JP2011173935A - Highly pure trialkyl gallium and method for producing the same - Google Patents
Highly pure trialkyl gallium and method for producing the same Download PDFInfo
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本発明は、高純度トリアルキルガリウム及びその製法に関するものである。高純度トリアルキルガリウムは、例えば、エピタキシャル成長法による高機能の化合物半導体の製造原料として有用な化合物である。 The present invention relates to high-purity trialkylgallium and a method for producing the same. High-purity trialkylgallium is a useful compound as a raw material for producing a highly functional compound semiconductor by, for example, an epitaxial growth method.
従来、高純度トリアルキルガリウムの製法としては、例えば、三塩化ガリウムとトリメチルアルミニウムとをメシチレン中で反応させてトリメチルガリウムを製造する方法が知られている。しかしながら、この方法では、大量のメシチレンが必要であるため、容量の大きな反応釜の使用により操作が煩雑となり、工業的な高純度トリアルキルガリウムの製法としては不適であった（例えば、特許文献１参照）。 Conventionally, as a method for producing high-purity trialkylgallium, for example, a method for producing trimethylgallium by reacting gallium trichloride and trimethylaluminum in mesitylene is known. However, since this method requires a large amount of mesitylene, the use of a large-capacity reaction kettle makes the operation complicated and is not suitable as an industrial high-purity trialkylgallium production method (for example, Patent Document 1). reference).
本発明の課題は、上記問題点を解決し、簡便な方法によって、高純度トリアルキルガリウム及びその方法を提供することにある。 An object of the present invention is to solve the above problems and provide a high-purity trialkylgallium and a method thereof by a simple method.
本発明の課題は、ケイ素原子の含有量が0.1質量ppm以下であることを特徴とする、高純度トリアルキルガリウムによって解決される。 The object of the present invention is solved by high-purity trialkylgallium, characterized in that the silicon atom content is 0.1 mass ppm or less.
本発明の課題は、又、一般式（１） The subject of this invention is also general formula (1).
（式中、Ｒ１は、炭素原子数１〜６のアルキル基を示す。）
で示されるトリアルキルガリウムと一般式（２）
(In the formula, R 1 represents an alkyl group having 1 to 6 carbon atoms.)
And the general formula (2)
（式中、Ｒ２は、炭素原子数５〜１２のアルキル基を示す。）
で示されるトリアルキルアミンとを反応させてガリウム−アミン錯体を形成させ、次いで、反応混合物を蒸留して該ガリウム−アミン錯体を取得した後、該ガリウム−アミン錯体からトリアルキルアミンを解離させて、遊離のトリアルキルガリウムを得ることを特徴とする、高純度トリアルキルガリウムの製法によっても解決される。
(In the formula, R 2 represents an alkyl group having 5 to 12 carbon atoms.)
To form a gallium-amine complex, and then the reaction mixture is distilled to obtain the gallium-amine complex, and then the trialkylamine is dissociated from the gallium-amine complex. This can also be solved by a method for producing high-purity trialkylgallium, which is characterized by obtaining free trialkylgallium.
本発明により、エピタキシャル成長法による高機能の化合物半導体の製造原料として有用な高純度トリアルキルガリウム及びその製法を提供することができる。 According to the present invention, it is possible to provide a high-purity trialkylgallium useful as a raw material for producing a highly functional compound semiconductor by an epitaxial growth method and a method for producing the same.
本発明に反応において使用するトリアルキルガリウムは、前記の一般式（１）で示される。その一般式（１）において、Ｒ１は、炭素数１〜６のアルキル基を示し、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基が挙げられるが、好ましくはメチル基、エチル基である（即ち、トリアルキルガリウムが、トリメチルガリウム、トリエチルガリウム）。なお、これらの基は、各種異性体も含む。 The trialkylgallium used in the reaction of the present invention is represented by the general formula (1). In the general formula (1), R 1 represents an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Group, that is, an ethyl group (that is, trialkylgallium is trimethylgallium, triethylgallium). These groups include various isomers.
本発明に反応において使用するトリアルキルアミンは、前記の一般式（２）で示される。その一般式（２）において、Ｒ２は、炭素数５〜１２のアルキル基であり、例えば、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基が挙げられるが、好ましくはn-オクチル基である（即ち、トリアルキルアミンが、トリ-n-オクチルアミン）。なお、これらの基は、各種異性体も含む。 The trialkylamine used in the reaction in the present invention is represented by the general formula (2). In the general formula (2), R 2 is an alkyl group having 5 to 12 carbon atoms, and examples thereof include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. But is preferably an n-octyl group (ie, trialkylamine is tri-n-octylamine). These groups include various isomers.
