JP2002212130A - Organotitanium compound, raw material solution containing the same and titanium-containing dielectric thin film - Google Patents
Organotitanium compound, raw material solution containing the same and titanium-containing dielectric thin filmInfo
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- JP2002212130A JP2002212130A JP2001004627A JP2001004627A JP2002212130A JP 2002212130 A JP2002212130 A JP 2002212130A JP 2001004627 A JP2001004627 A JP 2001004627A JP 2001004627 A JP2001004627 A JP 2001004627A JP 2002212130 A JP2002212130 A JP 2002212130A
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- raw material
- thin film
- compound
- dielectric thin
- titanium
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ＤＲＡＭ（ダイナ
ミックランダムアクセスメモリー）等の誘電体メモリ
ー、誘電体フィルター等に用いられる複合酸化物系誘電
体薄膜を有機金属化学蒸着法（Metal Organic Chemical
Vapor Deposition、以下、ＭＯＣＶＤ法という。）に
より形成するための原料として好適な有機チタン化合物
に関する。更に詳しくはこの有機チタン化合物を含む溶
液原料並びにこれから作られたチタン含有誘電体薄膜に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a composite oxide dielectric thin film used for a dielectric memory such as a DRAM (Dynamic Random Access Memory) or a dielectric filter by a metal organic chemical vapor deposition method.
Vapor Deposition, hereinafter referred to as MOCVD method. The present invention relates to an organotitanium compound suitable as a raw material for forming the compound according to (1). More specifically, the present invention relates to a solution raw material containing the organic titanium compound and a titanium-containing dielectric thin film produced therefrom.
【０００２】[0002]
【従来の技術】ＤＲＡＭの集積度が急ピッチで増大する
につれて、キャパシタとして用いられる誘電体薄膜は、
従来のＳｉＯ2では対応が難しくなりつつあり、より誘
電率の高い誘電体材料が求められている。かかる誘電体
材料の例としては、チタン酸鉛（ＰＴ）、チタン酸ジル
コン酸鉛（ＰＺＴ）、チタン酸ジルコン酸ランタン鉛
（ＰＬＺＴ）、チタン酸ストロンチウム（ＳＴ）、チタ
ン酸バリウム（ＢＴ）、チタン酸バリウムストロンチウ
ム（ＢＳＴ）等が挙げられる。2. Description of the Related Art As the degree of integration of DRAMs increases at a rapid pace, dielectric thin films used as capacitors have become
Conventional SiO 2 is becoming difficult to cope with, and a dielectric material having a higher dielectric constant is required. Examples of such dielectric materials include lead titanate (PT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), strontium titanate (ST), barium titanate (BT), titanium Barium strontium acid (BST) and the like.
【０００３】このような複合酸化物系誘電体薄膜の形成
方法については、金属アルコキシド原料を用いてスピン
コートで基板上に成膜するゾルゲル法がこれまで盛んに
研究されてきた。ゾルゲル法は、金属成分を気化させな
いため、膜の組成制御は容易である。しかし、ＤＲＡＭ
のキャパシタ用電極は段差があり、集積度が高くなるほ
ど段差が大きく、かつ複雑になるので、スピンコート法
では基板となる電極状に均一に誘電体薄膜を形成するこ
とが難しい。As a method of forming such a complex oxide-based dielectric thin film, a sol-gel method of forming a film on a substrate by spin coating using a metal alkoxide raw material has been actively studied. Since the sol-gel method does not vaporize metal components, it is easy to control the composition of the film. But DRAM
The capacitor electrode has a step, and the higher the degree of integration, the larger the step and the more complicated it becomes. Therefore, it is difficult to form a dielectric thin film uniformly on the electrode serving as a substrate by the spin coating method.
