JP3119128B2 - High purity Ti complex, method for producing the same, and liquid composition for forming BST film - Google Patents
High purity Ti complex, method for producing the same, and liquid composition for forming BST filmInfo
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- JP3119128B2 JP3119128B2 JP07194874A JP19487495A JP3119128B2 JP 3119128 B2 JP3119128 B2 JP 3119128B2 JP 07194874 A JP07194874 A JP 07194874A JP 19487495 A JP19487495 A JP 19487495A JP 3119128 B2 JP3119128 B2 JP 3119128B2
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、誘電体膜、半導体
膜、光学薄膜、表面強化膜、薄膜触媒等として有用なＴ
ｉを含む金属酸化物薄膜を、化学気相析出法（ＣＶＤ
法）にて形成するための原料として好適な高純度Ｔｉ錯
体及びその製造方法並びにＢＳＴ膜形成用液体組成物に
関する。The present invention relates to a T film useful as a dielectric film, a semiconductor film, an optical thin film, a surface enhancement film, a thin film catalyst and the like.
A metal oxide thin film containing i is deposited by chemical vapor deposition (CVD).
The present invention relates to a high-purity Ti complex suitable as a raw material for forming by the method, a method for producing the same, and a liquid composition for forming a BST film.
【０００２】[0002]
【従来の技術】従来、チタン酸ストロンチウム、チタン
酸バリウムストロンチウム（ＢＳＴ）、チタン酸ジルコ
ン酸鉛等のＴｉ含有誘電体薄膜形成用のＣＶＤ原料とし
て、各種金属アルコキシド化合物やＴｉＤＰＭ（本明細
書において、「ＤＰＭ」はジピバロイルメタン：（ＣＨ
３）３−Ｃ−ＣＯ−ＣＨ２−ＣＯ−Ｃ−（ＣＨ３）３を
示す。）錯体が、Ｂａ、Ｓｒ、Ｚｒ等のアルコキシド化
合物やＤＰＭ錯体と共に用いられている。2. Description of the Related Art Conventionally, various metal alkoxide compounds and TiDPM (herein referred to as "strontium titanate, barium strontium titanate (BST), lead zirconate titanate, etc.) "DPM" is dipivaloylmethane: (CH
3) 3 -C-CO-CH 2 -CO-C- (CH 3) shows a 3. ) Complexes are used together with alkoxide compounds such as Ba, Sr and Zr and DPM complexes.
【０００３】これらのＣＶＤ原料のうち、ＴｉＤＰＭ錯
体については、特開平５−２７１２５３号公報に「高純
度チタン錯体及びその製造方法」として、Ｔｉ（Ｒ１）
２（Ｒ２）２（Ｒ１はアセチルアセトン、３，５−ヘプ
タンジオン、ジピバロイルメタン等のβ−ジケトン、Ｒ
２はメトキシ、エトキシ、イソプロポキシ（以下「Ｏ−
ｉ−Ｐｒ」と記す。）、ノルマルプロポキシ、ノルマル
ブトキシ等のアルコキシ基）と、これを製造する方法が
開示されている。なお、この特開平５−２７１２５３号
公報に具体的な実施例として挙げられているＴｉＤＰＭ
錯体は、Ｔｉ（Ｏ−ｉ−Ｐｒ）２（ＤＰＭ）２のみであ
る。[0003] Among these CVD raw materials, the TiDPM complex is described in Japanese Patent Application Laid-Open No. 5-271253 as "High purity titanium complex and method for producing the same".
2 (R2) 2 (R1 is a β-diketone such as acetylacetone, 3,5-heptanedione, dipivaloylmethane, R
2 is methoxy, ethoxy, isopropoxy (hereinafter "O-
i-Pr ". ), Normal propoxy, normal butoxy and the like) and a method for producing the same. Incidentally, the TiDPM disclosed as a specific example in Japanese Patent Application Laid-Open No. 5-271253 is disclosed.
The complex is only Ti (Oi-Pr) 2 (DPM) 2 .
【０００４】[0004]
【発明が解決しようとする課題】ＣＶＤ法によるＢＳＴ
膜形成用原料として、Ｂａ（ＤＰＭ）２，Ｓｒ（ＤＰ
Ｍ）２と共に、Ｔｉ（Ｏ−ｉ−Ｐｒ）２（ＤＰＭ）２を
用いた場合、Ｂａ（ＤＰＭ）２、Ｓｒ（ＤＰＭ）２の熱
分解温度３５０〜４１０℃に対して、Ｔｉ（Ｏ−ｉ−Ｐ
ｒ）２（ＤＰＭ）２の熱分解温度が２７０℃（２５５〜
２９０℃）と低いために、成膜時に気相でのＴｉ（Ｏ−
ｉ−Ｐｒ）２（ＤＰＭ）２の分解反応が進み易く、気相
分解種の基板への吸着確率が増大する。このため、表面
に凹凸がある基板に対する成膜時の段差被覆性が悪化す
るという欠点がある。SUMMARY OF THE INVENTION BST by CVD
Ba (DPM) 2 , Sr (DP
When Ti (Oi-Pr) 2 (DPM) 2 is used together with M) 2 , the thermal decomposition temperature of Ba (DPM) 2 and Sr (DPM) 2 is 350 to 410 ° C., and Ti (O− i-P
r) 2 (DPM) 2 has a thermal decomposition temperature of 270 ° C. (255 to
290 ° C.), so that Ti (O—
The decomposition reaction of i-Pr) 2 (DPM) 2 easily proceeds, and the probability of adsorption of the gas phase decomposition species to the substrate increases. For this reason, there is a disadvantage that the step coverage at the time of film formation on a substrate having irregularities on the surface is deteriorated.
