JP4266285B2 - Method for producing vanadium tris (β-diketonate) - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、酸化バナジウム含有薄膜を、化学気相成長法（ＣＶＤ法）にて形成するための原料であるバナジウムトリス（β−ジケトネート）の製造方法に関する。
【０００２】
【従来の技術】
第４８回応用物理学関係連合講演会予稿集、３０ｐ−ＹＡ−１２，ｐ５６１（２００１．３）で、渡辺らは、不揮発性メモリ用強誘電体薄膜として優れた強誘電性と無疲労特性を持つ（Ｂｉ４−ｘＬａｘ）Ｔｉ３Ｏ１２（０＜ｘ＜４）（以下ＢＬＴと表す）のＴｉサイトの一部をＶで置換した（Ｂｉ４−ｘＬａｘ）（Ｔｉ３−ｙＶｙ）Ｏ１２（０＜ｘ＜４，０＜ｙ＜３）（以下ＢＬＴＶと表す）が、ＢＬＴより低温の成膜で良好な特性が得られたと報告している。
【０００３】
ＣＶＤ法の原料供給法には大きく分けて二つの方法がある。純品原料化合物をそのままあるいは不活性なキャリヤーガスに同伴させＣＶＤ室に導入する方法Ａと、原料化合物を有機溶媒に溶解し、その溶液をフラッシュ蒸発させて、ＣＶＤ室に導入する方法Ｂである。いずれの場合でもこの各原料化合物の混合ガスが基板に到達する前に互いに反応して揮発性の低いものになったり、リガンド交換が起きて性質が違った物になる可能性がある。よって、各原料化合物がＣＶＤに供するまで反応変質がないことが要求される。
【０００４】
前出の渡辺らは、ＢＬＴＶ薄膜をＭＯＣＶＤ法で形成する際、Ｖ原料としてバナジウムトリエトキシドオキシド（以下ＶＯ（ＯＥｔ）３と表す）の蒸気をキャリヤーガスに同伴させＣＶＤ室に導入する、原料供給法Ａにより良好な結果を得ている。しかし、複数の原料化合物を一つの有機溶媒に溶解し、その溶液をフラッシュ蒸発させてＣＶＤ室に導入する方法Ｂでは、Ｌａ原料として使用されるランタントリス（ジピバロイルメタネート）（以下Ｌａ（ｄｐｍ）３と表す）と、ＶＯ（ＯＥｔ）３などのアルコキシドは、ＣＶＤに供する前に配位子の交換反応を起こしやすく問題である。
【０００５】
酸化ランタンのＭＯＣＶＤ用原料として、揮発性の高い化合物は、Ｌａ（ｄｐｍ）３が最も有力である。そのためＬａ、Ｔｉ、Ｖの３元素の化合物を溶解した一液に用いられるＶの配位子は、Ｌａの配位子と同じであることが好ましい。それはバナジウムトリス（ジピバロイルメタネート）（以下Ｖ（ｄｐｍ）３と表す）等である。
【０００６】
Ｓｅｒｇｉｏ Ｄｉｌｌｉ ａｎｄ Ｅｍｉｌｉｏｓ Ｐａｔｓａｌｉｄｅｓ，Ａｕｓｔ．Ｊ．Ｃｈｅｍ．，１９７６，ｖｏｌ．２９，２３８９によれば、オキシ硫酸バナジウムＶＯＳＯ４・３Ｈ２Ｏの温水溶液を攪拌しながら亜ジチオン酸ナトリウムＮａ２Ｓ２Ｏ４水溶液に加え、次いでジピバロイルメタン（以下ｄｐｍＨと表す）のメタノール水溶液を加えると、茶色の結晶固体が得られた。これを水とエタノール水溶液で洗い、真空乾燥してＶ（ｄｐｍ）３を得た。この合成法では反応に大量の水を用いているので、生成Ｖ（ｄｐｍ）３に吸着した水を完全に除去するのは長時間の乾燥でも難しい。吸着した水はＣＶＤ原料の劣化を促進し、また分解機構に影響を与えるため好ましくない。さらに原料に含まれるＮａは、生成Ｖ（ｄｐｍ）３に不純物として多く残る可能性が高く、これは電子材料に用いられるＣＶＤ原料として好ましくない。一般に、電子材料のＣＶＤ材の不純物金属元素量は各５〜１ｐｐｍ程度以下が望まれている。
