JP2002069027A - HAFNIUM ALKOXYTRIS(beta-DIKETONATE), METHOD FOR MANUFACTURING THE SAME AND METHOD FOR MANUFACTURING OXIDE FILM USING THE SAME - Google Patents
HAFNIUM ALKOXYTRIS(beta-DIKETONATE), METHOD FOR MANUFACTURING THE SAME AND METHOD FOR MANUFACTURING OXIDE FILM USING THE SAMEInfo
- Publication number
- JP2002069027A JP2002069027A JP2000301239A JP2000301239A JP2002069027A JP 2002069027 A JP2002069027 A JP 2002069027A JP 2000301239 A JP2000301239 A JP 2000301239A JP 2000301239 A JP2000301239 A JP 2000301239A JP 2002069027 A JP2002069027 A JP 2002069027A
- Authority
- JP
- Japan
- Prior art keywords
- dpm
- oipr
- hafnium
- compound
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、常誘電体膜、光学
薄膜、触媒薄膜、固体電解質薄膜等として有用なＨｆ含
有酸化物膜を、化学気相成長法（ＣＶＤ法）にて形成す
るための原料として好適なＨｆ化合物、その製造方法お
よびそれを用いたＨｆ含有酸化物薄膜の製法に関する。The present invention relates to a method for forming an Hf-containing oxide film useful as a paraelectric film, an optical thin film, a catalyst thin film, a solid electrolyte thin film, etc. by a chemical vapor deposition (CVD) method. The present invention relates to a Hf compound suitable as a raw material for a compound, a method for producing the compound, and a method for producing an Hf-containing oxide thin film using the compound.
【０００２】[0002]
【従来の技術】最近ＬＳＩの高集積化に伴い、ＳｉＯ２
に代わるゲート絶縁膜が要望されており、その候補とし
て、Ｈｆ含有酸化物膜ＨｆＯ２、ＨｆＯ２−ＳｉＯ２な
どが検討されている。この極薄膜を再現性よくＣＶＤで
作るには、安定で成膜しやすく、かつ高純度の化合物が
必要である。この目的にはハフニウムターシャリブトキ
シド（Ｈｆ（ＯｔＢｕ）４と表す）やハフニウムテトラ
キス（ジピバロイルメタネート）（Ｈｆ（ｄｐｍ）４と
表す）が検討されている。しかし前者は低温で成膜でき
るが再現性が悪く、活性が高く取扱いがやや難しいとい
う欠点がある。後者は安定であるが成膜温度が高いとい
う欠点がある。2. Description of the Related Art Recently, with the increasing integration of LSI, SiO 2
There is a demand for a gate insulating film that can be used instead of HfO 2 , and Hf-containing oxide films HfO 2 , HfO 2 —SiO 2, and the like are being studied as candidates. In order to produce such an ultrathin film by CVD with good reproducibility, a compound having high purity, which is stable and easy to form a film, is required. For this purpose, hafnium tertiary butoxide (expressed as Hf (OtBu) 4 ) and hafnium tetrakis (dipivaloyl methanate) (expressed as Hf (dpm) 4 ) are being studied. However, the former can be formed at a low temperature, but has the drawback that the reproducibility is poor, the activity is high, and the handling is somewhat difficult. The latter is stable, but has the disadvantage that the film formation temperature is high.
【０００３】ＷＯ ９８／５１８３７（１９９８．１
１）は、Ｚｒ（ｄｐｍ）４の代わりにＺｒ（ＯｉＰｒ）
２（ｄｐｍ）２やＺｒ２（ＯｉＰｒ）６（ｄｐｍ）２の
新規化合物を使うと低温で析出し好ましいことを開示し
ているが、Ｈｆ（ＯｉＰｒ）２（ｄｐｍ）２やＨｆ
２（ＯｉＰｒ）６（ｄｐｍ）２については言及していな
い。該特許および該特許発明者の論文Ｉｎｏｒｇ．Ｃｈ
ｅｍ．Ｖｏｌ．３８，１４３２（１９９９）では、Ｈｆ
（ＯｉＰｒ）２（ｄｐｍ）２は混合物で、再結晶操作で
Ｈｆ２（ＯｉＰｒ）６（ｄｐｍ）２とＨｆ（ｄｐｍ）４
に分けられることを開示している。Ｈｆ２（ＯｉＰｒ）
６（ｄｐｍ）２は二量体のため、分子量が大きくその昇
華温度は高くなる。確かにＨｆ（ＯｉＰｒ）２（ｄｐ
ｍ）２やＨｆ２（ＯｉＰｒ）６（ｄｐｍ）２の熱分解温
度は、Ｚｒ化合物の挙動から推測して下がるだろうが、
必要な昇華温度が単量体に比べ高くなってしまうのは好
ましくない。[0003] WO 98/51837 (1998.1)
1) Zr (OiPr) instead of Zr (dpm) 4
2 (dpm) 2 and Zr 2 (OiPr) 6 (dpm ) 2 of discloses that preferred to precipitate at a low temperature using our novel compounds, Hf (OiPr) 2 (dpm ) 2 and Hf
2 (OiPr) 6 (dpm) 2 is not mentioned. The patent and the inventor's dissertation Inorg. Ch
em. Vol. 38, 1432 (1999), Hf
(OiPr) 2 (dpm) 2 is a mixture, which is Hf 2 (OiPr) 6 (dpm) 2 and Hf (dpm) 4 by a recrystallization operation.
Is disclosed. Hf 2 (OiPr)
Since 6 (dpm) 2 is a dimer, its molecular weight is large and its sublimation temperature is high. Certainly, Hf (OiPr) 2 (dp
m) The thermal decomposition temperature of 2 and Hf 2 (OiPr) 6 (dpm) 2 will be lowered by speculation from the behavior of the Zr compound,
It is not preferable that the required sublimation temperature is higher than that of the monomer.
