JP4225607B2 - Method for producing bismuth-containing composite metal oxide film - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、化学気相成長法（ＣＶＤ法）を利用して形成する、ビスマス含有複合金属酸化膜のビスマス源となるビスマス化合物と他の金属化合物とからつくられるビスマス含有複合金属酸化膜に関する。
【０００２】
【従来の技術および発明が解決しようとする課題】
不揮発性メモリー、ＤＲＡＭのキャパシタ材料などへの応用として、ビスマス含有金属複合酸化膜の開発が盛んに行われ、特にＣＶＤ法による膜形成に適したビスマス源となる化合物の開発が期待されている。
【０００３】
近年、酸化物系のセラミックスあるいは層状セラミックスなどの製法としてＣＶＤ法を用いることが行われるようになっており、例えば、ＳｒＢｉ2 Ｔａ2 Ｏ9 の金属複合酸化膜を強誘電体膜として不揮発メモリーに用いた場合、該金属複合酸化膜は、従来の強誘電体メモリーの問題点を解決可能な、優れた薄膜であることが知られている。
【０００４】
しかしながら、ＣＶＤ法に適した各金属源化合物は、これまでに提案されたものが必ずしも十分な特性を有しているとは言えなかった。例えば、従来のビスマス源として用いられていた化合物は比較的耐熱性が高く、分解温度が高いため成長速度が低く、高融点であるためにＣＶＤ装置への供給性や揮発性が他の金属源と比べて劣っていた。該化合物と揮発性、分解性の優れた他の金属源とを用いて金属複合酸化膜の成膜を行った場合には、両者の分解温度の違いから、薄膜形成プロセスにおけるビスマス／他の金属比の制御が困難であった。
【０００５】
さらに、トリフェニルビスマスやトリ（ｏ−トリル）ビスマスなどのビスマス源では、成膜時に必要な酸素原子を分子内に持たないため、これらのビスマス源を用いる場合には、酸素含有ガスなどの酸素源を共存させる必要があった。しかしながら、酸素含有ガスを共存させた場合には他の材料の分解析出に悪影響を及ぼす欠点があった。また、特開平９−６７１９７号公報などに提案されているビスマスのアルコキシド化合物のように、分子内に酸素原子を持った構造のビスマス化合物では、上記酸素源の問題は解決されている。しかしながら、これらの化合物は高融点の固体であるため、ＣＶＤ装置による成膜の際、該化合物をアルゴンガスなどのキャリアにより昇華同伴させて成膜室へ送る必要があるが、固体を昇華同伴させて使用する場合は、表面積の変化などにより試料の供給量が変化するために、厳密な供給量の制御が困難であった。
【０００６】
従って、本発明の目的は、比較的融点が低く、室温で液体またはわずかな加温で液化し、取り扱いが容易で成膜室への供給性に優れ、また昇華ではなく蒸発によって気化が可能で気化速度を一定に保つことができ、成膜室への原料の供給量の制御が容易であり、さらに、熱安定性や分解温度がＣＶＤ原料に好適なビスマス化合物を用いてなるビスマス含有複合金属酸化膜を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者等は、検討を重ねた結果、ビスマス源の原料としてエーテル基含有アルコキシド化合物としたビスマス化合物を用いてなるビスマス含有複合金属酸化膜が、上記目的を達成し得ることを知見した。
【０００８】
本発明は、上記知見に基づきなされたもので、化学気相成長法により、ＡＢｉ2Ｂ2Ｏ9（式中、ＡはＳｒまたはＢａを表し、ＢはＴａまたはＮｂを表す）で表されるビスマス含有複合金属酸化膜を成膜するに際し、下記［化２］（前記［化１］と同じ）の一般式（Ｉ）で表されるビスマス化合物と、上記式ＡＢｉ2Ｂ2Ｏ9中のＡおよびＢを与える原料として、金属アルコキシド化合物、複合金属アルコキシド化合物〔但し、Ｓｒ［Ｍ（ＯＲ1）6-xＬｘ］2（式中、ｘは１〜６であり、ＭはＴａまたはＮｂであり、Ｒ1は直鎖または分岐鎖アルキル基であり、Ｌは下記［化２−１］（前記［化１−１］と同じ）の一般式（ II ）で表わされる、アミノアルコキシド基またはアルコキシアルコキシド基である）で表される化合物を除く〕またはβ−ジケトン金属錯体化合物とを用いることを特徴とするビスマス含有複合金属酸化膜の製造方法を提供するものである。
【０００９】
【化２】
【発明の実施の形態】
以下、本発明のビスマス含有複合金属酸化膜について詳細に説明する。