【０００４】そのため、ここ数年は、デバイスの高集積
度を見越して、段差被覆性（＝ステップカバレッジ性、
段差のある複雑形状の表面への付き回り性）に優れたＭ
ＯＣＶＤ法による誘電体薄膜の作製の研究が活性化して
きた。原料の有機金属化合物としては、ジピバロイルメ
タン（ＤＰＭ）等のβ−ジケトン化合物を配位子とする
有機金属錯体や金属アルコキシドが一般に使用されてい
る。Ｔｉ、Ｚｒ、Ｔａ等の金属の原料にはアルコキシド
とβ−ジケトン錯体の両方が使用され、ＳｒやＢａの原
料としては主にβ−ジケトン錯体が使用される。Therefore, in recent years, in view of the high degree of integration of devices, step coverage (= step coverage,
M with excellent step coverage on complex shaped surfaces with steps)
Research on the production of dielectric thin films by the OCVD method has been activated. As a raw material organometallic compound, an organometallic complex or a metal alkoxide having a β-diketone compound such as dipivaloylmethane (DPM) as a ligand is generally used. Both alkoxides and β-diketone complexes are used as raw materials for metals such as Ti, Zr, and Ta, and β-diketone complexes are mainly used as raw materials for Sr and Ba.
【０００５】ＭＯＣＶＤ法は、金属原料を減圧下で加熱
して気化させ、その蒸気を成膜室に輸送して基板上で熱
分解させることにより、生成した金属酸化物を基板上に
付着させる方法である。このＭＯＣＶＤ法による誘電体
薄膜の形成において、当初は、原料の有機金属化合物を
そのまま加熱して気化させ、発生した蒸気を成膜室に送
って成膜させていた。しかし、原料の有機金属化合物、
特にＭＯＣＶＤ法に推奨されているＤＰＭ錯体のような
化合物は安定性や気化性が悪く、使用中に気化性が低下
したり、或いは気化性を高めるために加熱温度を上げる
と、原料化合物の蒸気が成膜室に達する前に熱分解する
ことがある。そのため、原料を成膜室に安定して輸送す
ることが困難であり、高価な原料が一回の成膜ごとに使
い捨てになり、また膜の組成制御の困難で、良好な誘電
特性を持つ薄膜を安定して成膜できないという問題があ
った。[0005] The MOCVD method is a method in which a metal material is heated under reduced pressure to be vaporized, and the vapor is transported to a film forming chamber and thermally decomposed on the substrate, whereby the generated metal oxide is deposited on the substrate. It is. In the formation of a dielectric thin film by the MOCVD method, initially, an organic metal compound as a raw material is directly heated and vaporized, and the generated vapor is sent to a film forming chamber to form a film. However, the raw material organometallic compound,
In particular, compounds such as the DPM complex recommended for the MOCVD method have poor stability and vaporization properties. If the vaporization properties decrease during use, or if the heating temperature is increased in order to increase the vaporization properties, the vapor of the raw material compounds will increase. May be thermally decomposed before reaching the film forming chamber. For this reason, it is difficult to stably transport the raw materials to the film forming chamber, and expensive raw materials are thrown away after each film formation, and the film composition is difficult to control and the thin film has good dielectric properties. There was a problem that it was not possible to form a film stably.
【０００６】そのため、原料を安定して供給できる溶液
気化ＣＶＤ法が現在広く用いられている。この溶液気化
ＣＶＤ法はＭＯＣＶＤ法の改良であり、固体のＣＶＤ原
料を各種有機溶媒に溶解し、液体としてＣＶＤ装置に供
給する方法である。Ｔｉ含有誘電体薄膜形成用のＣＶＤ
原料としてはビスイソプロポキシビスジビバロイルメタ
ナートチタン（以下、［Ｔｉ(Ｏ-ｉ-Ｐｒ)2(ＤＰＭ)2］
という。）が一般に知られている。Therefore, a solution vaporization CVD method capable of stably supplying a raw material is widely used at present. This solution vaporization CVD method is an improvement of the MOCVD method, in which a solid CVD raw material is dissolved in various organic solvents and supplied as a liquid to a CVD apparatus. CVD for forming Ti-containing dielectric thin film
As a raw material, bisisopropoxybisdibivaloyl methanate titanium (hereinafter, [Ti (Oi-Pr) 2 (DPM) 2 ])
That. ) Is generally known.