【０００４】[0004]
【発明が解決しようとする課題】本課題は、Ｈｆ含有酸
化物膜ＨｆＯ２、ＨｆＯ２−ＳｉＯ２などの極薄膜を再
現性よくＣＶＤ法で低温で作るための、安定で成膜しや
すく、かつ高純度のＨｆ化合物を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide an ultra-thin film such as an Hf-containing oxide film HfO 2 or HfO 2 —SiO 2 at a low temperature by a CVD method with good reproducibility. Another object of the present invention is to provide a high-purity Hf compound.
【０００５】[0005]
【課題を解決するための手段】本発明のＨｆ化合物は、 Ｈｆ（ＯＲ）（Ｌ）３・・・・・・・・式Ｉ （Ｒは炭素数１〜４のアルキル基、Ｌはβ−ジケトネー
トを表す）で表される化合物である。本発明のＨｆ化合
物は、式ＩにおいてＲがイソプロピルまたはターシャリ
ブチル、Ｌがジピバロイルメタネートであるハフニウム
イソプロポキシトリス（ジピバロイルメタネート）Ｈｆ
（ＯｉＰｒ）（ｄｐｍ）３およびハフニウムターシャリ
ブトキシトリス（ジピバロイルメタネート）Ｈｆ（Ｏｔ
Ｂｕ）（ｄｐｍ）３である。本発明のＨｆ化合物の製造
方法は、ハフニウムテトラアルコキシド１モルとβ−ジ
ケトン３モルとを、有機溶媒中で反応させ、次いで溶媒
を留去し、次いで真空下で昇華精製する方法である。本
発明のＨｆ（ＯｉＰｒ）（ｄｐｍ）３あるいはＨｆ（Ｏ
ｔＢｕ）（ｄｐｍ）３の製造方法は、Ｈｆ（ＯｉＰｒ）
４あるいはＨｆ（ＯｔＢｕ）４１モルと、ジピバロイル
メタンｄｐｍＨ３モルとを、有機溶媒中で反応させ、次
いで溶媒を留去し、次いで真空下で昇華精製する方法で
ある。本発明のＨｆ含有酸化物薄膜の製法は、式Ｉの化
合物を用いて化学気相成長法により製造する方法であ
る。本発明のＨｆ含有酸化物薄膜の製法は、Ｈｆ（Ｏｉ
Ｐｒ）（ｄｐｍ）３あるいはＨｆ（ＯｔＢｕ）（ｄｐ
ｍ）３を用いて化学気相成長法により製造する方法であ
る。The Hf compound of the present invention is represented by the formula: Hf (OR) (L) 3 ... Formula I (R is an alkyl group having 1 to 4 carbon atoms, L is β- Which represents a diketonate). The hafnium isopropoxytris (dipivaloyl methanate) Hf compound of formula I wherein R is isopropyl or tert-butyl and L is dipivaloyl methanate in formula I
(OiPr) (dpm) 3 and hafnium tertiary butoxy tris (dipivaloyl methanate) Hf (Ot
Bu) (dpm) 3 . The method for producing the Hf compound of the present invention is a method in which 1 mol of hafnium tetraalkoxide and 3 mol of β-diketone are reacted in an organic solvent, the solvent is distilled off, and then sublimation purification is performed under vacuum. Hf (OiPr) (dpm) 3 or Hf (O
The production method of tBu) (dpm) 3 is Hf (OiPr)
4 or 1 mol of Hf (OtBu) 4 is reacted with 3 mol of dipivaloylmethane dpmH in an organic solvent, the solvent is distilled off, and then sublimation purification is performed under vacuum. The method for producing the Hf-containing oxide thin film of the present invention is a method for producing a compound of the formula I by a chemical vapor deposition method. The method for producing the Hf-containing oxide thin film of the present invention is based on Hf (Oi
Pr) (dpm) 3 or Hf (OtBu) (dp
m) This is a method of manufacturing by chemical vapor deposition using No. 3 .
【０００６】[0006]
【発明の実施の形態】本発明のＨｆ化合物は、 Ｈｆ（ＯＲ）（Ｌ）３・・・・・・・・式Ｉ （Ｒは炭素数１〜４のアルキル基、Ｌはβ−ジケトネー
トを表す）で表される化合物である。具体的にはＲはメ
チル、エチル、イソプロピル、ターシャリブチルよりな
る群から選ばれる１種である。またＬはジピバロイルメ
タネート（＝２，２，６，６−テトラメチル−３，５−
ヘプタンジオネート）、２，６−ジメチル−３，５−ヘ
プタンジオネート、２，２，６，６−テトラメチル−
３，５−オクタンジオネート、２，２，６−トリメチル
−３，５−ヘプタンジオネート、６−エチル−２，２−
ジメチル−３，５−オクタンジオネートなどである。こ
れらの化合物のうち容易に製造しうるＨｆ化合物は、Ｈ
ｆ（ＯｉＰｒ）（ｄｐｍ）３とＨｆ（ＯｔＢｕ）（ｄｐ
ｍ）３である。以下これらの化合物を例にとり詳細に述
べる。BEST MODE FOR CARRYING OUT THE INVENTION The Hf compound of the present invention is represented by the formula: Hf (OR) (L) 3 ... Formula I (R is an alkyl group having 1 to 4 carbon atoms, L is β-diketonate ). Specifically, R is one selected from the group consisting of methyl, ethyl, isopropyl and tertiary butyl. L is dipivaloyl methanate (= 2,2,6,6-tetramethyl-3,5-
Heptandionate), 2,6-dimethyl-3,5-heptanedionate, 2,2,6,6-tetramethyl-
3,5-octandionate, 2,2,6-trimethyl-3,5-heptanedionate, 6-ethyl-2,2-
And dimethyl-3,5-octandionate. Of these compounds, the Hf compound that can be easily produced is H
f (OiPr) (dpm) 3 and Hf (OtBu) (dp
m) 3 . Hereinafter, these compounds will be described in detail using examples.