本発明のビスマス含有複合金属酸化膜に係る上記一般式（Ｉ）で表されるビスマス化合物は、ＣＶＤ装置内での取り扱いおよび成膜室への供給速度の制御が容易であり、量産性の高い成膜が可能なＣＶＤ原料となりうるものである。
【００１１】
本発明のビスマス含有複合金属酸化膜の原料の一つとして用いられる上記一般式（Ｉ）で表されるビスマス化合物の具体例としては、下記［化３］〜［化６］に示す化合物Ｎｏ．１〜４等が挙げられる。ただし、本発明は以下の例示化合物により何ら限定されるものではない。
【００１２】
【化３】
【化４】
【化５】
【化６】
上記一般式（Ｉ）で表されるビスマス化合物のうち、Ｒ1 およびＲ2 がともにメチル基で、ｎが１である化合物が好ましい。
【００１７】
本発明に係る上記一般式（Ｉ）で表されるビスマス化合物の製造は、例えば次の合成例のようにして行うことができる。
【００１８】
合成例１（化合物Ｎｏ．１の合成例）
１Ｌの遮光丸底フラスコに、１−メトキシ−２−メチル−２−プロパノール３０．０ｇ、ナトリウム５．５２ｇおよび乾燥ＴＨＦ１００ｍｌを仕込んだ後、６０℃で５時間攪拌し、ナトリウムが消失したことを確認した。次に、フラスコ内を氷温まで冷却し、乾燥ＴＨＦ３５０ｍｌおよび塩化ビスマス２５．２４ｇを加えた。再び加熱してＴＨＦの還流下で３０時間攪拌した。減圧してＴＨＦを留去した後、ヘキサン８００ｍｌを加え、加温して残留物を溶解した。濾過して不溶物を除き、濾液を脱溶媒して、粗結晶３２．６ｇ（収率７８．６％）を得た。この粗結晶を減圧蒸留（０．０８ｔｏｒｒ、バス温度１３５〜１４４℃）し、白色固体２４．０ｇ（収率５７．９％）を得た。
【００１９】
得られた結晶について、ＩＣＰによるビスマス含有量、ＮＭＲ、融点および蒸気圧を測定した。それらの結果を以下に示す。
（１）ＩＣＰ
硝酸に溶解してサンプルを用いてＩＣＰを測定したところ、ビスマス含有量４０．３％（理論含有量４０．３％）であった。
（２）ＮＭＲ
13Ｃ−ＮＭＲ（重クロロホルム中：δ値）を測定したところ、次のピークを検出した。
・３０．３１９ ｐｐｍ
・５８．４３１ ｐｐｍ
・７２．２０４ ｐｐｍ
・８３．８２０ ｐｐｍ
また、 1Ｈ−ＮＭＲ（重クロロホルム中：δ値）を測定したところ、次のピークを検出した。
・１．１１７３ ｐｐｍ：ｓ，１８Ｈ
・３．１７２４ ｐｐｍ：ｓ，６Ｈ
・３．２７８０ ｐｐｍ：ｓ，９Ｈ
（３）融点および蒸気圧
微量融点測定装置を用いて融点を測定したところ、４９℃であった。また蒸気圧を測定したところ以下の結果を得た。
０．１Ｔｏｒｒ／ ９９℃
０．２Ｔｏｒｒ／１０７℃
０．３Ｔｏｒｒ／１１２℃
０．４Ｔｏｒｒ／１１５℃
【００２０】
合成例２（化合物Ｎｏ．２の合成例）
２００ｍｌの遮光丸底フラスコに、塩化ビスマス６．３１ｇに乾燥ベンゼン５０ｍｌを加えて攪拌しながら、１−メトキシ−２−プロパノール４０ｍｌにナトリウム１．３８ｇを溶解してできる溶液を室温で滴下した。次に、６０℃で３０時間攪拌し、乾燥ベンゼン４０ｍｌを追加して６０℃で濾過を行った。濾液を脱溶媒して淡褐色液体を得た後、減圧蒸留（約０．１ｔｏｒｒ、バス温度１５０℃）し、透明粘稠液体８．２５ｇ（収率８６．６％）を得た。
【００２１】
得られた結晶について、ＩＣＰによるビスマス含有量、ＮＭＲを測定した。それらの結果を以下に示す。
（１）ＩＣＰ
硝酸に溶解してサンプルを用いてＩＣＰを測定したところ、ビスマス含有量４３．７％（理論含有量４３．９％）であった。
（２）ＮＭＲ
13Ｃ−ＮＭＲ（重クロロホルム中：δ値）を測定したところ、次のピークを検出した。
・２３．７８７ ｐｐｍ
・５８．４３１ ｐｐｍ
・６７．０２９ ｐｐｍ
・８２．１０９ ｐｐｍ
また、 1Ｈ−ＮＭＲ（重クロロホルム中：δ値）を測定したところ、次のピークを検出した。
・１．１３５６ ｐｐｍ，１．１５１４ ｐｐｍ：ｄ，９Ｈ
・３．０２０５ ｐｐｍ：ｓ，９Ｈ
・３．１００４ ｐｐｍ，３．１１３８ ｐｐｍ：ｄ，６Ｈ
・４．８２２４ ｐｐｍ：ｓ，３Ｈ
【００２２】