【０００７】[0007]
【発明が解決しようとする課題】しかし、この［Ｔｉ
(Ｏ-ｉ-Ｐｒ)2(ＤＰＭ)2］を溶液気化ＣＶＤ材料に用い
る場合、［Ｔｉ(Ｏ-ｉ-Ｐｒ)2(ＤＰＭ)2］は有機溶媒へ
の溶解度が１．０ｍｏｌ／Ｌ以下と低いため、原料の供
給量が制限されてしまう問題があった。また、［Ｔｉ
(Ｏ-ｉ-Ｐｒ)2(ＤＰＭ)2］は５００℃未満の成膜温度で
は成膜速度が小さいという問題もあった。However, this [Ti
When (Oi-Pr) 2 (DPM) 2 ] is used for a solution vaporized CVD material, the solubility of [Ti (Oi-Pr) 2 (DPM) 2 ] in an organic solvent is 1.0 mol / L or less. Therefore, there is a problem that the supply amount of the raw material is limited. Also, [Ti
(Oi-Pr) 2 (DPM) 2 ] has a problem that the film formation rate is low at a film formation temperature of less than 500 ° C.
【０００８】本発明の目的は、有機溶媒への溶解度が高
い有機チタン化合物を提供することにある。本発明の別
の目的は、高い成膜速度が得られ、熱安定性、気化安定
性に優れた有機チタン化合物及びこれを含む溶液原料を
提供することにある。An object of the present invention is to provide an organic titanium compound having high solubility in an organic solvent. Another object of the present invention is to provide an organotitanium compound capable of obtaining a high film forming rate, having excellent thermal stability and vaporization stability, and a solution raw material containing the same.
【０００９】[0009]
【課題を解決するための手段】請求項１に係る発明は、
次の式（１）に示される有機チタン化合物である。According to the first aspect of the present invention,
An organic titanium compound represented by the following formula (1).
【化４】 但し、結合基Ｏ-ｉ-Ｐｒは次の式（２）で表されるイソ
プロポキシド基であり、ｄｍｈｄは次の式（３）で表さ
れる２，６−ジメチル−３，５−ヘプタンジオン残基で
ある。Embedded image Here, the bonding group Oi-Pr is an isopropoxide group represented by the following formula (2), and dmhd is 2,6-dimethyl-3,5-heptane represented by the following formula (3). It is a dione residue.
【００１０】[0010]
【化５】 Embedded image
【００１１】[0011]
【化６】 本発明の化合物は従来用いられてきたＤＰＭ化合物のメ
チル基の１つを水素に置き換えることにより、有機溶媒
との親和性を増加させたため、有機溶媒への溶解度が向
上する。Embedded image The compound of the present invention has increased affinity for an organic solvent by replacing one of the methyl groups of a conventionally used DPM compound with hydrogen, thereby improving the solubility in the organic solvent.
【００１２】請求項２に係る発明は、請求項１記載の有
機チタン化合物を有機溶媒に溶解した溶液原料である。
請求項３に係る発明は、請求項２に係る発明であって、
有機溶媒がテトラヒドロフラン（以下、ＴＨＦとい
う。）、メチルテトラヒドロフラン、ｎ−オクタン、イ
ソオクタン、ヘキサン、シクロヘキサン、ピリジン、ル
チジン、酢酸ブチル又は酢酸アミルからなる群より選ば
れた１種又は２種以上の溶媒である溶液原料である。請
求項１に係る有機チタン化合物と上記溶媒とを混合した
溶液原料は上記溶媒を混合しない場合と比較して原料を
安定に供給できるためＭＯＣＶＤ法により成膜したとき
に更に一層堆積速度、即ち成膜速度が大きくなる。ま
た、高い溶解度が得られるため、この溶液原料を用いて
ＭＯＣＶＤ法により成膜することにより大量にＭＯＣＶ
Ｄ装置に原料を供給できる。The invention according to claim 2 is a solution raw material in which the organic titanium compound according to claim 1 is dissolved in an organic solvent.
The invention according to claim 3 is the invention according to claim 2,
The organic solvent is one or more solvents selected from the group consisting of tetrahydrofuran (hereinafter referred to as THF), methyltetrahydrofuran, n-octane, isooctane, hexane, cyclohexane, pyridine, lutidine, butyl acetate or amyl acetate; This is a solution raw material. The solution raw material in which the organic titanium compound according to claim 1 is mixed with the solvent can supply the raw material more stably as compared with the case where the solvent is not mixed. The film speed increases. Further, since high solubility can be obtained, a large amount of MOCV can be formed by forming a film by MOCVD using this solution raw material.