【０００７】本発明のＨｆ（ＯｉＰｒ）（ｄｐｍ）３あ
るいはＨｆ（ＯｔＢｕ）（ｄｐｍ）３の製造方法は、Ｈ
ｆ（ＯｉＰｒ）４あるいはＨｆ（ＯｔＢｕ）４１モルと
ジピバロイルメタンｄｐｍＨ３モルとを、有機溶媒中で
反応させ、次いで溶媒を留去し、次いで真空下で昇華精
製する方法である。純Ｈｆ（ＯｉＰｒ）４の他に１モル
のイソプロパノールが配位したＨｆ（ＯｉＰｒ）４・ｉ
ＰｒＯＨアダクト物も原料として使える。アダクト物を
分解後、蒸留して得たＨｆ（ＯｉＰｒ）４であれば、反
応が進み易く、不純物が少なくできるので好ましい。Ｈ
ｆ（ＯｔＢｕ）（ｄｐｍ）３の原料であるＨｆ（ＯｔＢ
ｕ）４は、蒸気圧の高い室温で液体の化合物で、精留に
よって容易に高純度化できる。The method for producing Hf (OiPr) (dpm) 3 or Hf (OtBu) (dpm) 3 of the present invention
In this method, 1 mol of f (OiPr) 4 or Hf (OtBu) 4 is reacted with 3 mol of dipivaloylmethane dpmH in an organic solvent, the solvent is distilled off, and then sublimation purification is performed under vacuum. Hf (OiPr) 4 · i coordinated with 1 mol of isopropanol in addition to pure Hf (OiPr) 4
PrOH adducts can also be used as raw materials. It is preferable to use Hf (OiPr) 4 obtained by decomposing the adduct and then distilling it because the reaction can easily proceed and impurities can be reduced. H
Hf (OtB) which is a raw material of f (OtBu) (dpm) 3
u) 4 is a compound having a high vapor pressure and being liquid at room temperature, which can be easily purified by rectification.
【０００８】反応の有機溶媒としては、トルエンやヘキ
サン、ヘプタン、オクタンなどが使える。反応温度はそ
れらの沸点で、還流状態で行う。反応時間は１〜２０時
間である。反応後、副生したイソプロパノールあるいは
ターシャリブタノールと、溶媒を常圧ならびに減圧で留
去する。次いで残った釜残物を細かく砕き昇華管へ仕込
み、０．３Ｔｏｒｒで昇温していくと、１９０〜２００
℃付近で白色の昇華物が管壁に析出する。これが本発明
のＨｆ（ＯｉＰｒ）（ｄｐｍ）３およびＨｆ（ＯｔＢ
ｕ）３である。As the organic solvent for the reaction, toluene, hexane, heptane, octane and the like can be used. The reaction is carried out at the boiling point and at the reflux temperature. The reaction time is 1 to 20 hours. After the reaction, the by-produced isopropanol or tertiary butanol and the solvent are distilled off under normal pressure and reduced pressure. Next, the remaining pot residue was finely crushed and charged into a sublimation tube, and the temperature was raised at 0.3 Torr.
At around ℃, white sublimate precipitates on the tube wall. This corresponds to Hf (OiPr) (dpm) 3 and Hf (OtB) of the present invention.
u) 3 .
【０００９】実施例１で得られたＨｆ（ＯｉＰｒ）（ｄ
ｐｍ）３についての分析結果と物性は、以下のとおりで
ある。 （１）組成分析 ＩＣＰ発光分光分析の結果 Ｈｆ分析値 ２３．１ｗｔ％ （理論値２２．７ｗｔ
％） （２）不純物分析 ＩＣＰ発光分光分析の結果（単位ｐｐｍ） Ａｌ １１０ Ｃａ ４０ Ｆｅ ２ Ｍｇ＜１ Ｔｉ＜１ Ｚｒ １７００ であった。全Ｃｌ分析の結果Ｃｌは５ｐｐｍであった。 （３）ＥＩ−ＭＳ 測定条件 測定装置：ＪＥＯＬ ＡＸ５０５Ｗ イオン化法：ＥＩ イオン源温度：２２０℃ イオン化エネルギー：７０ｅＶ 測定結果を図１に示した。 Ｈｆは同位体が５種あるが、３５．１％が１８０Ｈｆで
あることを考慮し、主なｍ／ｚと強度（％）とそのイオ
ン種を以下に列挙した。分子イオンＨｆ（ＯｉＰｒ）
（ｄｐｍ）３ ＋（ｍ／ｚ＝７８８）はなかった。 ｍ／ｚ＝７２９（６３％）Ｈｆ（ｄｐｍ）３ ＋６７３
（１００％）Ｈｆ（ｄｐｍ）２（（Ｍｅ３Ｃ）ＣＯＣＨ
Ｃ（Ｈ）Ｏ）＋６０５（９８％）Ｈｆ（ＯｉＰｒ）（ｄ
ｐｍ）２ ＋ （４）蒸気圧 気体飽和法による測定値 ０．１Ｔｏｒｒ／１６０℃ （５）性状と融点 白色の結晶で、その融点は２００℃以上である。 （６）ＴＧ−ＤＴＡ 測定条件 試料重量：８．５４ｍｇ 雰囲気：Ａｒ １０Ｔｏｒｒ 昇温速度：１０．０ｄｅｇ／ｍｉｎ 測定結果を図２に示した。昇温していくと１９０℃付近
までに熱分解が生じていることがわかる。Ｈｆ（ｄｐ
ｍ）４が４００℃まででは、熱分解が起こらないのに比
べて、Ｈｆ（ＯｉＰｒ）（ｄｐｍ）３は明らかに低温で
熱分解が起こる。 （７）溶解度 溶媒１リットルに室温で溶解する量（ｇ）を調べた結果
を表１に示した。比較のため下段にＨｆ（ｄｐｍ）４の
値を示した。表１に示すとおり、Ｈｆ（ＯｉＰｒ）（ｄ
ｐｍ）３は、Ｈｆ（ｄｐｍ）４より溶けやすい。The Hf (OiPr) (d) obtained in Example 1
The analysis results and physical properties of (pm) 3 are as follows. (1) Composition analysis Results of ICP emission spectroscopy Hf analysis value 23.1 wt% (theoretical value 22.7 wt%