本発明のビスマス含有複合金属酸化膜を成膜するための原料である上記一般式（Ｉ）で表されるビスマス化合物以外の金属源化合物としては、例えば、Ｔａ（ＯＥｔ）5 、Ｔａ（Ｏｉ−Ｐｒ）5 、Ｔａ（Ｏｔ−Ｂｕ）5 、Ｔａ（Ｏｔ−Ｐｅｎ）5 、Ｎｂ（ＯＥｔ）5 、Ｎｂ（Ｏｉ−Ｐｒ）5 、Ｎｂ（Ｏｔ−Ｂｕ）5 、Ｎｂ（Ｏｔ−Ｐｅｎ）5 、Ｓｒ（ＯＥｔ）2 、Ｓｒ（Ｏｉ−Ｐｒ）2 、Ｓｒ（Ｏｔ−Ｂｕ）2 、Ｓｒ（Ｏｔ−Ｐｅｎ）2 、Ｂａ（ＯＥｔ）2 、Ｂａ（Ｏｉ−Ｐｒ）2 、Ｂａ（Ｏｔ−Ｂｕ）2 、Ｂａ（Ｏｔ−Ｐｅｎ）2 などの金属アルコキシド化合物、Ｓｒ〔Ｔａ（ＯＥｔ）6 〕2 、Ｓｒ〔Ｎｂ（ＯＥｔ）6 〕2 、Ｂａ〔Ｔａ（ＯＥｔ）6 〕2 、Ｂａ〔Ｎｂ（ＯＥｔ）6 〕2 などの複合金属アルコキシド化合物、ジピバロイルメタナトバリウム、ジピバロイルメタナトストロンチウム、ピバロイルイソプロピオニルメタナトバリウム、ピバロイルイソプロピオニルメタナトストロンチウム、ジイソプロピオニルメタナトバリウム、ジイソプロピオニルメタナトストロンチウム、１−（２' −メトキシエトキシ）−２，２，６，６−テトラメチル−３，５−ヘプタンジオナトバリウム、１−（２' −メトキシエトキシ）−２，２，６，６−テトラメチル−３，５−ヘプタンジオナトストロンチウムなどのβ−ジケトン金属錯体化合物などが好ましく用いられる。（上記式中、Ｅｔはエチル基を示し、ｉ−Ｐｒはイソプロピル基を示し、ｔ−Ｂｕは第三ブチル基を示し、ｔ−Ｐｅｎは第三ペンチル基を示す。）
【００２３】
本発明のビスマス含有複合金属酸化膜〔ＡＢｉ2 Ｂ2 Ｏ9 〕（成膜後）中のビスマスと他の金属〔Ａ及びＢ〕との組成比は特に制限されず、強誘電性を示すような範囲に適宜設定されるが、好ましくは、〔Ｂｉ／Ａ／Ｂ〕＝１．８〜２．５／１／１．８〜２．５である。
【００２４】
本発明のビスマス含有複合金属酸化膜は、不揮発性メモリー、ＤＲＡＭのキャパシタ材料などの用途に用いられる。
【００２５】
本発明のビスマス含有複合金属酸化膜を成膜するために用いるＣＶＤ法としては、例えば、熱ＣＶＤ，プラズマＣＶＤ，光ＣＶＤなどの方法を挙げることができるが、一般にＣＶＤ装置に採用されるＣＶＤ法であれば特に制限を受けない。
【００２６】
【実施例】
以下、実施例をもって本発明を更に詳細に説明する。しかしながら、本発明は以下の実施例によって何ら制限を受けるものではない。
【００２７】
（実施例１）ＳｒＢｉ2 Ｔａ2 Ｏ9 膜の作成
熱ＣＶＤ装置の内圧を５Ｔｏｒｒに調整し、熱分解炉にはＰｔ／ＳｉＯ2 ／Ｓｉ基板を置き、基板温度を４００℃に調整した。
ビスマス源として、前記化合物Ｎｏ．１ ２０ｇを原料容器に充填し、この容器を７０℃に調整し液体とした。この容器にアルゴンガス導入し、蒸発した化合物Ｎｏ．１を同伴させ、原料ガスとした。
ストロンチウム源として、１−（２' −メトキシエトキシ）−２，２，６，６−テトラメチル−３，５−ヘプタンジオナトストロンチウム ２０ｇを原料容器に充填し、２００℃に調整した。この容器にアルゴンガス導入し、蒸発した１−（２' −メトキシエトキシ）−２，２，６，６−テトラメチル−３，５−ヘプタンジオナトストロンチウムを同伴させ、原料ガスとした。
タンタル源として、Ｔａ（ＯＥｔ）5 ２０ｇを原料容器に充填し、１００℃に調整した。この容器にアルゴンガス導入し、蒸発したＴａ（ＯＥｔ）5 を同伴させ、原料ガスとした。
【００２８】
化合物Ｎｏ. １の同伴ガス（アルゴン）の流量を６０ｍｌ／ｍｉｎ、ストロンチウム源の同伴ガスの流量を５０ｍｌ／ｍｉｎ、タンタル源の同伴ガスの流量を４０ｍｌ／ｍｉｎとして、これら３種のガスを基板へと導き、熱分解により堆積させた後、酸素とアルゴンの混合ガス雰囲気下、８００℃で３０分結晶化処理を行った。
【００２９】
基板を取り出し、生成した薄膜のＸ線回折分析を行ったところ、ＳｒＢｉ2 Ｔａ2 Ｏ9 であることが確認された。
【００３０】
（実施例２）ＳｒＢｉ2 Ｔａ2 Ｏ9 膜の作成
熱ＣＶＤ装置の内圧を５Ｔｏｒｒに調整し、熱分解炉にはＰｔ／ＳｉＯ2 ／Ｓｉ基板を置き、基板温度を４００℃に調整した。
ビスマス源として、前記化合物Ｎｏ．１ ２０ｇを原料容器に充填し、この容器を７０℃に調整し液体とした。この容器にアルゴンガス導入し、蒸発した化合物Ｎｏ．１を同伴させ、原料ガスとした。
ストロンチウム−タンタル源として、Ｓｒ〔Ｔａ（ＯＥｔ）6 〕2 ２０ｇを原料容器に充填し、１５０℃に調整した。この容器にアルゴンガス導入し、蒸発したＳｒ〔Ｔａ（ＯＥｔ）6 〕2 を同伴させ、原料ガスとした。
【００３１】
化合物Ｎｏ. １の同伴ガス（アルゴン）の流量を６０ｍｌ／ｍｉｎ、ストロンチウム−タンタル源の同伴ガスの流量を５０ｍｌ／ｍｉｎとして、これら２種のガスを基板へと導き、熱分解により堆積させた後、酸素とアルゴンの混合ガス雰囲気下、８００℃で３０分結晶化処理を行った。
【００３２】