【０００５】熱安定性の良い材料としてＴｉＣｌ２（Ｄ
ＰＭ）２（熱分解温度３３０℃（３２０〜３４０℃））
も知られているが、このものは、分子中に塩化物イオン
（Ｃｌ−）を含んでいるために、ＢＳＴ膜形成用原料と
して用いた場合、この塩素が不純物として膜中に取り込
まれてしまうという問題がある。[0005] TiCl 2 (D
PM) 2 (pyrolysis temperature 330 ° C (320-340 ° C))
Although this is also known, since it contains chloride ions (Cl − ) in the molecule, when used as a raw material for forming a BST film, this chlorine is taken into the film as an impurity. There is a problem.
【０００６】また、複合組成の金属酸化物膜の形成に当
り、ＣＶＤ原料の供給方法として、原料となる金属化合
物を有機溶媒に溶解した溶液を気化器に液体状態で供給
し、気化器で溶媒と共に加熱気化させ、ガスとしてＣＶ
Ｄ成膜室に供給する方法が知られているが、この方法に
おいて、Ｔｉ化合物中に不純物としてＯＨ基が含まれて
いると、Ｂａ（ＤＰＭ）２、Ｓｒ（ＤＰＭ）２がＯＨ基
に対して非常に反応活性が高いため、ＯＨ基と反応して
気化特性が低下し、気化器内部での残留物の増加、ガス
配管、シャワーヘッド等への分解物の析出量の増加を引
き起こす上に、膜の組成コントロールが困難となるとい
った問題が生じる。In forming a metal oxide film having a composite composition, as a method for supplying a CVD raw material, a solution in which a metal compound as a raw material is dissolved in an organic solvent is supplied in a liquid state to a vaporizer, and the solvent is supplied to the vaporizer. Together with heating and vaporization, and as a gas CV
A method of supplying the Ti compound to the D film formation chamber is known. In this method, when an OH group is contained as an impurity in the Ti compound, Ba (DPM) 2 and Sr (DPM) 2 It has a very high reaction activity and reacts with OH groups to lower the vaporization characteristics, causing an increase in residues inside the vaporizer and an increase in the amount of decomposition products deposited on gas pipes, showerheads, etc. This makes it difficult to control the composition of the film.
【０００７】本発明は上記従来の問題点を解決し、著し
く高純度であるため不純物による問題がなく、しかも、
熱分解温度が高く、気相分解による段差被覆性の低下の
問題もない高純度Ｔｉ錯体及びその製造方法、並びに、
この高純度Ｔｉ錯体を用いたＢＳＴ膜形成用液体組成物
を提供することを目的とする。[0007] The present invention solves the above-mentioned conventional problems, and has extremely high purity, so that there is no problem due to impurities.
A high-purity Ti complex having a high thermal decomposition temperature and no problem of lowering step coverage due to gas-phase decomposition, and a method for producing the same; and
An object of the present invention is to provide a liquid composition for forming a BST film using the high-purity Ti complex.
【０００８】[0008]
【課題を解決するための手段】本発明の高純度Ｔｉ錯体
は、下記化学式（Ｉ）で表される高純度Ｔｉ錯体であっ
てＯＨ基の含有量が０．１重量％以下、塩素含有量が５
ｐｐｍ以下であることを特徴とする。Pure Ti complexes of the present invention According to an aspect of the Tsu der high purity Ti complex represented by the following formula (I)
The OH group content is 0.1% by weight or less, and the chlorine content is 5%.
ppm or less .
【０００９】 ［ＴｉＯ（ＤＰＭ）２］２ ……（Ｉ） （ただし、（Ｉ）式中、ＤＰＭはジピバロイルメタンを
示す。）［ＴｉＯ（ＤＰＭ）２］２は、熱分解温度が３
２５℃（３００〜３５０℃）と、従来のＴｉ（Ｏ−ｉ−
Ｐｒ）２（ＤＰＭ）２よりも高く、Ｂａ（ＤＰＭ）２や
Ｓｒ（ＤＰＭ）２とほぼ同等の熱分解温度である。従っ
て、気相分解種の基板への吸着が低減され、段差被覆性
が良好となる。[TiO (DPM) 2 ] 2 (I) (where DPM represents dipivaloylmethane in the formula (I)) [TiO (DPM) 2 ] 2 has a thermal decomposition temperature of 3
25 ° C (300-350 ° C) and conventional Ti (O-i-
Pr) 2 (DPM) higher than 2, is substantially equal to the thermal decomposition temperature and Ba (DPM) 2 and Sr (DPM) 2. Therefore, adsorption of the gas phase decomposition species to the substrate is reduced, and the step coverage is improved.
【００１０】しかも、［ＴｉＯ（ＤＰＭ）２］２はＯＨ
基含有量０．１重量％以下、塩素含有量５ｐｐｍ以下の
高純度に精製可能であるため、不純物汚染の問題もな
く、高純度なＴｉ酸化物薄膜を形成することができる。In addition, [TiO (DPM) 2 ] 2 is OH
Since it can be purified to a high purity with a group content of 0.1% by weight or less and a chlorine content of 5 ppm or less, a high-purity Ti oxide thin film can be formed without a problem of impurity contamination.