【０００７】
そこで、アルカリ金属塩を原料とせず、非水溶液の反応系で、ＣＶＤ材料として有用なＶ（ｄｐｍ）３を合成する方法が必要となった。
Ｄｉｃｔｉｏｎａｒｙ ｏｆ Ｉｎｏｒｇａｎｉｃ Ｃｏｍｐｏｕｎｄｓ ｖｏｌ．２ ｐ１５２１（Ｃｈａｐｍａｎ＆Ｈａｌｌ，１９９２）には、バナジウムトリス（アセチルアセトネート）（以下Ｖ（ａｃａｃ）３と表す）が、ＶＣｌ３・６Ｈ２ＯまたはＶＣｌ３と塩基存在下、エタノール中でアセチルアセトンと反応させて合成できることが記載されている。しかし、Ｖ（ｄｐｍ）３の合成には言及されていない。
【０００８】
【発明が解決しようとする課題】
本課題は、バナジウムトリス（β−ジケトネート）の製造方法、特にバナジウムトリス（ジピバロイルメタネート）の製造方法を提供することである。さらに各金属元素不純物が５ｐｐｍ以下の高純度バナジウムトリス（β−ジケトネート）の製造方法を提供することである。
【０００９】
【課題を解決するための手段】
本発明は、三塩化バナジウムとβ−ジケトンとアンモニアガスを有機溶媒中で反応させ、副生塩化アンモニウムを濾過分離し、次いで溶媒と未反応原料を留去し、次いで、真空蒸留または昇華回収するバナジウムトリス（β−ジケトネート）の製造方法である。
【００１０】
本発明は、三塩化バナジウムとβ−ジケトンとアンモニアガスをアルコール中で反応させ、反応後、生成バナジウムトリス（β−ジケトネート）を溶解する無極性溶媒に置換して副生塩化アンモニウムを濾過分離し、次いで溶媒と未反応原料を留去し、次いで、真空蒸留または昇華回収するバナジウムトリス（β−ジケトネート）の製造方法である。
【００１１】
本発明は、三塩化バナジウムとβ−ジケトンとアンモニアガスをアルコールと、生成バナジウムトリス（β−ジケトネート）を溶解する無極性溶媒との混合溶媒中で反応させ、副生塩化アンモニウムを濾過分離し、次いで溶媒と未反応原料を留去し、次いで、真空蒸留または昇華回収するバナジウムトリス（β−ジケトネート）の製造方法である。
【００１２】
本発明は、上記発明により、バナジウムトリス（ジピバロイルメタネート）中の金属元素不純物が各５ｐｐｍ以下である高純度バナジウムトリス（ジピバロイルメタネート）の製造方法である。
【００１３】
本発明は、上記発明においてβ−ジケトネートが、ジピバロイルメタネート（すなわち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、２，４−オクタンジオネートであるバナジウムトリス（β−ジケトネート）の製造方法である。
【００１４】
【発明の実施の形態】
本発明は、前述のＤｉｃｔｉｏｎａｒｙ ｏｆ Ｉｎｏｒｇａｎｉｃ Ｃｏｍｐｏｕｎｄｓに記載のＶ（ａｃａｃ）３の製法を基に改良を加えた方法である。
【００１５】
例としてＶ（ｄｐｍ）３の製造方法を以下に述べる。
Ｖ（ｄｐｍ）３の製造方法は、ＶＣｌ３１モルとｄｐｍＨ３モルとアンモニアガスとを有機溶媒中で室温付近で反応させ、副生塩化アンモニウムを濾過分離し、次いで溶媒を留去し、次いで真空下で蒸留あるいは昇華精製する方法である。ｄｐｍＨの仕込量は、ＶＣｌ３１モルに対し３モル以上で、好ましくは３．３〜５モルである。