基板を取り出し、生成した薄膜のＸ線回折分析を行ったところ、ＳｒＢｉ2 Ｔａ2 Ｏ9 であることが確認された。
【００３３】
【発明の効果】
本発明のビスマス含有複合金属酸化膜は、ＣＶＤ法で成膜するに際し、ビスマス源として、ビスマスのエーテル基含有アルコキシド化合物を用いることにより、該化合物が常温またはわずかな加温により液体であるため、基板への供給量の制御が容易かつ安定供給が可能で、量産性を高めることができるものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a bismuth-containing composite metal oxide film formed by using a chemical vapor deposition method (CVD method) and formed from a bismuth compound serving as a bismuth source of a bismuth-containing composite metal oxide film and another metal compound.
[0002]
[Background Art and Problems to be Solved by the Invention]
As an application to nonvolatile memory, DRAM capacitor materials, and the like, bismuth-containing metal composite oxide films have been actively developed, and in particular, development of a compound serving as a bismuth source suitable for film formation by CVD is expected.
[0003]
In recent years, the CVD method has been used as a manufacturing method for oxide ceramics or layered ceramics. For example, a metal composite oxide film of SrBi 2 Ta 2 O 9 is used as a ferroelectric film in a nonvolatile memory. When used, the metal composite oxide film is known to be an excellent thin film that can solve the problems of conventional ferroelectric memories.
[0004]
However, it has not been said that the metal source compounds suitable for the CVD method have sufficient characteristics as previously proposed. For example, a compound used as a conventional bismuth source has a relatively high heat resistance, a high decomposition temperature, a low growth rate, and a high melting point. It was inferior compared with. When a metal composite oxide film is formed using the compound and another metal source having excellent volatility and decomposability, bismuth / other metals in the thin film formation process due to the difference in decomposition temperature between them. Controlling the ratio was difficult.
[0005]