【００１１】このような本発明の高純度Ｔｉ錯体は、ジ
クロロ・ビス（ジピバロイルメタナト）チタン錯体（Ｔ
ｉＣｌ２（ＤＰＭ）２）を有機溶媒に溶解した溶液に純
水を加えた後、撹拌下、アルカリ剤を添加して水層のｐ
Ｈを６．０〜８．０として白濁させ、次いで、有機層を
分取して純水で洗浄した後、加熱還流して結晶を得る、
本発明の高純度Ｔｉ錯体の製造方法により容易に製造す
ることができる。The high-purity Ti complex of the present invention is a dichlorobis (dipivaloylmethanato) titanium complex (T
After adding pure water to a solution in which iCl 2 (DPM) 2 ) is dissolved in an organic solvent, an alkaline agent is added under stirring to add p
H was adjusted to 6.0 to 8.0 to make it cloudy, then the organic layer was separated, washed with pure water, and heated to reflux to obtain crystals.
It can be easily produced by the method for producing a high-purity Ti complex of the present invention.
【００１２】また、この方法において、得られた結晶を
非プロトン性溶媒で精製することにより、高純度Ｔｉ錯
体のＯＨ基や残留塩素等の不純物含有量を著しく低いも
のとすることができる。Further, in this method, the content of impurities such as OH groups and residual chlorine of the high-purity Ti complex can be remarkably reduced by purifying the obtained crystals with an aprotic solvent.
【００１３】本発明のＢＳＴ膜形成用液体組成物は、こ
のような本発明の高純度Ｔｉ錯体とビス（ジピバロイル
メタナト）バリウム錯体（Ｂａ（ＤＰＭ）２）及び／又
はビス（ジピバロイルメタナト）ストロンチウム錯体
（Ｓｒ（ＤＰＭ）２）とを、特定の有機溶媒に溶解して
なるものである。The liquid composition for forming a BST film of the present invention comprises the high purity Ti complex of the present invention and a bis (dipivaloylmethanato) barium complex (Ba (DPM) 2 ) and / or bis (dipi (Valloylmethanato) strontium complex (Sr (DPM) 2 ) dissolved in a specific organic solvent.
【００１４】この本発明のＢＳＴ膜形成用液体組成物に
あっては、Ｔｉ原料として用いる高純度Ｔｉ錯体が、Ｏ
Ｈ基含有量が著しく低い、非常に高純度なものであるた
め、Ｂａ（ＤＰＭ）２、Ｓｒ（ＤＰＭ）２のような、Ｏ
Ｈ基に対して反応活性な原料との組み合わせにおいて、
気化特性を損なうことがなく、従って、気化器内部での
残留物の増加、ガス配管、シャワーヘッド等への分解物
の析出量の増加等の問題を引き起こすことなく、所望の
組成のＢＳＴ膜を効率的に成膜することができる。In the liquid composition for forming a BST film according to the present invention, the high-purity Ti complex used as a Ti raw material contains O
Since the H group content is extremely low and the purity is extremely high, it is difficult to obtain O (O) such as Ba (DPM) 2 and Sr (DPM) 2.
In combination with a raw material reactive to the H group,
A BST film having a desired composition can be formed without impairing the vaporization characteristics and without causing problems such as an increase in residues inside the vaporizer and an increase in the amount of decomposition products deposited on gas pipes and showerheads. A film can be formed efficiently.
【００１５】本発明のＢＳＴ膜形成用液体組成物におい
て、有機溶媒としては、ピリジン及び／又はルチジン、
或いはピリジン及び／又はルチジンとテトラヒドロフラ
ンと の混合溶媒を用いる。In the liquid composition for forming a BST film of the present invention, pyridine and / or lutidine ,
Alternatively , a mixed solvent of pyridine and / or lutidine and tetrahydrofuran is used .
【００１６】[0016]
【発明の実施の形態】本発明の高純度Ｔｉ錯体は、後掲
の実施例１の分析結果から推定されるように、１個のＴ
ｉ原子に対して、２個のジピバロイルメタンのカルボニ
ル基の酸素と、他のＴｉ原子と共有する２個の酸素との
合計６個の酸素が配位した構造を有する（ジピバロイル
メタナイト）チタン錯体である。BEST MODE FOR CARRYING OUT THE INVENTION The high-purity Ti complex of the present invention has a single T complex as estimated from the analysis results of Example 1 described later.
It has a structure in which a total of six oxygens, i.e., oxygen of the carbonyl group of two dipivaloylmethanes and two oxygens shared with other Ti atoms, are coordinated with respect to the i atom (dipivaloyl) Ilmethanite) titanium complex.
【００１７】この本発明の高純度Ｔｉ錯体を製造するに
は、まず、後掲の実施例１で示されるように、ＴｉＣｌ
２（ＤＰＭ）２を出発原料として用い、これをトルエ
ン、キシレン、メシチレン等の芳香族炭化水素、或い
は、ペンタン、ノルマルヘキサン等の脂肪族炭化水素等
の有機溶媒に、１．０〜４０重量％濃度となるように溶
解し、得られた溶液に純水を加え、激しく撹拌しなが
ら、水層のｐＨが６．０〜８．０、好ましくはｐＨ７．
０〜７．５の弱アルカリ性となって白濁が生成するまで
アンモニア水等のアルカリ剤を滴下する。ここで、Ｔｉ
Ｃｌ２（ＤＰＭ）２溶液に対する純水の添加量は５〜２
０倍程度とするのが好ましい。また、用いるアンモニア
水の濃度は０．１〜５Ｎ程度のものが好適である。In order to produce the high-purity Ti complex of the present invention, first, as shown in Example 1 below, TiCl
2 (DPM) 2 is used as a starting material, and is added to an organic solvent such as an aromatic hydrocarbon such as toluene, xylene or mesitylene, or an aliphatic hydrocarbon such as pentane or normal hexane in an amount of 1.0 to 40% by weight. The resulting solution was dissolved to a concentration, pure water was added to the resulting solution, and the pH of the aqueous layer was 6.0 to 8.0, preferably pH 7.0, with vigorous stirring.