Raw materials can be supplied to the D apparatus.
【００１３】[0013]
【発明の実施の形態】本発明の有機チタン化合物は、前
述した式（１）に示される化合物である。式（１）に示
されるＯ-ｉ-Ｐｒは前述した式（２）で表されるイソプ
ロポキシド基であり、ｄｍｈｄは前述した式（３）で表
される２，６−ジメチル−３，５−ヘプタンジオン残基
である。BEST MODE FOR CARRYING OUT THE INVENTION The organic titanium compound of the present invention is a compound represented by the above formula (1). Oi-Pr represented by the formula (1) is an isopropoxide group represented by the formula (2), and dmhd is 2,6-dimethyl-3, represented by the formula (3). 5-heptanedione residue.
【００１４】また、本発明の溶液原料は、請求項１記載
の有機チタン化合物を有機溶媒に溶解することにより調
製される。有機溶媒はＴＨＦ、メチルテトラヒドロフラ
ン、ｎ−オクタン、イソオクタン、ヘキサン、シクロヘ
キサン、ピリジン、ルチジン、酢酸ブチル又は酢酸アミ
ルからなる群より選ばれた１種又は２種以上の溶媒であ
る。更に、本発明のチタン含有誘電体薄膜は、請求項２
又は３記載の溶液原料を用いてＭＯＣＶＤ法により作製
される。上記溶媒を用いることにより、溶液原料をより
安定して気化室や成膜室まで送込むことができ、結果と
してＭＯＣＶＤにおける薄膜の成長速度が促進される。The solution raw material of the present invention is prepared by dissolving the organic titanium compound according to claim 1 in an organic solvent. The organic solvent is one or more solvents selected from the group consisting of THF, methyltetrahydrofuran, n-octane, isooctane, hexane, cyclohexane, pyridine, lutidine, butyl acetate or amyl acetate. Further, the titanium-containing dielectric thin film of the present invention is characterized in that:
Alternatively, it is manufactured by the MOCVD method using the solution raw material described in 3. By using the above-mentioned solvent, the solution raw material can be more stably sent to the vaporization chamber or the film formation chamber, and as a result, the growth rate of the thin film in MOCVD is accelerated.
【００１５】固体である原料化合物をそのまま減圧下で
加熱し、気化させる方法では配管全てを加熱しておく必
要があり、加熱されていない部分があると析出してしま
い、配管が閉塞する。また、加熱された状態で長時間保
存されるため、材質の変質が起こり、気化しにくくな
り、原料の供給量が減少してしまう。この結果、成膜速
度が減少してしまう。固体原料化合物を溶媒に溶解して
溶液とした場合は、室温で気化室まで原料を供給できる
ため、配管の閉塞が少なくなり、原料が加熱されている
時間が短く、原料の変質が抑制できるので安定して原料
を供給でき、成膜速度は促進される。In a method in which a solid raw material compound is directly heated under reduced pressure and vaporized, it is necessary to heat the entire pipe, and if there is an unheated portion, it precipitates and the pipe is blocked. In addition, since the material is stored for a long time in a heated state, the quality of the material is changed, it is difficult to vaporize, and the supply amount of the raw material is reduced. As a result, the film forming speed decreases. In the case where the solid raw material compound is dissolved in a solvent to form a solution, the raw material can be supplied to the vaporization chamber at room temperature. Raw materials can be supplied stably, and the film formation speed is accelerated.