(2) Impurity analysis The result of ICP emission spectroscopy (unit: ppm) was Al 110 Ca 40 Fe 2 Mg <1 Ti <1 Zr 1700. As a result of total Cl analysis, Cl was 5 ppm. (3) EI-MS measurement conditions Measuring apparatus: JEOL AX505W Ionization method: EI Ion source temperature: 220 ° C. Ionization energy: 70 eV The measurement results are shown in FIG. Although Hf has five isotopes, considering that 35.1% is 180 Hf, main m / z, intensity (%) and ionic species are listed below. Molecular ion Hf (OiPr)
There was no (dpm) 3 + (m / z = 788). m / z = 729 (63%) Hf (dpm) 3 + 673
(100%) Hf (dpm) 2 ((Me 3 C) COCH
C (H) O) + 605 (98%) Hf (OiPr) (d
pm) 2 + (4) Vapor pressure Measured value by gas saturation method 0.1 Torr / 160 ° C (5) Properties and melting point White crystals, the melting point of which is 200 ° C or higher. (6) TG-DTA measurement conditions Sample weight: 8.54 mg Atmosphere: Ar 10 Torr Heating rate: 10.0 deg / min The measurement results are shown in FIG. It can be seen that as the temperature increases, thermal decomposition occurs up to around 190 ° C. Hf (dp
m) 4 does not undergo thermal decomposition up to 400 ° C., whereas Hf (OiPr) (dpm) 3 obviously undergoes thermal decomposition at low temperatures. (7) Solubility Table 1 shows the result of examining the amount (g) of dissolution in 1 liter of the solvent at room temperature. For comparison, the value of Hf (dpm) 4 is shown in the lower part. As shown in Table 1, Hf (OiPr) (d
(pm) 3 is more soluble than Hf (dpm) 4 .
【００１０】[0010]
【表１】 [Table 1]
【００１１】実施例２で得られたＨｆ（ＯｔＢｕ）（ｄ
ｐｍ）３についての分析結果と物性は、以下のとおりで
ある。 （１）組成分析 ＩＣＰ発光分光分析の結果 Ｈｆ分析値 ２２．５ｗｔ％ （理論値２２．３ｗｔ
％） （２）不純物分析 ＩＣＰ発光分光分析の結果（単位ｐｐｍ） Ａｌ １０ Ｃａ ３０ Ｆｅ ２ Ｍｇ＜１ Ｔｉ＜１ Ｚｒ １３００ であった。全Ｃｌ分析の結果Ｃｌは＜１ｐｐｍであっ
た。 （３）蒸気圧 気体飽和法による測定値 ０．１Ｔｏｒｒ／１７０℃ （４）性状と融点 白色の結晶で、その融点は２００℃以上である。 （５）ＴＧ−ＤＴＡ 測定条件 試料重量：１３．５ｍｇ 雰囲気：Ａｒ １気圧 昇温速度：１０．０ｄｅｇ／ｍｉｎ 測定結果を図３に示した。Ｈｆ（ＯｔＢｕ）（ｄｐｍ）
３は、Ｈｆ（ｄｐｍ）４に近い熱安定性を持ち、Ｈｆ
（ＯｉＰｒ）（ｄｐｍ）３に比べて熱分解しにくい。The Hf (OtBu) (d) obtained in Example 2
The analysis results and physical properties of (pm) 3 are as follows. (1) Composition analysis Results of ICP emission spectroscopy Hf analysis value 22.5 wt% (theoretical value 22.3 wt%
%) (2) Impurity analysis The result of ICP emission spectroscopy (unit: ppm) was Al 10 Ca 30 Fe 2 Mg <1 Ti <1 Zr 1300. As a result of total Cl analysis, Cl was <1 ppm. (3) Vapor pressure Measured value by gas saturation method 0.1 Torr / 170 ° C (4) Properties and melting point White crystals, the melting point of which is 200 ° C or higher. (5) TG-DTA measurement conditions Sample weight: 13.5 mg Atmosphere: Ar 1 atm Heating rate: 10.0 deg / min The measurement results are shown in FIG. Hf (OtBu) (dpm)
3 has a thermal stability close to Hf (dpm) 4 and
It is harder to thermally decompose than (OiPr) (dpm) 3 .
【００１２】Ｈｆ（ＯｉＰｒ）（ｄｐｍ）３およびＨｆ
（ＯｔＢｕ）（ｄｐｍ）３は単量体なので、Ｈｆ２（Ｏ
ｉＰｒ）６（ｄｐｍ）２に比較して蒸気圧は高いはず
で、この性質はＣＶＤ原料として好ましい。Ｈｆ（Ｏｉ
Ｐｒ）（ｄｐｍ）３およびＨｆ（ＯｔＢｕ）（ｄｐｍ）
３のＣＶＤ室への供給方法は、担持昇華法や溶液フラッ
シュ法が使える。ＣＶＤで酸化物を形成するために、Ｃ
ＶＤ室を酸素などの酸化性ガスを含んだ雰囲気にする。
ＣＶＤ法としては、熱ＣＶＤ、光ＣＶＤ、プラズマＣＶ
Ｄ等が使える。Hf (OiPr) (dpm) 3 and Hf
Since (OtBu) (dpm) 3 is a monomer, Hf 2 (O
The vapor pressure should be higher than iPr) 6 (dpm) 2 , and this property is preferable as a CVD raw material. Hf (Oi
Pr) (dpm) 3 and Hf (OtBu) (dpm)
As for the method of supplying to the CVD chamber of No. 3 , a supported sublimation method or a solution flash method can be used. In order to form an oxide by CVD, C
The VD chamber is set to an atmosphere containing an oxidizing gas such as oxygen.