An alkaline agent such as aqueous ammonia is dropped until the mixture becomes weakly alkaline at 0 to 7.5 and cloudy. Where Ti
The amount of pure water added to the Cl 2 (DPM) 2 solution is 5-2.
It is preferably set to about 0 times. The concentration of the aqueous ammonia used is preferably about 0.1 to 5 N.
【００１８】次いで有機層を分取して純水で洗浄した
後、用いた有機溶媒の沸点より１０〜５０℃高いオイル
バスの温度で加熱還流することにより、残留水分やＯＨ
基を共沸により除去すると共に、濃縮し、結晶を得る。Next, the organic layer is separated, washed with pure water, and then heated to reflux in an oil bath at a temperature higher by 10 to 50 ° C. than the boiling point of the organic solvent used to obtain residual water and OH.
The groups are removed azeotropically and concentrated to give crystals.
【００１９】この結晶は、トルエン、キシレン、メシチ
レン等の非プロトン性有機溶媒を用いて、再結晶後、減
圧下で溶媒を昇華させる精製を繰り返し行うことによ
り、ＯＨ基含有量０．１重量％以下で残留塩素含有量が
５ｐｐｍ以下の高純度［ＴｉＯ（ＤＰＭ）２］２を得る
ことができる。The crystals are recrystallized using an aprotic organic solvent such as toluene, xylene or mesitylene, and then repeatedly purified by sublimation of the solvent under reduced pressure to give an OH group content of 0.1% by weight. High purity [TiO (DPM) 2 ] 2 having a residual chlorine content of 5 ppm or less can be obtained below.
【００２０】本発明の高純度Ｔｉ錯体において、［Ｔｉ
Ｏ（ＤＰＭ）２］２のＯＨ基含有量が０．１重量％を超
えると、Ｂａ（ＤＰＭ）２やＳｒ（ＤＰＭ）２等のＯＨ
基に対して反応活性の高い他の原料と共に複合金属酸化
物膜形成用液体組成物とした場合、気化特性を劣化さ
せ、気化器内部での残留物の増加、ガス配管、シャワー
ヘッド等への分解物の析出量の増加、膜組成のずれを引
き起こす。In the high purity Ti complex of the present invention, [Ti
When the OH group content of O (DPM) 2 ] 2 exceeds 0.1% by weight, OH such as Ba (DPM) 2 or Sr (DPM) 2
When a liquid composition for forming a composite metal oxide film is used together with other raw materials having a high reaction activity with respect to the group, the vaporization characteristics are degraded, the residue inside the vaporizer is increased, and the gas piping, shower head, etc. This causes an increase in the amount of decomposition products deposited and a shift in film composition.
【００２１】また、残留塩素含有量が５ｐｐｍを超える
と、得られるＴｉ酸化物膜の純度が損なわれる。When the residual chlorine content exceeds 5 ppm, the purity of the obtained Ti oxide film is impaired.
【００２２】従って、本発明の高純度Ｔｉ錯体は、ＯＨ
基の含有量が０．１重量％以下、塩素含有量が５ｐｐｍ
以下とする。Therefore, the high purity Ti complex of the present invention is
Group content is less than 0.1% by weight, chlorine content is 5ppm
The following is assumed .
【００２３】本発明のＢＳＴ膜形成用液体組成物は、こ
のような本発明の［ＴｉＯ（ＤＰＭ）２］２とＢａ（Ｄ
ＰＭ）２及び／又はＳｒ（ＤＰＭ）２とを所望の膜組成
となるように有機溶媒に溶解したものである。The liquid composition for forming a BST film of the present invention comprises the [TiO (DPM) 2 ] 2 of the present invention and Ba (D
PM) 2 and / or Sr (DPM) 2 are dissolved in an organic solvent so as to have a desired film composition.
【００２４】ここで、有機溶媒としては、ピリジン及び
／又はルチジン、或いはピリジン及び／又はルチジンと
テトラヒドロフラン（ＴＨＦ）との混合溶媒を用いる。
［ＴｉＯ（ＤＰＭ）２］２とＢａ（ＤＰＭ）２及び／又
はＳｒ（ＤＰＭ）２とは、このような有機溶媒に、その
合計濃度が１〜２０重量％となるように溶解するのが好
ましい。Here, pyridine and organic solvents are used as the organic solvent.
And / or lutidine or a mixed solvent of pyridine and / or lutidine and tetrahydrofuran (THF) is used.
[TiO (DPM) 2 ] 2 and Ba (DPM) 2 and / or Sr (DPM) 2 are preferably dissolved in such an organic solvent so that the total concentration thereof is 1 to 20% by weight. .