【００１６】[0016]
【実施例】次に本発明の実施例を比較例とともに説明す
る。 ＜実施例１＞有機チタン化合物として［Ｔｉ(Ｏ-ｉ-Ｐ
ｒ)2(ｄｍｈｄ)2］を次の方法により合成した。先ずテ
トライソプロポキシチタン［Ｔｉ(Ｏ-ｉ-Ｐｒ)4］を出
発原料として用い、これを有機溶媒としてトルエンに１
〜５重量％となるように溶解した。次いでこの溶解液に
［Ｔｉ(Ｏ-ｉ-Ｐｒ)4］に対して２倍モル量のＨｄｍｈ
ｄを加え、この溶液を有機溶媒の沸点より高い温度で２
時間加熱還流することにより、反応させた。この反応液
を減圧下で濃縮し、白色結晶を得た。次にこの白色結晶
をトルエンを用いて再結晶後、減圧下で昇華させる精製
を繰返し行うことにより精製した結晶を得た。得られた
結晶の同定は1Ｈ-ＮＭＲ（Ｃ6Ｈ6）、質量分析及び元素
分析により行った。1Ｈ-ＮＭＲ分析の結果ではδ＝５．
４３６０（ｓ、１Ｈ、ｄｍｈｄ-ＣＨ）、２．４０５３
（ｍ、１Ｈ、ｄｍｈｄ-ＣＨ）、２．２７６１（ｍ、１
Ｈ、ｄｍｈｄ-ＣＨ）、１．２３４８（ｄ、６Ｈ、ｄｍ
ｈｄ-ＣＨ3）、１．１０１９（ｄ、３Ｈ、ｄｍｈｄ-Ｃ
Ｈ3）、１．０２１３（ｄ、３Ｈ、ｄｍｈｄ-ＣＨ3）、
１．９４６３（ｄ、６Ｈ、ｉＰｒＯ-ＣＨ3）、３．９８
６２（ｍ、１Ｈ、ｉＰｒＯ-ＣＨ）であった。元素分析
の結果では、Ｔｉ９．７％（理論値１０．０）、Ｃ６
０．３％（理論値６０．０）、Ｈ９．８％（理論値１
０．０）、Ｏ２０．２％（理論値２０．０）であった。
質量分析ではｍ／Ｚ＝４１７［Ｔｉ(Ｏ-ｉ-Ｐｒ)(ｄｍ
ｈｄ)2］、３５８［ＴｉＯ(ｄｍｈｄ)2］、３２１［Ｔ
ｉ(Ｏ-ｉ-Ｐｒ)2(ｄｍｈｄ)2］であった。Next, examples of the present invention will be described together with comparative examples. <Example 1> [Ti (OiP) was used as an organic titanium compound.
r) 2 (dmhd) 2 ] was synthesized by the following method. First, tetraisopropoxy titanium [Ti (Oi-Pr) 4 ] was used as a starting material, and this was used as an organic solvent in toluene.
-5% by weight. Next, a twice molar amount of Hdmh with respect to [Ti (Oi-Pr) 4 ] was added to this solution.
d and add the solution at a temperature above the boiling point of the organic solvent.
The reaction was carried out by heating and refluxing for an hour. The reaction solution was concentrated under reduced pressure to obtain white crystals. Next, the white crystals were recrystallized using toluene, and then repeatedly purified by sublimation under reduced pressure to obtain purified crystals. The obtained crystals were identified by 1 H-NMR (C 6 H 6 ), mass spectrometry and elemental analysis. As a result of 1 H-NMR analysis, δ = 5.
4360 (s, 1H, dmhd-CH), 2.4053
(M, 1H, dmhd-CH), 2.2761 (m, 1
H, dmhd-CH), 1.2348 (d, 6H, dm
hd-CH 3 ), 1.109 (d, 3H, dmhd-C
H 3), 1.0213 (d, 3H, dmhd-CH 3),
1.9463 (d, 6H, iPrO- CH 3), 3.98
62 (m, 1H, iPrO-CH). According to the result of elemental analysis, Ti 9.7% (theoretical value 10.0), C6
0.3% (theoretical 60.0), H9.8% (theoretical 1
0.0) and O20.2% (theoretical 20.0).
In mass spectrometry, m / Z = 417 [Ti (Oi-Pr) (dm
hd) 2 ], 358 [TiO (dmhd) 2 ], 321 [T
i (Oi-Pr) 2 (dmhd) 2 ].