アンモニアガスは、有機溶媒中にＶＣｌ３とｄｐｍＨとを溶解あるいは分散させた溶液中のガス吹き込み管からバブリングにより供給する。この方法はアンモニアガスと反応溶液との接触面積が大きくなるため、反応が進みやすいので好ましい。
【００１６】
反応の有機溶媒としてメタノール、エタノールなどのアルコールを用いると、ＶＣｌ３を溶解するため反応が進みやすく好ましい。しかし生成したＶ（ｄｐｍ）３はアルコールに溶けない。副生成物である塩化アンモニウムもアルコールにほとんど溶けないので、一緒に析出してしまい、濾過分離することができない。よって反応後に、Ｖ（ｄｐｍ）３を溶解し、副生塩化アンモニウムを溶かさない無極性溶媒、例えばトルエン、ヘキサン、ヘプタン、オクタンなどに交換する必要がある。Ｖ（ｄｐｍ）３の溶媒１リットルに室温で溶解する量を調べたところ、トルエンには４１０ｇ、ヘキサンには２５０ｇであった。これに対しエタノールにはわずか＜１０ｇであった。
【００１７】
反応の有機溶媒としてはじめからトルエン、ヘキサンなどを用いる場合は、ＶＣｌ３が溶解しないため反応時間が長くなる。よって、溶媒としてはトルエン又はヘキサンなどの無極性溶媒とメタノール又はエタノールなどのアルコールとの混合溶媒を用いることが好ましい。
【００１８】
合成して得られた粗製Ｖ（ｄｐｍ）３は、昇華または蒸留により精製する。Ｖ（ｄｐｍ）３の蒸気圧、昇華圧は、多くの金属ｄｐｍの中では高い。よってこの操作で多くの金属ｄｐｍ塩や、未反応の塩化物や酸化物などが除かれるので、ほとんどの金属元素不純物は除くことができる。市販のＶＣｌ３を用いて金属元素不純物が各５ｐｐｍ以下の精製Ｖ（ｄｐｍ）３を得ることが容易にできる。より高純度のＶＣｌ３を原料として用いれば、さらに不純物の少ないＶ（ｄｐｍ）３とすることもできる。
【００１９】
【実施例１】
リフラックスコンデンサー、攪拌子、滴下ロート、アンモニアガス導入用ディップチューブを備えた５００ｍｌ三つ口フラスコを真空置換しアルゴンガス雰囲気とした。無水ＶＣｌ３２５．５ｇ（０．１６ｍｏｌ）と脱水したエタノール２００ｍｌを仕込み、室温で攪拌してＶＣｌ３を溶解した。ここにｄｐｍＨ１３７．５ｇ（０．７５ｍｏｌ）と脱水エタノール１００ｍｌの混合溶液を滴下ロートより添加した。この後、反応フラスコを水冷しながらアンモニアガスをディップチューブより０．１ｌ／ｍｉｎで５時間導入すると、液中に生成物が析出しはじめ、液温もわずかに上昇した。８０〜９０℃のオイルバスで７時間還流し、溶媒のエタノールを釜温度１００℃、圧力１〜２Ｔｏｒｒで留去した。ここに脱水トルエン３００ｍｌを添加して生成Ｖ（ｄｐｍ）３を溶解し、そのまま室温で１時間攪拌した。副生塩化アンモニウムの結晶を濾過で分離し、さらにこのケーキを脱水トルエン２５０ｍｌで洗い流して白色の塩化アンモニウムを分離した。濾液を釜温度１００〜１３０℃、圧力１〜２Ｔｏｒｒで溶媒や未反応ｄｐｍＨを留去し、粗製Ｖ（ｄｐｍ）３を得た。
この粗製Ｖ（ｄｐｍ）３を、加熱温度１５５℃、圧力０．１〜０．２Ｔｏｒｒで昇華し、精製品８９．６ｇを得た。収率９２％であった。
【００２０】
回収した昇華物は茶色の固体で、融点は１５５〜１６０℃であった。前述のＳｅｒｇｉｏ Ｄｉｌｌｉらの文献によれば、Ｖ（ｄｐｍ）３の融点は１５８℃であり、これにほぼ一致した。またＶ含量は８．５６％で、理論値８．４８％にほぼ一致した。このことより実施例１で昇華精製して得た結晶はＶ（ｄｐｍ）３と同定した。
【００２１】
ＩＣＰ−ＭＳにより微量金属不純物を定量した。