Furthermore, since bismuth sources such as triphenyl bismuth and tri (o-tolyl) bismuth do not have oxygen atoms necessary for film formation in the molecule, oxygen such as oxygen-containing gas is used when these bismuth sources are used. The sources needed to coexist. However, the coexistence of an oxygen-containing gas has a defect that adversely affects the decomposition and precipitation of other materials. Further, in the case of a bismuth compound having a structure having an oxygen atom in the molecule, such as a bismuth alkoxide compound proposed in Japanese Patent Laid-Open No. 9-67197, the problem of the oxygen source is solved. However, since these compounds are high-melting solids, it is necessary to send the compounds to the film formation chamber by sublimation with a carrier such as argon gas during film formation by a CVD apparatus. When the sample is used, the supply amount of the sample changes due to a change in the surface area or the like, and thus it is difficult to strictly control the supply amount.
[0006]
Therefore, the object of the present invention is that it has a relatively low melting point, is liquefied at room temperature or liquefied by slight heating, is easy to handle and has excellent supply to the film formation chamber, and can be vaporized by evaporation rather than sublimation. The vaporization rate can be kept constant, the supply amount of the raw material to the film forming chamber can be easily controlled, and the bismuth-containing composite metal using a bismuth compound suitable for the CVD raw material in terms of thermal stability and decomposition temperature It is to provide an oxide film.
[0007]
[Means for Solving the Problems]
As a result of repeated studies, the present inventors have found that a bismuth-containing composite metal oxide film using a bismuth compound as an ether group-containing alkoxide compound as a bismuth source material can achieve the above object.