【００２５】本発明の高純度Ｔｉ錯体は、これをそのま
ま固体状態で常法に従ってＣＶＤ原料として用いること
もでき、また、上述の如く、必要に応じて他の金属化合
物と共に有機溶媒に溶解して従来と同様にしてＣＶＤ原
料として用いることもできる。The high-purity Ti complex of the present invention can be used as it is in a solid state as a raw material for CVD according to a conventional method. Alternatively, as described above, it can be dissolved in an organic solvent together with another metal compound as necessary. It can be used as a CVD raw material in the same manner as in the prior art.
【００２６】[0026]
【実施例】実施例１：高純度［ＴｉＯ（ＤＰＭ）２］２
の合成 ＴｉＣｌ２（ＤＰＭ）２のトルエン溶液（３０重量％濃
度）２００ｍｌに純水１５００ｍｌを加え激しく撹拌し
ながら、ゆっくりと水層のｐＨが中性から弱アルカリに
なるまでアンモニア水（１．２重量％）の滴下を行い、
溶液中に白濁が起こりはじめた所を終点とした。次い
で、トルエン層を分離して純水で十分に洗浄した後、溶
液をオイルバスの温度１３０〜１５０℃で加熱還流し、
残留水分、ＯＨ基を共沸により除去した後、濃縮し、白
色結晶を得た。この結晶をトルエンで再結晶した後、減
圧下、１９０℃で昇華精製を行った。EXAMPLES Example 1 High Purity [TiO (DPM) 2 ] 2
To 200 ml of a toluene solution (30% by weight) of TiCl 2 (DPM) 2 , 1500 ml of pure water was added, and under vigorous stirring, ammonia water (1.2%) was slowly added until the pH of the aqueous layer became neutral to weakly alkaline. % By weight)
The point at which cloudiness began to occur in the solution was defined as the end point. Then, after separating the toluene layer and thoroughly washing with pure water, the solution was heated to reflux at an oil bath temperature of 130 to 150 ° C.,
After removing residual water and OH groups by azeotropic distillation, the mixture was concentrated to obtain white crystals. After recrystallizing these crystals with toluene, sublimation purification was performed at 190 ° C. under reduced pressure.
【００２７】得られた結晶の同定は、１Ｈ−ＮＭＲ（Ｃ
６Ｄ６＋ｄ−ＴＨＦ）、質量分析、元素分析により行っ
た。結果は下記の通りである。１ Ｈ−ＮＭＲ：δ：5.9331（２Ｈ，−ＣＨ），1.563
（３６Ｈ，Ｃ（ＣＨ３）３) 元素分析：（計算値）Ｔｉ＝11.12%、 Ｃ＝61.39%、 Ｈ＝8.90%、 Ｏ＝18.59% （実測値）Ｔｉ＝11.08%、 Ｃ＝61.45%、 Ｈ＝8.64%、 Ｏ＝18.59% 質量分析：図１に示す通り、M/Z860の分子イオンピーク
が確認されている。The obtained crystals were identified by 1 H-NMR (C
6 D 6 + d-THF) , mass spectrometry, was carried out by elemental analysis. The results are as follows. 1 H-NMR: δ: 5.9331 (2H, —CH), 1.563
(36H, C (CH 3 ) 3 ) Elemental analysis: (calculated value) Ti = 11.12%, C = 61.39%, H = 8.90%, O = 18.59% (actual value) Ti = 11.08%, C = 61.45%, H = 8.64%, O = 18.59% Mass spectrometry: As shown in FIG. 1, the molecular ion peak of M / Z860 is confirmed.
【００２８】以上の分析結果より、得られた［ＴｉＯ
（ＤＰＭ）２］２の構造式としては、下記の構造が推定
される。From the above analysis results, the obtained [TiO 2
(DPM) 2 ] As the structural formula of 2 , the following structure is estimated.
【００２９】[0029]
【化１】 Embedded image
【００３０】なお、得られた［ＴｉＯ（ＤＰＭ）２］２
結晶の元素分析により、残留Ｃｌ量は＜１ｐｐｍであ
り、また、ＩＲ分析によりＯＨ基は＜０．１重量％であ
ることが確認された。The obtained [TiO (DPM) 2 ] 2
Elemental analysis of the crystals confirmed a residual Cl content of <1 ppm, and IR analysis confirmed that the OH groups were <0.1% by weight.
【００３１】この［ＴｉＯ（ＤＰＭ）２］２結晶につい
て、Ａｒ気流下、昇温速度１０℃／ｍｉｎでＴＧ分析を
行ったところ、図２に示す如く、この［ＴｉＯ（ＤＰ
Ｍ）２］２は、２００℃から気化を開始し、３６０℃で
１００％気化することが確認された。The [TiO (DPM) 2 ] 2 crystal was subjected to TG analysis under an Ar gas flow at a temperature rising rate of 10 ° C./min. As shown in FIG.
M) 2 ] 2 started to vaporize at 200 ° C. and was confirmed to vaporize at 360 ° C. by 100%.
【００３２】また、この［ＴｉＯ（ＤＰＭ）２］２結晶
をＡｌ容器内に密封し、Ａｒ気流下、昇温速度１０℃／
ｍｉｎでＤＴＡ分析を行ったところ、熱分解温度は、３
２５℃（３００〜３５０℃）であることが確認された。The [TiO (DPM) 2 ] 2 crystal was sealed in an Al container and heated at a rate of 10 ° C. /
When DTA analysis was carried out at a min.
It was confirmed that the temperature was 25 ° C (300 to 350 ° C).