ＴＧ−ＤＴＡによる測定
測定条件
試料 ６．０２ｍｇ
雰囲気 Ａｒ１気圧
昇温速度 １０．０ｄｅｇ／ｍｉｎ
測定結果を図１に示した。
９９％以上の減量で、完全に蒸発した。よってこのＶ（ｄｐｍ）３は熱安定性も高く蒸発残さもなく、ＣＶＤ原料として好ましいことがわかる。
【００２３】
【実施例２】
リフラックスコンデンサー、攪拌子、滴下ロート、アンモニアガス導入用ディップチューブを備えた１Ｌ三つ口フラスコを真空置換しアルゴンガス雰囲気とした。無水ＶＣｌ３２０．５ｇ（０．１３ｍｏｌ）と、脱水したエタノール２００ｍｌとトルエン２００ｍｌを仕込み、室温で攪拌してＶＣｌ３を溶解した。ここにｄｐｍＨ１１２．４ｇ（０．６１ｍｏｌ）を滴下ロートより添加した。この後、アンモニアガスをディップチューブより０．１ｌ／ｍｉｎで５時間導入すると、液中に副生塩化アンモニウムが析出し、液温も上昇した。８０〜９０℃のオイルバスで７時間還流し、副生塩化アンモニウムの結晶を濾過で分離し、さらにこのケーキを脱水トルエン３００ｍｌで洗い流して白色の塩化アンモニウムを分離した。濾液を釜温度１００〜１３０℃、圧力１〜２Ｔｏｒｒで減圧加熱し、溶媒や未反応ｄｐｍＨを留去し、粗製Ｖ（ｄｐｍ）３を得た。
粗製Ｖ（ｄｐｍ）３を、加熱温度１５５℃、圧力０．１〜０．２Ｔｏｒｒで昇華し、精製物７０．５ｇを得た。収率９０％であった。
回収した昇華精製物の特性は、実施例１で得たＶ（ｄｐｍ）３と同じであった。
【００２４】
【発明の効果】
本発明の製造方法によれば、不純物金属元素が各５ｐｐｍ以下で吸着水のない、ＭＯＣＶＤ材に好適なＶ（ｄｐｍ）３が収率９０％以上で得られる。
【図面の簡単な説明】
【図１】Ｖ（ｄｐｍ）３のＴＧ−ＤＴＡによる測定結果を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing vanadium tris (β-diketonate), which is a raw material for forming a vanadium oxide-containing thin film by chemical vapor deposition (CVD).
[0002]
[Prior art]
In the 48th Applied Physics Related Conference Proceedings, 30p-YA-12, p561 (2001.3), Watanabe et al. Showed excellent ferroelectricity and fatigue-free characteristics as a ferroelectric thin film for nonvolatile memory. A part of the Ti site of (Bi 4-x La x ) Ti 3 O 12 (0 <x <4) (hereinafter referred to as BLT) is substituted with V (Bi 4-x La x ) (Ti 3-y V y ) O 12 (0 <x <4, 0 <y <3) (hereinafter referred to as BLTV) reports that good characteristics were obtained at a lower temperature than BLT.