【００１７】＜実施例２＞有機チタン化合物として実施
例１で合成した［Ｔｉ(Ｏ-ｉ-Ｐｒ)2(ｄｍｈｄ)2］を用
意した。この有機チタン化合物をＴＨＦに０．１ｍｏｌ
／Ｌの濃度で溶解して溶液原料を得た。また、有機チタ
ン化合物の他に、有機ストロンチウム化合物としてビス
（ジピバロイルメタナト）ストロンチウム錯体［Ｓｒ
(ＤＰＭ)2］、有機バリウム化合物としてビス（ジピバ
ロイルメタナト）バリウム錯体［Ｂａ(ＤＰＭ)2］をそ
れぞれ用意し、これらの化合物をＴＨＦにそれぞれ０．
１ｍｏｌ／Ｌの濃度で溶解して２つの溶液原料を得た。
上記３種の化合物の溶液原料を用いて、Ｓｒ原料を０．
３ｍｌ／ｍｉｎ、Ｂａ原料を０．３ｍｌ／ｍｉｎ、Ｔｉ
原料を０．６ｍｌ／ｍｉｎとなるように、それぞれ各流
量を制御しながら混合室に送って混合し、この混合溶液
を気化室で気化させ、気化した蒸気を成膜室に搬送し
て、ＭＯＣＶＤ法によりＴｉ含有誘電体薄膜を成膜し
た。基板として、シリコン基板を用い、基板温度を４５
０℃とした。［Ｓｒ(ＤＰＭ)2］、［Ｂａ(ＤＰＭ)2］及
び［Ｔｉ(Ｏ-ｉ-Ｐｒ)2(ｄｍｈｄ)2］の気化温度をそれ
ぞれ２５０℃にした。また、反応圧力を２Ｔｏｒｒにそ
れぞれ設定した。キャリアガスとしてＨｅガスを用い、
その流量を２５０ｓｃｃｍとした。また、反応ガスとし
て、Ｏ2を用い、その流量を１．０ｓｌｍとした。Example 2 [Ti (Oi-Pr) 2 (dmhd) 2 ] synthesized in Example 1 was prepared as an organic titanium compound. 0.1 mol of this organic titanium compound in THF
/ L to obtain a solution raw material. In addition to the organotitanium compound, a bis (dipivaloylmethanato) strontium complex [Sr
(DPM) 2 ] and a bis (dipivaloylmethanato) barium complex [Ba (DPM) 2 ] as an organic barium compound, respectively, and these compounds were added to THF in an amount of 0.1% respectively.
It was dissolved at a concentration of 1 mol / L to obtain two solution raw materials.
Using the solution raw materials of the above three compounds, the Sr raw material was reduced to 0.
3ml / min, Ba raw material 0.3ml / min, Ti
The raw materials are fed to the mixing chamber while controlling the respective flow rates so as to be 0.6 ml / min, and mixed, the mixed solution is vaporized in the vaporization chamber, and the vaporized vapor is transported to the film formation chamber, and is subjected to MOCVD. A Ti-containing dielectric thin film was formed by the method. A silicon substrate was used as the substrate, and the substrate temperature was set to 45.
0 ° C. [Sr (DPM) 2 ], [Ba (DPM) 2 ] and [Ti (Oi-Pr) 2 (dmhd) 2 ] were each set to a vaporization temperature of 250 ° C. The reaction pressure was set to 2 Torr. Using He gas as a carrier gas,
The flow rate was 250 sccm. In addition, O 2 was used as a reaction gas, and the flow rate was 1.0 slm.
【００１８】＜比較例１＞有機チタン化合物として［Ｔ
ｉ(Ｏ-ｉ-Ｐｒ)2(ＤＰＭ)2］を用いた以外は実施例２と
同様にして成膜した。 ＜比較評価１＞基板温度４５０℃で成膜した実施例２及
び比較例１のＴｉ含有誘電体薄膜の成膜速度を測定し
た。表１にそれぞれ示す。<Comparative Example 1> [T] was used as an organotitanium compound.
i (Oi-Pr) 2 (DPM) 2 ] was used in the same manner as in Example 2. <Comparative Evaluation 1> The film forming rates of the Ti-containing dielectric thin films of Example 2 and Comparative Example 1 formed at a substrate temperature of 450 ° C. were measured. The results are shown in Table 1.
【００１９】[0019]
【表１】 表１より明らかなように、比較例１に比べて実施例２で
は低温での成膜においても大きな成膜速度を有している
ことがわかる。これにより、基板温度を低く設定するこ
とができる。[Table 1] As is clear from Table 1, it can be seen that Example 2 has a higher film formation rate even in film formation at a lower temperature than Comparative Example 1. Thereby, the substrate temperature can be set low.