[0008]
The present invention has been made based on the above findings, and is represented by ABi 2 B 2 O 9 (wherein A represents Sr or Ba and B represents Ta or Nb) by chemical vapor deposition. In forming a bismuth-containing composite metal oxide film, a bismuth compound represented by the general formula (I) of the following [Chemical Formula 2] (same as the above [Chemical Formula 1]) and the above formula ABi 2 B 2 O 9 As raw materials for providing A and B, metal alkoxide compounds, composite metal alkoxide compounds [wherein Sr [M (OR 1 ) 6-x Lx] 2 (wherein x is 1 to 6, M is Ta or Nb) R 1 is a linear or branched alkyl group, L is an aminoalkoxide group or alkoxy represented by the following general formula ( II ) of [Chemical 2-1] (same as [Chemical 1-1] above) Or an alkoxide group)] or The present invention provides a method for producing a bismuth-containing composite metal oxide film characterized by using a β-diketone metal complex compound.
[0009]
[Chemical formula 2]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the bismuth-containing composite metal oxide film of the present invention will be described in detail.
The bismuth compound represented by the above general formula (I) relating to the bismuth-containing composite metal oxide film of the present invention is easy to handle in the CVD apparatus and control the supply rate to the film formation chamber, and has high mass productivity. It can be a CVD raw material capable of film formation.
[0011]
Specific examples of the bismuth compound represented by the general formula (I) used as one of the raw materials for the bismuth-containing composite metal oxide film of the present invention include compound Nos. 3 to 6 below. 1-4 etc. are mentioned. However, this invention is not limited at all by the following exemplary compounds.
[0012]
[Chemical 3]
[Formula 4]
[Chemical formula 5]
[Chemical 6]
Of the bismuth compounds represented by the above general formula (I), compounds in which R 1 and R 2 are both methyl groups and n is 1 are preferred.
[0017]
The production of the bismuth compound represented by the general formula (I) according to the present invention can be performed, for example, as in the following synthesis example.
[0018]
Synthesis Example 1 (Synthesis Example of Compound No. 1)
A 1 L light-shielded round bottom flask was charged with 30.0 g of 1-methoxy-2-methyl-2-propanol, 5.52 g of sodium and 100 ml of dry THF, and stirred at 60 ° C. for 5 hours to confirm that sodium had disappeared. did. Next, the inside of the flask was cooled to ice temperature, and 350 ml of dry THF and 25.24 g of bismuth chloride were added. The mixture was heated again and stirred for 30 hours under reflux of THF. After depressurizing and distilling off THF, 800 ml of hexane was added and heated to dissolve the residue. The insoluble material was removed by filtration, and the filtrate was desolvated to obtain 32.6 g of crude crystals (yield 78.6%). The crude crystals were distilled under reduced pressure (0.08 torr, bath temperature 135 to 144 ° C.) to obtain 24.0 g (yield 57.9%) of a white solid.
[0019]
About the obtained crystal | crystallization, the bismuth content by ICP, NMR, melting | fusing point, and vapor pressure were measured. The results are shown below.
(1) ICP
When ICP was measured using a sample dissolved in nitric acid, the bismuth content was 40.3% (theoretical content 40.3%).
(2) NMR
When 13 C-NMR (in deuterated chloroform: δ value) was measured, the following peak was detected.
・ 30.319 ppm
58.431 ppm
72.204 ppm
・ 83.820 ppm
Further, when 1 H-NMR (in deuterated chloroform: δ value) was measured, the following peak was detected.
・ 1.1173 ppm: s, 18H
3.1724 ppm: s, 6H
-3.2780 ppm: s, 9H
(3) Melting point and vapor pressure When the melting point was measured using a micro melting point measuring apparatus, it was 49 ° C. When the vapor pressure was measured, the following results were obtained.