[0003]
There are roughly two types of CVD material supply methods. A method A in which a pure raw material compound is introduced into the CVD chamber as it is or accompanied by an inert carrier gas, and a method B in which the raw material compound is dissolved in an organic solvent, the solution is flash-evaporated and introduced into the CVD chamber. . In any case, there is a possibility that the mixed gas of each raw material compound reacts with each other before reaching the substrate to become less volatile, or a ligand exchange occurs to have a different property. Therefore, it is required that there is no reaction alteration until each raw material compound is subjected to CVD.
[0004]
The above-mentioned Watanabe et al., When forming a BLTV thin film by the MOCVD method, introduces a vapor of vanadium triethoxide oxide (hereinafter referred to as VO (OEt) 3 ) as a V raw material into a CVD chamber with a carrier gas. Good results have been obtained by feeding method A. However, in the method B in which a plurality of raw material compounds are dissolved in one organic solvent and the solution is flash evaporated to be introduced into the CVD chamber, lanthanum tris (dipivaloylmethanate) (hereinafter referred to as La (Denoted as (dpm) 3 ) and alkoxides such as VO (OEt) 3 are problematic because they easily cause a ligand exchange reaction before being subjected to CVD.
[0005]
As a raw material for MOCVD of lanthanum oxide, La (dpm) 3 is the most powerful compound with high volatility. Therefore, it is preferable that the ligand of V used for the 1 liquid which melt | dissolved the compound of 3 elements of La, Ti, and V is the same as the ligand of La. It is vanadium tris (dipivaloylmethanate) (hereinafter referred to as V (dpm) 3 ).
[0006]
Sergio Dilli and Emilias Patsalides, Aust. J. et al. Chem. , 1976, vol. According to US Pat. No. 29,2389, a warm aqueous solution of vanadium oxysulfate VOSO 4 .3H 2 O was added to an aqueous sodium dithionite Na 2 S 2 O 4 solution with stirring, and then dipivaloylmethane (hereinafter referred to as dpmH) When a methanol aqueous solution was added, a brown crystalline solid was obtained. This was washed with water and an aqueous ethanol solution and vacuum-dried to obtain V (dpm) 3 . Since a large amount of water is used for the reaction in this synthesis method, it is difficult to completely remove the water adsorbed on the generated V (dpm) 3 even by drying for a long time. The adsorbed water is not preferable because it promotes the deterioration of the CVD raw material and affects the decomposition mechanism. Further, it is highly possible that Na contained in the raw material remains as an impurity in the generated V (dpm) 3 , which is not preferable as a CVD raw material used for an electronic material. In general, the amount of impurity metal elements in the CVD material of the electronic material is desired to be about 5 to 1 ppm or less.
[0007]
Therefore, a method for synthesizing V (dpm) 3 useful as a CVD material in a non-aqueous reaction system without using an alkali metal salt as a raw material has become necessary.
Dictionary of Inorganic Compounds vol. The 2 p1521 (Chapman & Hall, 1992 ), ( expressed as follows V (acac) 3) vanadium tris (acetylacetonate) is, VCl 3 · 6H 2 O or VCl 3 and the presence of a base, is reacted with acetylacetone in ethanol Can be synthesized. However, no mention is made of the synthesis of V (dpm) 3 .
[0008]
[Problems to be solved by the invention]
This subject is providing the manufacturing method of vanadium tris ((beta) -diketonate), especially the manufacturing method of vanadium tris (dipivaloylmethanate). Furthermore, it is providing the manufacturing method of highly purified vanadium tris ((beta) -diketonate) whose each metal element impurity is 5 ppm or less.
[0009]
[Means for Solving the Problems]
In the present invention, vanadium trichloride, β-diketone and ammonia gas are reacted in an organic solvent, by-product ammonium chloride is separated by filtration, then the solvent and unreacted raw material are distilled off, and then vacuum distillation or sublimation recovery is performed. This is a method for producing vanadium tris (β-diketonate).