【００２０】＜実施例３＞有機チタン化合物として実施
例１で合成した［Ｔｉ(Ｏ-ｉ-Ｐｒ)2(ｄｍｈｄ)2］を用
い、基板温度を５５０℃とした以外は実施例２と同様に
して成膜した。 ＜比較例２＞有機チタン化合物として［Ｔｉ(Ｏ-ｉ-Ｐ
ｒ)2(ＤＰＭ)2］を用い、基板温度を５５０℃とした以
外は実施例２と同様にして成膜した。 ＜比較評価２＞基板温度５５０℃で成膜した実施例３及
び比較例２のＴｉ含有誘電体薄膜の成膜速度を測定し
た。表２にそれぞれ示す。Example 3 Same as Example 2 except that [Ti (Oi-Pr) 2 (dmhd) 2 ] synthesized in Example 1 was used as the organotitanium compound and the substrate temperature was changed to 550 ° C. To form a film. <Comparative Example 2> [Ti (OiP)
r) 2 (DPM) 2 ], and a film was formed in the same manner as in Example 2 except that the substrate temperature was 550 ° C. <Comparative Evaluation 2> The film forming rates of the Ti-containing dielectric thin films of Example 3 and Comparative Example 2 formed at a substrate temperature of 550 ° C. were measured. The results are shown in Table 2.
【００２１】[0021]
【表２】 表２により明らかなように、比較例２に比べ実施例３で
は高温での成膜においても成膜速度を大きくすることが
できることが判る。[Table 2] As is clear from Table 2, it can be seen that the film forming rate in Example 3 can be increased even in film formation at a high temperature as compared with Comparative Example 2.
【００２２】＜実施例４＞有機チタン化合物として実施
例１で合成した［Ｔｉ(Ｏ-ｉ-Ｐｒ)2(ｄｍｈｄ)2］を用
意した。また有機溶媒としてＴＨＦ、ｎ−オクタン、酢
酸ブチル及びピリジンをそれぞれ用意し、これら有機溶
媒に有機チタン化合物をそれぞれ溶解して溶液原料を調
製した。Example 4 [Ti (Oi-Pr) 2 (dmhd) 2 ] synthesized in Example 1 was prepared as an organic titanium compound. Further, THF, n-octane, butyl acetate, and pyridine were prepared as organic solvents, and organic titanium compounds were dissolved in these organic solvents to prepare solution raw materials.
【００２３】＜比較例３＞有機チタン化合物として［Ｔ
ｉ(Ｏ-ｉ-Ｐｒ)2(ＤＰＭ)2］を用いた以外は実施例４と
同様にして溶解した。 ＜比較評価３＞実施例４及び比較例３の有機チタン化合
物の各有機溶媒における溶解度を測定した。表３にそれ
ぞれ示す。<Comparative Example 3> [T] was used as an organotitanium compound.
i (Oi-Pr) 2 (DPM) 2 ], except that i was dissolved in the same manner as in Example 4. <Comparative Evaluation 3> The solubility of the organic titanium compounds of Example 4 and Comparative Example 3 in each organic solvent was measured. The results are shown in Table 3.
【００２４】[0024]
【表３】 表３より明らかなように、比較例３の溶解度に比べ、実
施例４の溶解度はそれぞれ大きく、各種有機溶媒への溶
解度も大きいことが判った。また溶解度が大きいことか
ら原料を大量に供給できるために成膜が効率よく行える
点で優れていることが判る。[Table 3] As is clear from Table 3, the solubility of Example 4 was higher than that of Comparative Example 3, and the solubility in various organic solvents was higher. In addition, since the solubility is high, a large amount of the raw material can be supplied, so that it is excellent in that the film can be efficiently formed.