前記トリアルキルアミンの使用量は、トリアルキルガリウム1モルに対して、好ましくは0.6〜1.5モル、更に好ましくは0.8〜1.2モルである。なお、これらのトリアルキルアミンは、単独又は二種以上を混合して使用しても良い。 The amount of the trialkylamine used is preferably 0.6 to 1.5 mol, more preferably 0.8 to 1.2 mol, per 1 mol of trialkylgallium. In addition, you may use these trialkylamine individually or in mixture of 2 or more types.
本発明のガリウム−アミン錯体の形成は、例えば、トリアルキルガリウムとトリアルキルアミンとを混合し、攪拌させながら反応させる等の方法によって行われる。その際の温度は、好ましくは30〜150℃、更に好ましくは40〜110℃であり、圧力は特に制限されない。 The gallium-amine complex of the present invention is formed, for example, by a method of mixing trialkylgallium and trialkylamine and reacting them while stirring. The temperature at that time is preferably 30 to 150 ° C., more preferably 40 to 110 ° C., and the pressure is not particularly limited.
本発明では、先に得られた混合物を蒸留して当該ガリウム−アミン錯体を取得した後、当該ガリウム−アミン錯体からトリアルキルアミンを解離させて、遊離の高純度トリアルキルガリウムを得ることができる。 In this invention, after distilling the mixture obtained previously and obtaining the said gallium-amine complex, a trialkylamine can be dissociated from the said gallium-amine complex, and a free high purity trialkyl gallium can be obtained. .
前記反応混合物を蒸留して当該ガリウム−アミン錯体を取得する際の温度は、好ましくは50〜200℃、更に好ましくは100〜150℃であり、圧力は、好ましくは0.5〜101.3kPaA、更に好ましくは5〜10kPaAである。 The temperature at which the reaction mixture is distilled to obtain the gallium-amine complex is preferably 50 to 200 ° C, more preferably 100 to 150 ° C, and the pressure is preferably 0.5 to 101.3 kPaA, more preferably. 5 to 10 kPaA.
前記ガリウム−アミン錯体からトリアルキルアミンを解離させて、遊離の高純度トリアルキルガリウムを得る方法としては、例えば、当該ガリウム−アミン錯体を加熱して蒸留し、その流出物として得る等の方法によって行われる。その際の温度は、好ましくは100〜220℃、更に好ましくは130〜200℃であり、圧力は、好ましくは0.5〜101.3kPaA、更に好ましくは20〜50kPaAである。 As a method of dissociating trialkylamine from the gallium-amine complex to obtain free high-purity trialkylgallium, for example, by heating and distilling the gallium-amine complex and obtaining it as an effluent, etc. Done. The temperature at that time is preferably 100 to 220 ° C, more preferably 130 to 200 ° C, and the pressure is preferably 0.5 to 101.3 kPaA, more preferably 20 to 50 kPaA.
なお、前記ガリウム−アミン錯体の形成、蒸留によるガリウム−アミン錯体の取得及びガリウム−アミン錯体からトリアルキルアミンを解離させて、高純度トリアルキルガリウムを得る操作は、複数回行うことによって、より高純度のトリアルキルガリウムを得ることができる。又、トリアルキルガリウムは、公知の方法によって更に精製することもできる（例えば、非特許文献１参照）。
次に、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらに限定されるものではない。なお、トリアルキルガリウムの金属原子の分析は、誘導プラズマ発光分析法（ICP-OES法）にて行った。 Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto. The metal atom of trialkylgallium was analyzed by an induction plasma emission analysis method (ICP-OES method).