[0010]
In the present invention, vanadium trichloride, β-diketone, and ammonia gas are reacted in alcohol, and after the reaction, the produced vanadium tris (β-diketonate) is replaced with a nonpolar solvent, and by-product ammonium chloride is separated by filtration. Then, the solvent and unreacted raw material are distilled off, and then vacuum distillation or sublimation recovery is used for producing vanadium tris (β-diketonate).
[0011]
In the present invention, vanadium trichloride, β-diketone, and ammonia gas are reacted in a mixed solvent of alcohol and a nonpolar solvent that dissolves the generated vanadium tris (β-diketonate), and by-product ammonium chloride is separated by filtration. Next, the solvent and unreacted raw materials are distilled off, and then vacuum distillation or sublimation recovery is used for producing vanadium tris (β-diketonate).
[0012]
This invention is a manufacturing method of the high purity vanadium tris (dipivaloylmethanate) whose metal element impurities in vanadium tris (dipivaloylmethanate) are each 5 ppm or less by the said invention.
[0013]
In the present invention, β-diketonate is dipivaloylmethanate (that is, 2,2,6,6-tetramethyl-3,5-heptanedionate), 2,6-dimethyl-3,5- Heptanedionate, 2,2,6,6-tetramethyl-3,5-octanedionate, 2,2,6-trimethyl-3,5-heptanedionate, 6-ethyl-2,2-dimethyl-3 , 5-octanedionate, 2,4-octanedionate, a method for producing vanadium tris (β-diketonate).
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is an improved method based on the method of producing V (acac) 3 described in the above-mentioned Dictionary of Inorganic Compounds.
[0015]
As an example, a method for producing V (dpm) 3 will be described below.
V (dpm) 3 is produced by reacting 1 mol of VCl 3 , 3 mol of dpmH and ammonia gas in an organic solvent at about room temperature, filtering off by-product ammonium chloride, then distilling off the solvent, and then vacuuming. It is a method of distillation or sublimation purification under the following. The amount of dpmH charged is 3 mol or more, preferably 3.3 to 5 mol, per 1 mol of VCl 3 .
Ammonia gas is supplied by bubbling from a gas blowing tube in a solution in which VCl 3 and dpmH are dissolved or dispersed in an organic solvent. This method is preferable because the contact area between the ammonia gas and the reaction solution increases, and the reaction easily proceeds.
[0016]
When an alcohol such as methanol or ethanol is used as the organic solvent for the reaction, it is preferable that the reaction proceeds easily because VCl 3 is dissolved. However, the produced V (dpm) 3 does not dissolve in alcohol. Since the by-product ammonium chloride is hardly soluble in alcohol, it precipitates together and cannot be separated by filtration. Therefore, after the reaction, it is necessary to exchange V (dpm) 3 with a nonpolar solvent that does not dissolve by-product ammonium chloride, such as toluene, hexane, heptane, octane, and the like. When the amount dissolved in 1 liter of V (dpm) 3 solvent at room temperature was examined, it was 410 g for toluene and 250 g for hexane. In contrast, ethanol was only <10 g.
[0017]
When toluene, hexane or the like is used from the beginning as the organic solvent for the reaction, the reaction time becomes longer because VCl 3 is not dissolved. Therefore, it is preferable to use a mixed solvent of a nonpolar solvent such as toluene or hexane and an alcohol such as methanol or ethanol as the solvent.
[0018]
The crude V (dpm) 3 obtained by synthesis is purified by sublimation or distillation. V (dpm) 3 has a high vapor pressure and sublimation pressure among many metal dpm. Therefore, since many metal dpm salts, unreacted chlorides and oxides are removed by this operation, most metal element impurities can be removed. It is easy to obtain purified V (dpm) 3 having a metal element impurity of 5 ppm or less using commercially available VCl 3 . If higher-purity VCl 3 is used as a raw material, V (dpm) 3 with less impurities can be obtained.