【００２５】[0025]
【発明の効果】以上述べたように、本発明の一般式［Ｔ
ｉ(Ｏ-ｉ-Ｐｒ)2(ｄｍｈｄ)2］からなる有機チタン化合
物は、この化合物を原料としてＭＯＣＶＤ法により成膜
すると、従来の［Ｔｉ(Ｏ-ｉ-Ｐｒ)2(ＤＰＭ)2］に代表
される有機チタン化合物と比べて、有機溶媒への溶解度
が高いため、ＭＯＣＶＤ装置に大量に原料を供給するこ
とができる。本発明の有機チタン化合物を有機溶媒に溶
解した溶液原料は高い成膜速度でチタン含有誘電体薄膜
が得られる。また、熱安定性、気化安定性に優れるた
め、高い純度の薄膜が得られる。As described above, as described above, the general formula [T
When an organic titanium compound composed of i (Oi-Pr) 2 (dmhd) 2 ] is formed by MOCVD using this compound as a raw material, conventional [Ti (Oi-Pr) 2 (DPM) 2 ] The organic titanium compound has a higher solubility in an organic solvent than a typical organic titanium compound, so that a large amount of raw material can be supplied to the MOCVD apparatus. From the solution raw material obtained by dissolving the organic titanium compound of the present invention in an organic solvent, a titanium-containing dielectric thin film can be obtained at a high film forming rate. In addition, a high-purity thin film can be obtained because of its excellent thermal stability and vaporization stability.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 齋 篤 埼玉県大宮市北袋町１丁目297番地 三菱 マテリアル株式会社総合研究所内 (72)発明者 小木 勝実 埼玉県大宮市北袋町１丁目297番地 三菱 マテリアル株式会社総合研究所内 Ｆターム(参考） 4H006 AA01 AB78 AB91 4H049 VN05 VP01 VQ24 VR44 VU24 VW02 4K030 AA11 BA42 LA01 5F083 AD00 JA13 JA14 JA15 PR21 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Atsushi Sai 1-297 Kitabukurocho, Omiya City, Saitama Prefecture Inside the Mitsubishi Materials Research Institute (72) Inventor Katsumi Ogi 1-297 Kitabukurocho Omiya City, Saitama Mitsubishi Materials F-term in the Research Institute, Inc. (reference) 4H006 AA01 AB78 AB91 4H049 VN05 VP01 VQ24 VR44 VU24 VW02 4K030 AA11 BA42 LA01 5F083 AD00 JA13 JA14 JA15 PR21
Claims (4)
物。 【化１】 但し、結合基Ｏ-ｉ-Ｐｒは次の式（２）で表されるイソ
プロポキシド基であり、ｄｍｈｄは次の式（３）で表さ
れる２，６−ジメチル−３，５−ヘプタンジオン残基で
ある。 【化２】 【化３】 An organotitanium compound represented by the following formula (1): Embedded image Here, the bonding group Oi-Pr is an isopropoxide group represented by the following formula (2), and dmhd is 2,6-dimethyl-3,5-heptane represented by the following formula (3). It is a dione residue. Embedded image Embedded image
溶媒に溶解した溶液原料。2. A solution raw material obtained by dissolving the organic titanium compound according to claim 1 in an organic solvent.
テトラヒドロフラン、ｎ−オクタン、イソオクタン、ヘ
キサン、シクロヘキサン、ピリジン、ルチジン、酢酸ブ
チル又は酢酸アミルからなる群より選ばれた１種又は２
種以上の溶媒である請求項２記載の溶液原料。3. The organic solvent is one or two selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, n-octane, isooctane, hexane, cyclohexane, pyridine, lutidine, butyl acetate and amyl acetate.
3. The solution raw material according to claim 2, which is at least one kind of solvent.
有機金属化学蒸着法により作製されたチタン含有誘電体
薄膜。4. A titanium-containing dielectric thin film produced by a metal organic chemical vapor deposition method using the solution raw material according to claim 2.
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|---|---|---|---|
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|---|---|
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ID=18872785
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6872419B2 (en) * | 2002-01-21 | 2005-03-29 | Kabushikikaisha Kojundokagaku Kenkyusho | Method or process for producing PZT films at low substrate temperatures by chemical vapor deposition |
-
2001
- 2001-01-12 JP JP2001004627A patent/JP2002212130A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6872419B2 (en) * | 2002-01-21 | 2005-03-29 | Kabushikikaisha Kojundokagaku Kenkyusho | Method or process for producing PZT films at low substrate temperatures by chemical vapor deposition |
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