As the CVD method, thermal CVD, optical CVD, plasma CV
D etc. can be used.
【００１３】次に本発明のＨｆ（ＯｉＰｒ）（ｄｐｍ）
３およびＨｆ（ＯｔＢｕ）（ｄｐｍ）３のＣＶＤで基板
への堆積が確認される下限の基板温度を調べた結果（実
施例３、実施例４）約４００℃であった。この温度は、
Ｈｆ（ｄｐｍ）４（比較例１、２）の４５０℃に比べ、
約５０℃ほど低かった。これは一基あるＯｉＰｒ基また
はＯｔＢｕ基が酸素のある雰囲気で比較的低温で分解が
開始するためである。Next, Hf (OiPr) (dpm) of the present invention is used.
3 and Hf (OtBu) (dpm) 3 were examined for the lowest substrate temperature at which deposition on the substrate was confirmed by CVD (Examples 3 and 4). This temperature is
Hf (dpm) 4 (Comparative Examples 1 and 2)
It was as low as about 50 ° C. This is because one OiPr group or OtBu group starts to decompose at a relatively low temperature in an atmosphere containing oxygen.
【００１４】[0014]
【実施例１】Ｈｆ（ＯｉＰｒ）（ｄｐｍ）３の製造 リフラックスコンデンサー、温度計、攪拌羽根を備えた
５００ｍｌ四つ口フラスコを真空置換し、アルゴン雰囲
気とし、トルエン２００ｍｌを仕込み、次いでＨｆ（Ｏ
ｉＰｒ）４３４．７ｇ（８３．６ｍｍｏｌ）、ジピバロ
イルメタンｄｐｍＨ４６．４ｇ（２５２ｍｍｏｌ）を仕
込んだ。次いで攪拌下昇温し、加熱還流状態で１２時間
反応した。次いで減圧下で、溶媒、副生イソプロパノー
ルなどを留去し、最後は加熱浴温を１６０℃まで上げ揮
発分を除いた。フラスコ内の固体物を取り出し、細かく
粉砕し、昇華管に仕込んだ。０．３Ｔｏｒｒに減圧し、
加熱浴温２１０℃付近で大半が昇華し管壁に析出した。
黄色の固形物で４０．８ｇを回収した。同定の結果Ｈｆ
（ＯｉＰｒ）（ｄｐｍ）３（５２ｍｍｏｌ）であり、収
率は６２％であった。Example 1 Production of Hf (OiPr) (dpm) 3 A 500 ml four-necked flask equipped with a reflux condenser, a thermometer, and a stirring blade was replaced with a vacuum, an argon atmosphere was added, and 200 ml of toluene was charged.
34.7 g (83.6 mmol) of iPr) 4 and 46.4 g (252 mmol) of dipivaloylmethane dpmH were charged. Then, the temperature was raised with stirring, and the reaction was carried out for 12 hours in a heated reflux state. Then, the solvent, by-product isopropanol and the like were distilled off under reduced pressure. Finally, the heating bath temperature was raised to 160 ° C. to remove volatile components. The solid material in the flask was taken out, finely ground, and charged in a sublimation tube. Reduce the pressure to 0.3 Torr,
Almost all sublimate around the heating bath temperature of 210 ° C. and were deposited on the tube wall.
40.8 g was collected as a yellow solid. Identification result Hf
(OiPr) (dpm) 3 (52 mmol), and the yield was 62%.
【００１５】[0015]
【実施例２】Ｈｆ（ＯｔＢｕ）（ｄｐｍ）３の製造 リフラックスコンデンサー、温度計、攪拌子を備えた３
００ｍｌ三つ口フラスコを真空置換し、アルゴン雰囲気
とし、トルエン２００ｍｌを仕込み、次いでＨｆ（Ｏｔ
Ｂｕ）４２０．５ｇ（４４ｍｍｏｌ）、ジピバロイルメ
タンｄｐｍＨ２３．８ｇ（１２９ｍｍｏｌ）を仕込ん
だ。次いで攪拌下昇温し、加熱還流状態で８時間反応し
た。次いで減圧下で、溶媒、副生ターシャリブタノール
などを留去し、最後は加熱浴温を１２０℃まで上げ揮発
分を除いた。フラスコ内の固体物を取り出し、細かく粉
砕し、昇華管に仕込んだ。０．０２Ｔｏｒｒに減圧し、
加熱浴温１９０℃で９５％が昇華し管壁に析出した。白
色の固形物で２６．５ｇ｛Ｈｆ（ＯｔＢｕ）（ｄｐｍ）
３として３３ｍｍｏｌ｝であり、収率は７５％であっ
た。Example 2 Production of Hf (OtBu) (dpm) 3 3 equipped with a reflux condenser, thermometer and stirrer
A 00 ml three-necked flask was evacuated to an argon atmosphere, charged with 200 ml of toluene, and then charged with Hf (Ot
(Bu) 4 20.5 g (44 mmol) and dipivaloylmethane dpmH 23.8 g (129 mmol) were charged. Then, the temperature was raised with stirring, and the reaction was carried out for 8 hours in a heated reflux state. Then, the solvent, by-product tertiary butanol and the like were distilled off under reduced pressure, and finally the heating bath temperature was raised to 120 ° C. to remove volatile components. The solid material in the flask was taken out, finely ground, and charged in a sublimation tube. Reduce the pressure to 0.02 Torr,
At a heating bath temperature of 190 ° C., 95% sublimated and precipitated on the tube wall. 26.5g Hf (OtBu) (dpm) as a white solid
3 was 33 mmol｝, and the yield was 75%.