[0019]
[Example 1]
A 500 ml three-necked flask equipped with a reflux condenser, a stirrer, a dropping funnel, and a dip tube for introducing ammonia gas was vacuum-substituted to obtain an argon gas atmosphere. 25.5 g (0.16 mol) of anhydrous VCl 3 and 200 ml of dehydrated ethanol were charged and stirred at room temperature to dissolve VCl 3 . A mixed solution of 137.5 g (0.75 mol) of dpmH and 100 ml of dehydrated ethanol was added thereto from a dropping funnel. Thereafter, when ammonia gas was introduced from the dip tube at 0.1 l / min for 5 hours while cooling the reaction flask with water, the product started to precipitate in the liquid, and the liquid temperature slightly increased. The mixture was refluxed in an oil bath at 80 to 90 ° C. for 7 hours, and ethanol as a solvent was distilled off at a kettle temperature of 100 ° C. and a pressure of 1 to 2 Torr. To this was added 300 ml of dehydrated toluene to dissolve the produced V (dpm) 3 and the mixture was stirred at room temperature for 1 hour. By-product ammonium chloride crystals were separated by filtration, and the cake was washed with 250 ml of dehydrated toluene to separate white ammonium chloride. Solvent and unreacted dpmH were distilled off from the filtrate at a kettle temperature of 100 to 130 ° C. and a pressure of 1 to 2 Torr to obtain crude V (dpm) 3 .
The crude V (dpm) 3 was sublimated at a heating temperature of 155 ° C. and a pressure of 0.1 to 0.2 Torr to obtain 89.6 g of a purified product. The yield was 92%.
[0020]
The recovered sublimate was a brown solid, and the melting point was 155 to 160 ° C. According to the above-mentioned Sergio Dilli et al., The melting point of V (dpm) 3 is 158 ° C., which is almost consistent with this. The V content was 8.56%, which almost coincided with the theoretical value of 8.48%. From this, the crystal obtained by sublimation purification in Example 1 was identified as V (dpm) 3 .
[0021]
Trace metal impurities were quantified by ICP-MS.
Measurement measurement condition sample by TG-DTA 6.02 mg
Atmosphere Ar1 atmospheric pressure heating rate 10.0 deg / min
The measurement results are shown in FIG.
It evaporated completely with a weight loss of 99% or more. Therefore, it can be seen that V (dpm) 3 is preferable as a CVD raw material because it has high thermal stability and no evaporation residue.
[0023]
[Example 2]
A 1 L three-necked flask equipped with a reflux condenser, a stirrer, a dropping funnel, and a dip tube for introducing ammonia gas was vacuum-substituted to obtain an argon gas atmosphere. 20.5 g (0.13 mol) of anhydrous VCl 3, 200 ml of dehydrated ethanol and 200 ml of toluene were charged and stirred at room temperature to dissolve VCl 3 . Here, 112.4 g (0.61 mol) of dpmH was added from a dropping funnel. Thereafter, when ammonia gas was introduced from the dip tube at 0.1 l / min for 5 hours, by-product ammonium chloride was precipitated in the liquid, and the liquid temperature also increased. The mixture was refluxed in an oil bath at 80 to 90 ° C. for 7 hours, crystals of by-product ammonium chloride were separated by filtration, and the cake was washed with 300 ml of dehydrated toluene to separate white ammonium chloride. The filtrate was heated under reduced pressure at a kettle temperature of 100 to 130 ° C. and a pressure of 1 to 2 Torr, and the solvent and unreacted dpmH were distilled off to obtain crude V (dpm) 3 .
Crude V (dpm) 3 was sublimated at a heating temperature of 155 ° C. and a pressure of 0.1 to 0.2 Torr to obtain 70.5 g of a purified product. The yield was 90%.
The characteristics of the collected purified sublimation product were the same as V (dpm) 3 obtained in Example 1.
[0024]
【The invention's effect】
According to the production method of the present invention, V (dpm) 3 suitable for an MOCVD material having an impurity metal element of 5 ppm or less and no adsorbed water can be obtained with a yield of 90% or more.
[Brief description of the drawings]
FIG. 1 is a diagram showing a measurement result of TG-DTA of V (dpm) 3 .
Claims (6)
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