【００３３】実施例２：ＣＶＤ成膜試験 実施例１において、アンモニア水の滴下量を減らし、水
層のｐＨを弱酸性側とすることにより、残留塩素量が各
々４ｐｐｍ，６ｐｐｍ，２００ｐｐｍ，３０００ｐｐｍ
の［ＴｉＯ（ＤＰＭ）２］２結晶を得、これらの［Ｔｉ
Ｏ（ＤＰＭ）２］２結晶と実施例１で得られた残留塩素
含有量が＜１ｐｐｍの［ＴｉＯ（ＤＰＭ）２］２結晶と
をそれぞれＴｉ原料として用いると共に、Ｂａ（ＤＰ
Ｍ）２及びＳｒ（ＤＰＭ）２を併用してＣＶＤ法により
下記成膜条件でＢＳＴ（Ｂａ０．７Ｓｒ０．３Ｔｉ０．
１）膜の成膜を行った。Example 2: CVD film forming test In Example 1, the amount of residual chlorine was reduced to 4 ppm, 6 ppm, 200 ppm, and 3000 ppm by reducing the amount of the aqueous ammonia added and decreasing the pH of the aqueous layer to a slightly acidic side.
[TiO (DPM) 2 ] 2 crystals were obtained.
O (DPM) 2 ] 2 crystal and the [TiO (DPM) 2 ] 2 crystal obtained in Example 1 having a residual chlorine content of <1 ppm were used as Ti raw materials, respectively, and Ba (DP
M) 2 and Sr (DPM) 2 in combination with BST (Ba0.7Sr0.3Ti0.
1) A film was formed.
【００３４】成膜条件 ＣＶＤ装置：基板加熱式ＣＶＤ装置 反応ガス：Ｏ２ キャリアガス：Ａｒ 気化温度： ［ＴｉＯ（ＤＰＭ）２］２＝１８０℃ Ｂａ（ＤＰＭ）２＝２００℃ Ｓｒ（ＤＰＭ）２＝１９０℃ 成膜圧力：２．０ｔｏｒｒ 基板：Ｐｔ／Ｔｉ電極 基板温度：６００℃ 成膜厚さ：１０００ÅFilm forming conditions CVD apparatus: substrate heating type CVD apparatus Reaction gas: O2 Carrier gas: Ar Vaporization temperature: [TiO (DPM)2]2= 180 ° C Ba (DPM)2= 200 ° C Sr (DPM)2= 190 ° C. Deposition pressure: 2.0 torr Substrate: Pt / Ti electrode Substrate temperature: 600 ° C. Deposition thickness: 1000 °
【００３５】得られたＢＳＴ膜上に各々Ａｕ電極を蒸着
し、電気特性の評価を行い、結果を表１に示した。An Au electrode was vapor-deposited on each of the obtained BST films, and the electrical characteristics were evaluated. The results are shown in Table 1.
【００３６】[0036]
【表１】 [Table 1]
【００３７】実施例３：ＣＶＤ段差被覆性試験 特開平５−２７１２５３号公報記載のＴｉ（Ｏ−ｉ−Ｐ
ｒ）２（ＤＰＭ）２と、実施例１で製造した高純度［Ｔ
ｉＯ（ＤＰＭ）２］２とを用いて、図４に示す断面形状
のトレンチ基板１上に熱ＣＶＤ法により下記の条件で各
々ＴｉＯ２膜の成膜を行い、ＣＶＤ−ＴｉＯ２膜２の膜
厚ａと膜厚ｂとの比ａ／ｂ（ａ／ｂが１に近似している
ほど、段差被覆性が良い。）で段差被覆性の評価を行
い、結果を表２に示した。Example 3 Test of CVD step coverage Ti (OiP) described in JP-A-5-271253
r) 2 (DPM) 2 and the high-purity [T
Using TiO (DPM) 2 ] 2 , a TiO 2 film is formed on the trench substrate 1 having the cross-sectional shape shown in FIG. 4 by the thermal CVD method under the following conditions, and the CVD-TiO 2 film 2 is formed. The step coverage was evaluated based on the ratio a / b between the thickness a and the film thickness b (the closer the a / b was to 1, the better the step coverage). The results are shown in Table 2.
【００３８】成膜条件 気化温度： ［ＴｉＯ（ＤＰＭ）２］２＝１８０℃ Ｔｉ（Ｏ−ｉ−Ｐｒ）２（ＤＰＭ）２＝１４０℃ 成膜圧力：２．０ｔｏｒｒ 基板温度：６００℃Film formation conditions Vaporization temperature: [TiO (DPM) 2 ] 2 = 180 ° C. Ti (Oi-Pr) 2 (DPM) 2 = 140 ° C. Film formation pressure: 2.0 torr Substrate temperature: 600 ° C.
【００３９】また、Ｔｉ（Ｏ−ｉ−Ｐｒ）２（ＤＰＭ）
２について、実施例１と同様にしてＴＧ分析及びＤＴＡ
分析を行って、結果を図３及び表２に示した。Further, Ti (Oi-Pr) 2 (DPM)
About TG analysis and DTA about 2 similarly to Example 1.
The analysis was performed and the results are shown in FIG.