【００１６】[0016]
【実施例３】Ｈｆ（ＯｔＢｕ）（ｄｐｍ）３のＣＶＤに
よるＨｆＯ２膜の成膜 Ｈｆ（ＯｔＢｕ）（ｄｐｍ）３１４ｇをポーラスアルミ
ナ粒７０ｍｌに担持し、昇華供給用のシリンダーに充填
した。このシリンダーを１９０℃に保ち、充填層に予熱
したキャリヤーガスＡｒ５０ｓｃｃｍを通して、Ｈｆ
（ＯｔＢｕ）（ｄｐｍ）３を蒸発させ、ＣＶＤ室に送っ
た。シリンダーの内圧はほぼＣＶＤ室と同じであった。
これに、予熱したＯ２ガス２０ｓｃｃｍをＣＶＤ室入り
口で混合し、反応圧力１０Ｔｏｒｒ、３５０〜５００℃
の加熱されたＳｉ（１００）基板上に導き、熱分解堆積
させた。２０分間後、基板を取り出し膜厚測定をすると
４００℃で１０ｎｍのＨｆＯ２膜が形成されていた。４
５０℃、５００℃では約３０ｎｍであった。５００℃で
の成膜状況の再現性をみると、非常に安定していた。EXAMPLE 3 carries Hf and (OtBu) (dpm) deposition of Hf HfO 2 film by 3 of CVD (OtBu) (dpm) 3 14g in porous alumina grains 70 ml, was charged into a cylinder for sublimation supply. The cylinder was maintained at 190 ° C., and Hf was passed through a preheated carrier gas Ar of 50 sccm to the packed bed to pass Hf.
(OtBu) (dpm) 3 was evaporated and sent to the CVD chamber. The internal pressure of the cylinder was almost the same as in the CVD chamber.
A preheated O 2 gas of 20 sccm was mixed with the mixture at the entrance of the CVD chamber, and the reaction pressure was 10 Torr and the temperature was 350 to 500 ° C.
On a heated Si (100) substrate for thermal decomposition deposition. After 20 minutes, the substrate was taken out and the film thickness was measured. As a result, a 10 nm HfO 2 film was formed at 400 ° C. 4
It was about 30 nm at 50 ° C. and 500 ° C. The reproducibility of the film formation state at 500 ° C. was very stable.
【００１７】[0017]
【比較例１】Ｈｆ（ｄｐｍ）４のＣＶＤによるＨｆＯ２
膜の成膜 実施例３において、Ｈｆ（ＯｔＢｕ）（ｄｐｍ）３をＨ
ｆ（ｄｐｍ）４に代え、シリンダーの加熱温度を２２０
℃に代えた他は、実施例３と同様にした。加熱温度を上
げた理由はＨｆの供給量をほぼ同じにするためである。
４００℃では膜はほとんどなく、４５０℃で１０ｎｍの
ＨｆＯ２膜が形成され、５００℃で２０ｎｍとなった。
実施例３と比較例１の結果から、Ｈｆ（ＯｔＢｕ）（ｄ
ｐｍ）３のＨｆＯ２形成の下限温度はＨｆ（ｄｐｍ）４
のそれより、約５０℃低いことがわかる。Comparative Example 1 HfO 2 by CVD of Hf (dpm) 4
In Example 3, Hf (OtBu) (dpm) 3 was changed to H
f (dpm) 4 and the heating temperature of the cylinder is 220
The same procedure as in Example 3 was carried out except that the temperature was changed to ° C. The reason for increasing the heating temperature is to make the supply amount of Hf almost the same.
There was almost no film at 400 ° C., and a 10 nm HfO 2 film was formed at 450 ° C., and became 20 nm at 500 ° C.
From the results of Example 3 and Comparative Example 1, Hf (OtBu) (d
pm) Minimum Temperature of a HfO 2 formation of 3 Hf (dpm) 4
It can be seen that the temperature is lower by about 50 ° C.
【００１８】[0018]
【実施例４】Ｈｆ（ＯｉＰｒ）（ｄｐｍ）３のＣＶＤに
よるＨｆＯ２膜の成膜 Ｈｆ（ＯｉＰｒ）（ｄｐｍ）３のトルエン溶液（濃度
０．１ｍｏｌ／ｌ）０．１ｍｌ／ｍｉｎを２２０℃のフ
ラッシュ蒸発器に送り、予熱したＡｒガス０．３ｓｌｍ
とともに蒸発させ、ＣＶＤ室に送った。これに、予熱し
たＯ２ガス０．１ｓｌｍをＣＶＤ室入り口で混合し、反
応圧力１０Ｔｏｒｒ、３５０〜５００℃の加熱されたＳ
ｉ（１００）基板上に導き、熱分解堆積させた。２０分
間後、基板を取り出し膜厚測定をすると４００℃で約３
０ｎｍのＨｆＯ２膜が形成されていた。４５０℃、５０
０℃では約５０ｎｍであった。Example 4 Hf (OiPr) (dpm) 3 of the deposition of Hf HfO 2 film by CVD (OiPr) (dpm) 3 in toluene (concentration 0.1mol / l) 0.1ml / min of 220 ° C. Ar gas sent to flash evaporator and preheated 0.3 slm
And evaporated and sent to the CVD chamber. Then, 0.1 slm of pre-heated O 2 gas was mixed at the entrance of the CVD chamber, and the reaction pressure was 10 Torr and the heated S was heated at 350 to 500 ° C.
It was led on an i (100) substrate and pyrolyzed. After 20 minutes, the substrate is taken out and the film thickness is measured.
A 0 nm HfO 2 film was formed. 450 ° C, 50
At 0 ° C., it was about 50 nm.
