are provided a film forming composition, a thin film forming method, and a ferroelectric thin film formed by this method.
Claims (12)
一般式：（ＢｉｘＬａｙ）４Ｔｉ３Ｏ１２（式中、０＜ｘ＜１．３、０≦ｙ＜１）で示される複合金属化合物Ａと、Ｂｉ、Ｓｉ、Ｐｂ、Ｇｅ、Ｓｎ、Ａｌ、Ｇａ、Ｉｎ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｖ、Ｎｂ、Ｔａ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ｃｄ、Ｌｉ、Ｎａ及びＫのうちから選ばれる１種の元素から構成される金属酸化物Ｂの混合金属酸化物の薄膜を形成するための液状組成物であって、
該金属酸化物を構成する各金属の熱分解性有機金属化合物、加水分解性有機金属化合物、その部分加水分解物及び／又は重縮合物が、上式で示される金属原子比を与えるような割合で有機溶剤中に溶解している溶液からなり、形成されるＢＬＴ又はＢＴ強誘電体薄膜の結晶化温度が５８０℃以下であることを特徴とするＢＬＴ又はＢＴ強誘電体薄膜形成用組成物。In a composition for forming a ferroelectric thin film comprising an organometallic compound solution for forming a BLT or BT ferroelectric thin film,
General formula: (Bi x La y) (where, 0 <x <1.3,0 ≦ y <1) 4 Ti 3 O 12 and the composite metal compound A represented by, Bi, Si, Pb, Ge , Sn Al, Ga, In, Mg, Ca, Sr, Ba, V, Nb, Ta, Sc, Y, Ti, Zr, Hf, Cr, Mn, Fe, Co, Ni, Zn, Cd, Li, Na, and K a one consists element Rukin genus oxide liquid composition for forming a thin film of mixed alloy genus oxides of B selected from among,
A ratio such that the thermally decomposable organometallic compound, hydrolyzable organometallic compound, partially hydrolyzed product and / or polycondensate of each metal constituting the metal oxide give a metal atomic ratio represented by the above formula in Ri Do from a solution dissolved in an organic solvent, formed by BLT or BLT or BT ferroelectric thin film-forming composition the crystallization temperature of the BT ferroelectric thin film is characterized in der Rukoto 580 ° C. or less object.
一般式：（ＢｉｘＬａｙ）４Ｔｉ３Ｏ１２（式中、０＜ｘ＜１．３、０≦ｙ＜１）で示される複合金属化合物Ａと、（Ｂｉα，Ｌａ１−α）２ＳｉＯ５ （式中、０≦α≦１）で示される複合金属酸化物Ｂの混合複合金属酸化物（ただし、ＢとＡとのモル比Ｂ／Ａは０＜Ｂ／Ａ＜５）の薄膜を形成するための液状組成物であって、
該金属酸化物を構成する各金属の熱分解性有機金属化合物、加水分解性有機金属化合物、その部分加水分解物及び／又は重縮合物が、上式で示される金属原子比を与えるような割合で有機溶剤中に溶解している溶液からなることを特徴とするＢＬＴ又はＢＴ強誘電体薄膜形成用組成物。In a composition for forming a ferroelectric thin film comprising an organometallic compound solution for forming a BLT or BT ferroelectric thin film,
General formula: (Bi x La y) (where, 0 <x <1.3,0 ≦ y <1) 4 Ti 3 O 12 and the composite metal compound represented by A, (Bi α, La 1 -α) 2 SiO 5 (wherein 0 ≦ α ≦ 1) mixed metal oxide B of mixed metal oxide B (however, the molar ratio B / A between B and A is 0 <B / A <5) A liquid composition for forming a thin film,
A ratio such that the thermally decomposable organometallic compound, hydrolyzable organometallic compound, partially hydrolyzed product and / or polycondensate of each metal constituting the metal oxide give a metal atomic ratio represented by the above formula A composition for forming a BLT or BT ferroelectric thin film comprising a solution dissolved in an organic solvent .
一般式：（ＢｉｘＬａｙ）４Ｔｉ３Ｏ１２（式中、０＜ｘ＜１．３、０≦ｙ＜１）で示される複合金属化合物Ａと、（Ｂｉβ，Ｌａ１−α）２ＳｉＯ５ （式中、０≦α≦１、α＜β＜１．３α）で示される複合金属酸化物Ｂの混合複合金属酸化物（ただし、ＢとＡとのモル比Ｂ／Ａは０＜Ｂ／Ａ＜５）の薄膜を形成するための液状組成物であって、
該金属酸化物を構成する各金属の熱分解性有機金属化合物、加水分解性有機金属化合物、その部分加水分解物及び／又は重縮合物が、上式で示される金属原子比を与えるような割合で有機溶剤中に溶解している溶液からなることを特徴とするＢＬＴ又はＢＴ強誘電体薄膜形成用組成物。In a composition for forming a ferroelectric thin film comprising an organometallic compound solution for forming a BL or BT ferroelectric thin film,
General formula: (Bi x La y ) 4 Ti 3 O 12 (where, 0 <x <1.3, 0 ≦ y <1) and the composite metal compound A, and (Bi β , La 1-α ) 2 SiO 5 (wherein 0 ≦ α ≦ 1, α <β <1.3α) mixed metal oxide B mixed complex metal oxide (provided that the molar ratio B / A between B and A is 0) <B / A < 5) A liquid composition for forming a thin film,
A ratio such that the thermally decomposable organometallic compound, hydrolyzable organometallic compound, partially hydrolyzed product and / or polycondensate of each metal constituting the metal oxide give a metal atomic ratio represented by the above formula A composition for forming a BLT or BT ferroelectric thin film comprising a solution dissolved in an organic solvent .
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