【００４０】[0040]
【表２】 [Table 2]
【００４１】実施例４：ＢＳＴ溶液の気化特性評価 実施例１において、トルエンを溶媒として用いた共沸に
よる脱水工程を省くことにより、ＯＨ基が０．２重量
％、１重量％又は２重量％存在する［ＴｉＯ（ＤＰＭ）
２］２結晶を各々製造した。これらの［ＴｉＯ（ＤＰ
Ｍ）２］２結晶と、ＯＨ基の量が＜０．１％の、実施例
１で得られた高純度［ＴｉＯ（ＤＰＭ）２］２とを、そ
れぞれＢａ（ＤＰＭ）２、Ｓｒ（ＤＰＭ）２と共に表３
に示す無水溶媒に、Ｂａ：Ｓｒ：Ｔｉ＝０．５：０．
５：１なる組成比（モル比）で溶解した溶液を減圧濃縮
し、析出した固体の気化特性をＡｒ下でＴＧ分析して評
価し、結果を表３に示した。Example 4: Evaluation of the vaporization characteristics of the BST solution In Example 1, the azeotropic dehydration step using toluene as a solvent was omitted, so that the OH group was 0.2% by weight, 1% by weight or 2% by weight. Exists [TiO (DPM)
2 ] Two crystals were each produced. These [TiO (DP
M) 2 ] 2 crystal and the high-purity [TiO (DPM) 2 ] 2 obtained in Example 1, in which the amount of OH groups is <0.1%, were obtained by mixing Ba (DPM) 2 and Sr (DPM), respectively. Table 3 with 2 )
Ba: Sr: Ti = 0.5: 0.
The solution dissolved at a composition ratio (molar ratio) of 5: 1 was concentrated under reduced pressure, and the vaporization characteristics of the precipitated solid were evaluated by TG analysis under Ar. The results are shown in Table 3.
【００４２】[0042]
【表３】 [Table 3]
【００４３】[0043]
【発明の効果】以上詳述した通り、本発明の高純度Ｔｉ
錯体は、熱分解温度が高く、ＯＨ基や残留塩素等の不純
物含有量を著しく低減することができることから、
ＣＶＤ成膜に当り、気相でのＴｉ錯体の分解による気相
分解種の基板への吸着が低減され、成膜時の段差被覆性
が良好となる。 不純物汚染のない高純度で、電気特
性に優れたＴｉ酸化物膜を成膜できる。 Ｂａ（ＤＰ
Ｍ）２、Ｓｒ（ＤＰＭ）２等のＯＨ基に対する反応活性
の高い原料との組み合わせにおいて、これらの原料の気
化特性を損なうことがなく、従って、気化器内部での残
留物の増加、ガス配管、シャワーヘッド等への分解物の
析出量の増加等を引き起こすことなく、膜組成を容易に
コントロールして、所望の組成のＴｉ含有金属複合酸化
物膜を成膜できる。といった効果が奏される。従って、
本発明の高純度Ｔｉ錯体を、ＣＶＤ法によるＢＳＴ膜形
成原料等として用いることにより、１Ｇ以後に求められ
ている、微細で複雑な構造を有するメモリーデバイスの
誘電体薄膜を成膜することが可能となる。 As described in detail above, the high purity Ti of the present invention
Since the complex has a high thermal decomposition temperature and can significantly reduce the content of impurities such as OH groups and residual chlorine,
In CVD film formation, adsorption of the gas phase decomposition species to the substrate due to decomposition of the Ti complex in the gas phase is reduced, and the step coverage at the time of film formation is improved. A high-purity Ti oxide film free from impurity contamination and excellent in electric characteristics can be formed. Ba (DP
M) 2 , Sr (DPM) 2, etc., in combination with raw materials having a high activity for reacting with OH groups, do not impair the vaporization characteristics of these raw materials, and therefore increase the residue inside the vaporizer and increase the gas piping The film composition can be easily controlled and a Ti-containing metal composite oxide film having a desired composition can be formed without causing an increase in the amount of decomposition products deposited on a showerhead or the like. Such an effect is produced. Therefore,
By using the high-purity Ti complex of the present invention as a raw material for forming a BST film by a CVD method, it is possible to form a dielectric thin film of a memory device having a fine and complicated structure required after 1G. to become.
【００４４】このような本発明の高純度Ｔｉ錯体は、本
発明の高純度Ｔｉ錯体の製造方法により容易に製造され
る。[0044] High-purity Ti complexes of the present invention such as this are readily prepared by the method for producing a high purity Ti complexes of the present invention.
【００４５】請求項３の方法によれば、不純物含有量が
著しく少ない高純度Ｔｉ錯体を製造することができる。According to the method of claim 3, a high-purity Ti complex having an extremely small impurity content can be produced.
【００４６】請求項４のＢＳＴ膜形成用液体組成物によ
れば、気化特性を損なわずに同一の有機溶媒にＴｉ、Ｂ
ａ、Ｓｒ原料を溶解した溶液を調製することができ、こ
の溶液を気化器に供給し、気化器で溶媒と共に加熱気化
させ、ガスとしてＣＶＤ成膜室に供給するＣＶＤ原料供
給方法に安定に適応できる。According to the liquid composition for forming a BST film according to claim 4 , Ti and B can be added to the same organic solvent without impairing the vaporization characteristics.
a, a solution in which the Sr raw material is dissolved can be prepared, and this solution is supplied to a vaporizer, heated and vaporized together with a solvent in the vaporizer, and is stably adapted to a CVD raw material supply method of supplying a gas to a CVD film forming chamber. it can.
【図１】実施例１で製造した［ＴｉＯ（ＤＰＭ）２］２
結晶の質量分析結果を示すグラフである。FIG. 1 [TiO (DPM) 2 ] 2 produced in Example 1
4 is a graph showing the results of mass analysis of crystals.