実施例１（高純度トリメチルガリウムの合成）
攪拌装置、ヴィグリュー型蒸留塔（２つの受器を付属）及び滴下漏斗を備えた内容積100mlの反応容器に、窒素雰囲気にて、トリ-ｎ-オクチルアミン45g(126mmol)を加え、トリメチルガリウム（ケイ素原子を1質量ppm含む）18g(156mmol)をゆるやかに加え、攪拌しながら40℃で0.5時間攪拌させて、ガリウム−アミン錯体を形成させた。次いで、得られた反応混合物を減圧下で蒸留（100℃、7kPaA）し、低沸点成分（不純物）をドライアイスで冷却した受器に捕集し、ガリウム−アミン錯体を反応容器内に取得した。その後、ガリウム−アミン錯体を130〜200℃に加熱して減圧蒸留（40kPaA）し、流出物として、トリメチルガリウム12gを受器に得た（回収率；67％）。なお、得られたトリメチルガリウムは、ケイ素原子が0.05質量ppm以下、ケイ素原子以外の金属原子の合計含有量が0.56質量ppm以下（アルミニウム原子；0.09質量ppm以下、カルシウム原子；0.02質量ppm以下、カドミウム原子；0.03質量ppm以下、クロム原子；0.05質量ppm以下、銅原子；0.03質量ppm以下、鉄原子；0.05質量ppm以下、マグネシウム原子；0.02質量ppm以下、マンガン原子；0.02質量ppm以下、ナトリウム原子；0.1質量ppm未満、カリウム原子：0.1質量ppm未満、亜鉛原子；0.05質量ppm以下）しか混入していない高純度品であった。
Example 1 (Synthesis of high-purity trimethylgallium)
In a nitrogen atmosphere, 45 g (126 mmol) of tri-n-octylamine was added in a nitrogen atmosphere to a reaction vessel equipped with a stirrer, Vigreux-type distillation column (attached to two receivers) and a dropping funnel, 18 g (156 mmol) containing 1 mass ppm of silicon atoms was slowly added and stirred at 40 ° C. for 0.5 hours with stirring to form a gallium-amine complex. Subsequently, the obtained reaction mixture was distilled under reduced pressure (100 ° C., 7 kPaA), and low-boiling components (impurities) were collected in a receiver cooled with dry ice to obtain a gallium-amine complex in the reaction vessel. . Thereafter, the gallium-amine complex was heated to 130 to 200 ° C. and distilled under reduced pressure (40 kPaA), and 12 g of trimethylgallium was obtained as an effluent in the receiver (recovery rate: 67%). The obtained trimethylgallium has a silicon atom of 0.05 mass ppm or less and a total content of metal atoms other than silicon atoms of 0.56 mass ppm or less (aluminum atom; 0.09 mass ppm or less, calcium atom; 0.02 mass ppm or less, cadmium Atoms: 0.03 mass ppm or less, chromium atoms; 0.05 mass ppm or less, copper atoms; 0.03 mass ppm or less, iron atoms; 0.05 mass ppm or less, magnesium atoms; 0.02 mass ppm or less, manganese atoms; 0.02 mass ppm or less, sodium atoms; Less than 0.1 ppm by mass, potassium atom: less than 0.1 ppm by mass, zinc atom; 0.05 ppm by mass or less).
比較例１（トリメチルガリウムの合成）
実施例１において、トリ-ｎ-オクチルアミンの代わりに、トリ‐n-ブチルアミン26g(127mmol)を使用した以外は、実施例１と同様にトリメチルガリウムの合成を行った。その結果、得られたトリメチルガリウムは、ケイ素原子が0.3質量ppm混入している低純度品であった。
Comparative Example 1 (Synthesis of trimethylgallium)
In Example 1, trimethylgallium was synthesized in the same manner as in Example 1 except that 26 g (127 mmol) of tri-n-butylamine was used instead of tri-n-octylamine. As a result, the obtained trimethylgallium was a low-purity product containing 0.3 mass ppm of silicon atoms.
比較例２（トリメチルガリウムの合成）
実施例１において、トリ-ｎ-オクチルアミンの代わりに、N,N-ジメチルアニリン17g(140mmol)を使用した以外は、実施例１と同様にトリメチルガリウムの合成を行った。その結果、ガリウム−アミン錯体は形成したものの、N,N-ジメチルアニリンは解離せずに、遊離のトリメチルガリウムを得ることはできなかった。
Comparative Example 2 (Synthesis of trimethylgallium)
In Example 1, trimethylgallium was synthesized in the same manner as in Example 1 except that 17 g (140 mmol) of N, N-dimethylaniline was used instead of tri-n-octylamine. As a result, although a gallium-amine complex was formed, N, N-dimethylaniline was not dissociated and free trimethylgallium could not be obtained.