0.1 Torr / 99 ° C
0.2 Torr / 107 ° C
0.3 Torr / 112 ° C
0.4 Torr / 115 ° C
[0020]
Synthesis Example 2 (Synthesis Example of Compound No. 2)
A solution obtained by dissolving 1.38 g of sodium in 40 ml of 1-methoxy-2-propanol was added dropwise at room temperature to 50 ml of bismuth chloride added to 50 ml of dry benzene and stirred in a 200 ml light-shielded round bottom flask. Next, the mixture was stirred at 60 ° C. for 30 hours, and 40 ml of dry benzene was added, followed by filtration at 60 ° C. The filtrate was desolvated to obtain a light brown liquid, and then distilled under reduced pressure (about 0.1 torr, bath temperature 150 ° C.) to obtain 8.25 g of a transparent viscous liquid (yield 86.6%).
[0021]
About the obtained crystal | crystallization, the bismuth content and NMR by ICP were measured. The results are shown below.
(1) ICP
When ICP was measured using a sample dissolved in nitric acid, the bismuth content was 43.7% (theoretical content: 43.9%).
(2) NMR
When 13 C-NMR (in deuterated chloroform: δ value) was measured, the following peak was detected.
・ 23.787 ppm
58.431 ppm
・ 67.029 ppm
82.109 ppm
Further, when 1 H-NMR (in deuterated chloroform: δ value) was measured, the following peak was detected.
・ 1.1356 ppm, 1.1514 ppm: d, 9H
・ 3.0205 ppm: s, 9H
・ 3.1004 ppm, 3.1138 ppm: d, 6H
4.8224 ppm: s, 3H
[0022]
Examples of the metal source compound other than the bismuth compound represented by the general formula (I), which is a raw material for forming the bismuth-containing composite metal oxide film of the present invention, include Ta (OEt) 5 , Ta (Oi— Pr) 5 , Ta (Ot-Bu) 5 , Ta (Ot-Pen) 5 , Nb (OEt) 5 , Nb (Oi-Pr) 5 , Nb (Ot-Bu) 5 , Nb (Ot-Pen) 5 , Sr (OEt) 2 , Sr (Oi-Pr) 2 , Sr (Ot-Bu) 2 , Sr (Ot-Pen) 2 , Ba (OEt) 2 , Ba (Oi-Pr) 2 , Ba (Ot-Bu) 2 , metal alkoxide compounds such as Ba (Ot-Pen) 2 , Sr [Ta (OEt) 6 ] 2 , Sr [Nb (OEt) 6 ] 2 , Ba [Ta (OEt) 6 ] 2 , Ba [Nb (OEt) 6 ] Composite metal alkoxide compounds such as 2 , dipivaloylmeta Natobarium, dipivaloylmethanatostronium, pivaloylisopropionylmethanatobarium, pivaloylisopropionylmethanatostronium, diisopropionylmethanatobarium, diisopropionylmethanatostrontium, 1- (2'-methoxyethoxy) -2,2,6,6-tetramethyl-3,5-heptanedionatobarium, 1- (2'-methoxyethoxy) -2,2,6,6-tetramethyl-3,5-heptaneedionatostrontium Β-diketone metal complex compounds such as are preferably used. (In the above formula, Et represents an ethyl group, i-Pr represents an isopropyl group, t-Bu represents a tertiary butyl group, and t-Pen represents a tertiary pentyl group.)
[0023]
The composition ratio of bismuth and other metals [A and B] in the bismuth-containing composite metal oxide film [ABi 2 B 2 O 9 ] (after film formation) of the present invention is not particularly limited, and exhibits ferroelectricity. However, [Bi / A / B] is preferably 1.8 to 2.5 / 1 / 1.8 to 2.5.
[0024]
The bismuth-containing composite metal oxide film of the present invention is used for applications such as nonvolatile memory and DRAM capacitor materials.
[0025]
Examples of the CVD method used to form the bismuth-containing composite metal oxide film of the present invention include methods such as thermal CVD, plasma CVD, and photo-CVD, and the CVD method generally employed in a CVD apparatus. If so, there is no particular restriction.
[0026]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.
[0027]
Example 1 Preparation of SrBi 2 Ta 2 O 9 Film The internal pressure of the thermal CVD apparatus was adjusted to 5 Torr, a Pt / SiO 2 / Si substrate was placed in the pyrolysis furnace, and the substrate temperature was adjusted to 400 ° C.