【図２】実施例１で製造した［ＴｉＯ（ＤＰＭ）２］２
結晶のＴＧ分析結果を示すグラフである。FIG. 2 [TiO (DPM) 2 ] 2 produced in Example 1
4 is a graph showing the result of TG analysis of a crystal.
【図３】Ｔｉ（Ｏ−ｉ−Ｐｒ）２（ＤＰＭ）２のＴＧ分
析結果を示すグラフである。FIG. 3 is a graph showing a TG analysis result of Ti (Oi-Pr) 2 (DPM) 2 .
【図４】実施例３の段差被覆性評価方法を示す断面図で
ある。FIG. 4 is a cross-sectional view illustrating a step coverage evaluation method of Example 3.
１ トレンチ基板 ２ ＣＶＤ−ＴｉＯ２膜Reference Signs List 1 trench substrate 2 CVD-TiO 2 film
フロントページの続き (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 (56)参考文献 特開 平８−139043（ＪＰ，Ａ) 特開 平８−176826（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07F 7/28 C23C 16/40 H01L 21/205 ＣＡ（ＳＴＮ)Continuing from the front page (72) Katsumi Ogi 1-297 Kitabukuro-cho, Omiya-shi, Saitama Mitsui Materials Co., Ltd. General Research Laboratory (56) References JP-A-8-139043 (JP, A) JP-A-8- 176826 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) C07F 7/28 C23C 16/40 H01L 21/205 CA (STN)
Claims (4)
錯体であって、ＯＨ基の含有量が０．１重量％以下、塩
素含有量が５ｐｐｍ以下であることを特徴とする高純度
Ｔｉ錯体。 ［ＴｉＯ（ＤＰＭ）２］２ ……（Ｉ） （ただし、（Ｉ）式中、ＤＰＭはジピバロイルメタンを
示す。）1. High purity Ti represented by the following chemical formula (I)
A complex having an OH group content of 0.1% by weight or less and a salt
High purity characterized by having an elemental content of 5 ppm or less
Ti complex . [TiO (DPM) 2 ] 2 (I) (In the formula (I), DPM represents dipivaloylmethane.)
ト）チタン錯体（ＴｉＣｌ２（ＤＰＭ）２）を有機溶媒
に溶解した溶液に純水を加えた後、撹拌下、アルカリ剤
を添加して水層のｐＨを６．０〜８．０として白濁さ
せ、次いで、有機層を分取して純水で洗浄した後、加熱
還流して結晶を得ることを特徴とする請求項１に記載の
高純度Ｔｉ錯体の製造方法。2. Pure water is added to a solution in which a dichlorobis (dipivaloylmethanato) titanium complex (TiCl 2 (DPM) 2 ) is dissolved in an organic solvent. 2. The layer according to claim 1, wherein the pH of the layer is adjusted to 6.0 to 8.0 to make the layer cloudy, the organic layer is separated, washed with pure water, and heated to reflux to obtain crystals. A method for producing a pure Ti complex.
を非プロトン性溶媒で精製することを特徴とする高純度
Ｔｉ錯体の製造方法。3. A method according to claim 2, the method of producing a high purity Ti complex, characterized by purifying the resulting crystals in an aprotic solvent.
バロイルメタナト）バリウム錯体（Ｂａ（ＤＰＭ）２）
及び／又はビス（ジピバロイルメタナト）ストロンチウ
ム錯体（Ｓｒ（ＤＰＭ）２）とを、有機溶媒に溶解して
なるＢＳＴ膜形成用液体組成物であって、有機溶媒がピ
リジン及び／又はルチジン、或いはピリジン及び／又は
ルチジンとテトラヒドロフランとの混合溶媒であること
を特徴とするＢＳＴ膜形成用液体組成物。4. The high-purity Ti complex of claim 1 and a bis (dipivaloylmethanato) barium complex (Ba (DPM) 2 )
And / or a bis (dipivaloylmethanato) strontium complex (Sr (DPM) 2 ) dissolved in an organic solvent to form a BST film-forming liquid composition , wherein the organic solvent is
Lysine and / or lutidine, or pyridine and / or
Be a mixed solvent of lutidine and tetrahydrofuran
A liquid composition for forming a BST film, comprising:
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07194874A JP3119128B2 (en) | 1995-07-31 | 1995-07-31 | High purity Ti complex, method for producing the same, and liquid composition for forming BST film |
| KR1019960031489A KR100418164B1 (en) | 1995-07-31 | 1996-07-30 | High-Purity Ti complexes, Methods for Producing the same and BST Film-Forming Liquid compositions |
| US08/688,774 US5767302A (en) | 1995-07-31 | 1996-07-31 | High-purity TI complexes, methods for producing the same and BST film-forming liquid compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07194874A JP3119128B2 (en) | 1995-07-31 | 1995-07-31 | High purity Ti complex, method for producing the same, and liquid composition for forming BST film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0940682A JPH0940682A (en) | 1997-02-10 |
| JP3119128B2 true JP3119128B2 (en) | 2000-12-18 |
Family
ID=16331753
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|---|---|---|---|
| JP07194874A Expired - Fee Related JP3119128B2 (en) | 1995-07-31 | 1995-07-31 | High purity Ti complex, method for producing the same, and liquid composition for forming BST film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3119128B2 (en) |
-
1995
- 1995-07-31 JP JP07194874A patent/JP3119128B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0940682A (en) | 1997-02-10 |
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