【００１９】[0019]
【比較例２】Ｈｆ（ｄｐｍ）４のＣＶＤによるＨｆＯ２
膜の成膜 実施例４において、Ｈｆ（ＯｉＰｒ）３をＨｆ（ｄｐ
ｍ）４に代えた他は、実施例４と同様にした。４００℃
では膜はほとんどなく、４５０℃で約２０ｎｍのＨｆＯ
２膜が形成され、５００℃で約４０ｎｍとなった。実施
例４と比較例２の結果から、Ｈｆ（ＯｉＰｒ）３のＨｆ
Ｏ２形成の下限温度はＨｆ（ｄｐｍ）４のそれより、約
５０℃低いことがわかる。Comparative Example 2 HfO 2 by CVD of Hf (dpm) 4
In Example 4, Hf (OiPr) 3 was changed to Hf (dp
except that instead of m) 4 were the same as in Example 4. 400 ° C
Has almost no film, and about 20 nm of HfO
Two films were formed and had a thickness of about 40 nm at 500 ° C. From the results of Example 4 and Comparative Example 2, the Hf of Hf (OiPr) 3 was
It can be seen that the lower limit temperature of O 2 formation is about 50 ° C. lower than that of Hf (dpm) 4 .
【００２０】[0020]
【発明の効果】Ｈｆ（ＯｉＰｒ）（ｄｐｍ）３およびＨ
ｆ（ＯｔＢｕ）（ｄｐｍ）３は、Ｈｆ（ＯｔＢｕ）４よ
り安定で、取扱いしやすく、Ｈｆ（ｄｐｍ）４より低温
で成膜でき、再現性よくＨｆ含有酸化物膜を作れる。ゲ
ート絶縁膜のＨｆＯ２膜の量産に有効である。As described above, Hf (OiPr) (dpm) 3 and H
f (OtBu) (dpm) 3 is more stable and easier to handle than Hf (OtBu) 4, can be formed at a lower temperature than Hf (dpm) 4 , and can produce a Hf-containing oxide film with good reproducibility. This is effective for mass production of an HfO 2 film as a gate insulating film.
【図１】Ｈｆ（ＯｉＰｒ）（ｄｐｍ）３のＥＩ−ＭＳに
よる測定結果を示す図である。FIG. 1 is a diagram showing the measurement results of Hf (OiPr) (dpm) 3 by EI-MS.
【図２】Ｈｆ（ＯｉＰｒ）（ｄｐｍ）３の１０Ｔｏｒｒ
でのＴＧ−ＤＴＡによる測定結果を示す図である。FIG. 2 10 Torr of Hf (OiPr) (dpm) 3
FIG. 6 is a view showing a measurement result by TG-DTA in FIG.
【図３】Ｈｆ（ＯｔＢｕ）（ｄｐｍ）３の１気圧でのＴ
Ｇ−ＤＴＡによる測定結果を示す図である。FIG. 3. T at 1 atm of Hf (OtBu) (dpm) 3
It is a figure showing the measurement result by G-DTA.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4H006 AA01 AA02 AB40 AB78 AB84 AB91 AC91 AD11 AD17 BB11 BC31 4H049 VN07 VP01 VQ24 VR44 VS21 VT40 VU24 VV02 VW02 4K030 AA11 AA14 BA42 CA04 FA10 LA02 LA15 5F058 BA20 BC03 BF04 BF05 BF07 BF22 BF29 BG03 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA01 AA02 AB40 AB78 AB84 AB91 AC91 AD11 AD17 BB11 BC31 4H049 VN07 VP01 VQ24 VR44 VS21 VT40 VU24 VV02 VW02 4K030 AA11 AA14 BA42 CA04 FA10 LA02 LA15 5F004 BF30 BF03 BF03 BG03
Claims (6)
トを表す）で表される化合物。1. A compound represented by the formula Hf (OR) (L) 3 ... I (R represents an alkyl group having 1 to 4 carbon atoms and L represents β-diketonate).
シャリブチル、Ｌがジピバロイルメタネートであるハフ
ニウムアルコキシトリス（ジピバロイルメタネート）。2. Hafnium alkoxytris (dipivaloyl methanate) wherein R is isopropyl or tertiary butyl and L is dipivaloyl methanate.
−ジケトン３モルとを有機溶媒中で反応させ、次いで溶
媒を留去し、次いで真空下で昇華精製することを特徴と
する式Ｉの化合物の製造方法。(3) one mole of hafnium tetraalkoxide and β
-A process for the preparation of a compound of formula I, characterized by reacting 3 moles of diketone in an organic solvent, then distilling off the solvent and then purifying under vacuum under sublimation.
ハフニウムテトラターシャリブトキシド１モルと、ジピ
バロイルメタン３モルとを有機溶媒中で反応させ、次い
で溶媒を留去し、次いで真空下で昇華精製することを特
徴とする請求項２の化合物の製造方法。4. A reaction of 1 mol of hafnium tetraisopropoxide or hafnium tetratertiary butoxide with 3 mol of dipivaloylmethane in an organic solvent, followed by distilling off the solvent, followed by sublimation purification under vacuum. A method for producing the compound according to claim 2, characterized in that:
る化学気相成長法によるハフニウム含有酸化物薄膜の製
法。5. A method for producing a hafnium-containing oxide thin film by chemical vapor deposition using the compound according to claim 1.