As the bismuth source, the compound No. 1 was used. 1 20 g was filled into a raw material container, and this container was adjusted to 70 ° C. to obtain a liquid. Argon gas was introduced into this container and evaporated. 1 was used as a raw material gas.
As a strontium source, 20 g of 1- (2′-methoxyethoxy) -2,2,6,6-tetramethyl-3,5-heptanedionatostrontium was charged into a raw material container and adjusted to 200 ° C. Argon gas was introduced into this vessel, and evaporated 1- (2′-methoxyethoxy) -2,2,6,6-tetramethyl-3,5-heptanedionatostrontium was accompanied to obtain a raw material gas.
As a tantalum source, 20 g of Ta (OEt) 5 was filled in a raw material container and adjusted to 100 ° C. Argon gas was introduced into this container, and evaporated Ta (OEt) 5 was accompanied to obtain a raw material gas.
[0028]
Compound No. 1 entrained gas (argon) flow rate of 60 ml / min, strontium source entrained gas flow rate of 50 ml / min, tantalum source entrained gas flow rate of 40 ml / min, and these three gases to the substrate After being deposited by thermal decomposition, crystallization treatment was performed at 800 ° C. for 30 minutes in a mixed gas atmosphere of oxygen and argon.
[0029]
The substrate was taken out, was subjected to X-ray diffraction analysis of the resulting thin film, it was confirmed that the SrBi 2 Ta 2 O 9.
[0030]
(Example 2) Preparation of SrBi 2 Ta 2 O 9 film The internal pressure of the thermal CVD apparatus was adjusted to 5 Torr, a Pt / SiO 2 / Si substrate was placed in the pyrolysis furnace, and the substrate temperature was adjusted to 400 ° C.
As the bismuth source, the compound No. 1 was used. 1 20 g was filled into a raw material container, and this container was adjusted to 70 ° C. to obtain a liquid. Argon gas was introduced into this container and evaporated. 1 was used as a raw material gas.
As a strontium-tantalum source, 20 g of Sr [Ta (OEt) 6 ] 2 was filled in a raw material container and adjusted to 150 ° C. Argon gas was introduced into this vessel, and evaporated Sr [Ta (OEt) 6 ] 2 was entrained to obtain a raw material gas.
[0031]
After the flow rate of the entrained gas (argon) of Compound No. 1 is 60 ml / min and the flow rate of the entrained gas of the strontium-tantalum source is 50 ml / min, these two gases are led to the substrate and deposited by thermal decomposition. Then, crystallization treatment was performed at 800 ° C. for 30 minutes in a mixed gas atmosphere of oxygen and argon.
[0032]
The substrate was taken out, was subjected to X-ray diffraction analysis of the resulting thin film, it was confirmed that the SrBi 2 Ta 2 O 9.
[0033]
【The invention's effect】
When the bismuth-containing composite metal oxide film of the present invention is formed by the CVD method, since the bismuth source is an ether group-containing alkoxide compound of bismuth, the compound is liquid at normal temperature or slight heating, The supply amount to the substrate can be controlled easily and stably, and mass productivity can be improved.
Claims (3)
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|---|---|---|---|
| JP22324698A JP4225607B2 (en) | 1998-08-06 | 1998-08-06 | Method for producing bismuth-containing composite metal oxide film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22324698A JP4225607B2 (en) | 1998-08-06 | 1998-08-06 | Method for producing bismuth-containing composite metal oxide film |
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| JP4868639B2 (en) * | 2000-06-12 | 2012-02-01 | 株式会社Ａｄｅｋａ | Raw material for chemical vapor deposition and method for producing thin film using the same |
| KR100721365B1 (en) | 2003-04-08 | 2007-05-23 | 토소가부시키가이샤 | New bismuth compound, method for manufacturing thereof and method for manufacturing film |
| CN1610076A (en) | 2003-06-30 | 2005-04-27 | 松下电器产业株式会社 | Method for forming ferroelectric film and semiconductor device |
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