実施例２（高純度トリエチルガリウムの合成）
実施例１において、トリメチルガリウムの代わりにトリエチルガリウムを用いたこと以外、実施例１と同様に反応を行うと、ケイ素原子が0.1質量ppm以下の高純度トリエチルガリウムが得られる。
Example 2 (Synthesis of high-purity triethylgallium)
In Example 1, high purity triethylgallium having a silicon atom of 0.1 mass ppm or less is obtained by carrying out the reaction in the same manner as in Example 1 except that triethylgallium is used instead of trimethylgallium.
本発明は、高純度トリアルキルガリウム及びその製法に関するものである。高純度トリアルキルガリウムは、例えば、エピタキシャル成長法による高機能の化合物半導体の製造原料として有用な化合物である。 The present invention relates to high-purity trialkylgallium and a method for producing the same. High-purity trialkylgallium is a useful compound as a raw material for producing a highly functional compound semiconductor by, for example, an epitaxial growth method.
Claims (4)
で示されるトリアルキルガリウムと一般式（２）
で示されるトリアルキルアミンとを反応させてガリウム−アミン錯体を形成させ、次いで、反応混合物を蒸留して該ガリウム−アミン錯体を取得した後、該ガリウム−アミン錯体からトリアルキルアミンを解離させて、遊離のトリアルキルガリウムを得ることを特徴とする、高純度トリアルキルガリウムの製法。 General formula (1)
And the general formula (2)
To form a gallium-amine complex, and then the reaction mixture is distilled to obtain the gallium-amine complex, and then the trialkylamine is dissociated from the gallium-amine complex. A method for producing high-purity trialkylgallium, characterized by obtaining free trialkylgallium.
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| CN104860973A (en) * | 2015-05-12 | 2015-08-26 | 苏州普耀光电材料有限公司 | High-efficient purifying method for trimethyl gallium |
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| JP2008081451A (en) * | 2006-09-28 | 2008-04-10 | Ube Ind Ltd | High-purity trialkylgallium and its preparation method |
| JP5423039B2 (en) * | 2009-02-23 | 2014-02-19 | 宇部興産株式会社 | High purity trialkylgallium and method for producing the same |
| CN103965228A (en) * | 2013-01-30 | 2014-08-06 | 上海宏锐新材料科技有限公司 | Industrial purification method of triethyl gallium |
| JP2014037424A (en) * | 2013-10-07 | 2014-02-27 | Ube Ind Ltd | High-purity trialkyl gallium, and method of producing the same |
| JP2016029026A (en) * | 2014-02-07 | 2016-03-03 | 宇部興産株式会社 | Method for producing trialkylgallium |
| CN110343124A (en) * | 2019-07-31 | 2019-10-18 | 苏州普耀光电材料有限公司 | A method of trimethyl gallium is de-coordinated using mixed ligand agent |
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| JP2005008552A (en) * | 2003-06-19 | 2005-01-13 | Shin Etsu Chem Co Ltd | Method for purifying metal hydrocarbons |
| JP2008081451A (en) * | 2006-09-28 | 2008-04-10 | Ube Ind Ltd | High-purity trialkylgallium and its preparation method |
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| JPS4974199A (en) | 1972-11-17 | 1974-07-17 | ||
| JPS62185090A (en) * | 1986-02-10 | 1987-08-13 | Sumitomo Chem Co Ltd | Purification of alkylgallium |
| GB2201418B (en) * | 1987-02-27 | 1990-10-24 | Plessey Co Plc | Preparation of metal alkyls |
| JP4470682B2 (en) * | 2004-10-13 | 2010-06-02 | 住友化学株式会社 | Method for producing trimethylgallium |
| JP2008050268A (en) * | 2006-08-22 | 2008-03-06 | Ube Ind Ltd | High-purity trialkylgallium and method for producing the same |
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| JP2005008552A (en) * | 2003-06-19 | 2005-01-13 | Shin Etsu Chem Co Ltd | Method for purifying metal hydrocarbons |
| JP2008081451A (en) * | 2006-09-28 | 2008-04-10 | Ube Ind Ltd | High-purity trialkylgallium and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104860973A (en) * | 2015-05-12 | 2015-08-26 | 苏州普耀光电材料有限公司 | High-efficient purifying method for trimethyl gallium |
| CN104860973B (en) * | 2015-05-12 | 2017-06-09 | 苏州普耀光电材料有限公司 | The purification process of trimethyl gallium |
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