る化学気相成長法によるハフニウム含有酸化物薄膜の製
法。6. A method for producing a hafnium-containing oxide thin film by chemical vapor deposition using the compound according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000301239A JP2002069027A (en) | 2000-08-25 | 2000-08-25 | HAFNIUM ALKOXYTRIS(beta-DIKETONATE), METHOD FOR MANUFACTURING THE SAME AND METHOD FOR MANUFACTURING OXIDE FILM USING THE SAME |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000301239A JP2002069027A (en) | 2000-08-25 | 2000-08-25 | HAFNIUM ALKOXYTRIS(beta-DIKETONATE), METHOD FOR MANUFACTURING THE SAME AND METHOD FOR MANUFACTURING OXIDE FILM USING THE SAME |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002069027A true JP2002069027A (en) | 2002-03-08 |
Family
ID=18782807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000301239A Pending JP2002069027A (en) | 2000-08-25 | 2000-08-25 | HAFNIUM ALKOXYTRIS(beta-DIKETONATE), METHOD FOR MANUFACTURING THE SAME AND METHOD FOR MANUFACTURING OXIDE FILM USING THE SAME |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002069027A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005122229A1 (en) * | 2004-06-11 | 2005-12-22 | Mitsubishi Materials Corporation | Material for forming capacitor film |
| JP2007134733A (en) * | 2002-02-28 | 2007-05-31 | Hitachi Kokusai Electric Inc | Method of manufacturing semiconductor device |
| WO2007066546A1 (en) * | 2005-12-06 | 2007-06-14 | Tri Chemical Laboratories Inc. | Hafnium compound, hafnium thin film-forming material and method for forming hafnium thin film |
| JP2008124474A (en) * | 2002-03-18 | 2008-05-29 | Hitachi Kokusai Electric Inc | Manufacturing method for semiconductor device, and substrate processing apparatus |
-
2000
- 2000-08-25 JP JP2000301239A patent/JP2002069027A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007134733A (en) * | 2002-02-28 | 2007-05-31 | Hitachi Kokusai Electric Inc | Method of manufacturing semiconductor device |
| JP4505471B2 (en) * | 2002-02-28 | 2010-07-21 | 株式会社日立国際電気 | Semiconductor device manufacturing method and substrate processing apparatus |
| JP2008124474A (en) * | 2002-03-18 | 2008-05-29 | Hitachi Kokusai Electric Inc | Manufacturing method for semiconductor device, and substrate processing apparatus |
| JP4621241B2 (en) * | 2002-03-18 | 2011-01-26 | 株式会社日立国際電気 | Semiconductor device manufacturing method and substrate processing apparatus |
| WO2005122229A1 (en) * | 2004-06-11 | 2005-12-22 | Mitsubishi Materials Corporation | Material for forming capacitor film |
| WO2007066546A1 (en) * | 2005-12-06 | 2007-06-14 | Tri Chemical Laboratories Inc. | Hafnium compound, hafnium thin film-forming material and method for forming hafnium thin film |
| JP5128289B2 (en) * | 2005-12-06 | 2013-01-23 | 株式会社トリケミカル研究所 | Hafnium-based compound, hafnium-based thin film forming material, and hafnium-based thin film forming method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101138130B1 (en) | Metal compound, material for forming thin film and method for preparing thin film | |
| KR101498732B1 (en) | Process for forming the strontium-containing thin film | |
| WO2006043418A1 (en) | Alkoxide compound, thin film-forming material and method for forming thin film | |
| US6669990B2 (en) | Atomic layer deposition method using a novel group IV metal precursor | |
| KR20090059112A (en) | Imide complex, method for producing the same, metal-containing thin film and method for producing the same | |
| JP4022662B2 (en) | Zirconium alkoxytris (β-diketonate), production method thereof, and liquid composition for forming PZT film | |
| JP5311886B2 (en) | Raw material for forming strontium-containing thin film and method for producing the same | |
| JP3227891B2 (en) | Novel organometallic complexes and their ligands | |
| JP2002069027A (en) | HAFNIUM ALKOXYTRIS(beta-DIKETONATE), METHOD FOR MANUFACTURING THE SAME AND METHOD FOR MANUFACTURING OXIDE FILM USING THE SAME | |
| JP2003013227A (en) | Vapor deposition method for forming atom layer by using group iv metal precursor | |
| JP5042548B2 (en) | Metal-containing compound, method for producing the same, metal-containing thin film and method for forming the same | |
| JP3511228B2 (en) | Ethylcyclopentadienyl (1,5-cyclooctadiene) iridium, method for producing the same, and method for producing iridium-containing thin film using the same | |
| US6872419B2 (en) | Method or process for producing PZT films at low substrate temperatures by chemical vapor deposition | |
| JP2002030025A (en) | ZIRCONIUM TERTIARY BUTOCYTRIS (beta-DIKETONATE), METHOD FOR PRODUCING THE SAME AND METHOD FOR PRODUCING ZIRCONIUM- CONTAINING OXIDE THIN FILM USING THE SAME | |
| KR100508113B1 (en) | Organic metal complex and the preparation thereof | |
| JP4006892B2 (en) | Method for producing liquid double alkoxide of niobium, tantalum and alkaline earth metal, and method for producing complex oxide dielectric using the same | |
| JP4120321B2 (en) | Titanium complex for chemical vapor deposition and method for producing PZT thin film using the same | |
| JP2006312600A (en) | Metal compound, raw material for forming thin film, method for producing thin film and thin film | |
| JP4107924B2 (en) | Method for producing thin film and raw material composition for chemical vapor deposition used therefor | |
| JP2005060358A (en) | BISMUTH ALKOXIDE, ITS PRODUCTION METHOD, AND METHOD FOR PRODUCTION OF Bi-LAYERED FERROELECTRIC THIN FILM USING THE ALKOXIDE | |
| JP3858138B2 (en) | Niobium, liquid double alkoxides of tantalum and lithium, a method for producing the same, and a method for producing a complex oxide dielectric thin film using the same | |
| JP4266285B2 (en) | Method for producing vanadium tris (β-diketonate) | |
| JP4042959B2 (en) | Tris (diisobutyrylmethanate) neodymium and method for producing neodymium-substituted bismuth titanate ferroelectric thin film by chemical vapor deposition using the same | |
| JP3223800B2 (en) | Tantalum compound | |
| JP4296756B2 (en) | Method for producing titanium-containing dielectric thin film from organic titanium compound and solution raw material containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050627 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20050907 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080625 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20081125 |