JPH0649084A - Method for purifying organophosphine compound - Google Patents
Method for purifying organophosphine compoundInfo
- Publication number
- JPH0649084A JPH0649084A JP30830791A JP30830791A JPH0649084A JP H0649084 A JPH0649084 A JP H0649084A JP 30830791 A JP30830791 A JP 30830791A JP 30830791 A JP30830791 A JP 30830791A JP H0649084 A JPH0649084 A JP H0649084A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- organic
- halide
- sulfuric acid
- organophosphine
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機ホスフィン化合
物、特には、ＭＯＣＶＤ（Ｍｅｔａｌｏｒｇａｎｉｃ
Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏ
ｎ）法等により化合物半導体膜を形成する際の原料とな
る高純度有機ホスフィン化合物を得るための精製方法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic phosphine compound, particularly MOCVD (Metalorganic).
Chemical Vapor Deposition
The present invention relates to a purification method for obtaining a high-purity organic phosphine compound as a raw material when forming a compound semiconductor film by the method n) or the like.
【０００２】[0002]
【従来の技術】インジウム−リンを初めとするＩＩＩ−
Ｖ族化合物半導体薄膜は電子デバイスを作製する材料と
して有用である。化合物半導体薄膜を形成する方法とし
ては、（１）ＭＢＥ（Ｍｏｌｅｃｕｌａｒ Ｂｅａｍ
Ｅｐｉｔａｘｙ）、（２）ハライドＣＶＤ、（３）ＭＯ
ＣＶＤ、（４）ＭＯＭＢＥ（Ｍｅｔａｌｏｒｇａｎｉｃ
Ｍｏｌｅｃｕｌａｒ Ｂｅａｍ Ｅｐｉｔａｘｙ）など
がある。これらの中でもＭＯＣＶＤあるいはＭＯＭＢＥ
は結晶成長系内を高真空に保つ必要がなく原料の交換が
容易であることから、使用が高まり注目を浴びている結
晶成長法である。2. Description of the Related Art III-including indium-phosphorus
The group V compound semiconductor thin film is useful as a material for producing an electronic device. The method for forming the compound semiconductor thin film includes (1) MBE (Molecular Beam)
Epitaxy), (2) halide CVD, (3) MO
CVD, (4) MOMBE (Metalorganic
Molecular Beam Epitaxy) and the like. Among these, MOCVD or MOMBE
Is a crystal growth method that is attracting attention because it is easy to exchange raw materials without having to maintain a high vacuum in the crystal growth system.
【０００３】ところが、これらの方法によってＩＩＩ族
−リン化合物半導体を作製する場合、リン化合物の原料
として、毒性の高いリンの水素化物であるホスフィンを
用いているため、量産化に伴う原料の多量使用に不安が
もたれている。However, when a group III-phosphorus compound semiconductor is produced by these methods, since phosphine, which is a highly toxic phosphorus hydride, is used as a raw material for the phosphorus compound, a large amount of the raw material is used for mass production. I'm worried.
【０００４】そこで近年、このリン原料を、ホスフィン
に代えてアルキル或いはアリールホスフィン等の有機ホ
スフィン化合物を用いる方法が提案され、このうち、特
にモノアルキルまたはモノアリールホスフィンは半導体
膜への炭素の混入が少なく低毒性のホスフィン代替材料
と目されている（例えば、Ｊ．Ｃｒｙｓｔａｌ Ｇｒｏ
ｗｔｈ、７７（１９８６）１１）。Therefore, in recent years, a method of using an organic phosphine compound such as an alkyl or aryl phosphine in place of phosphine in the phosphorus raw material has been proposed. Among them, particularly in monoalkyl or monoaryl phosphine, carbon is not mixed in the semiconductor film. It is regarded as a phosphine alternative material with low toxicity and low toxicity (for example, J. Crystal Gro).
Wth, 77 (1986) 11).
【０００５】この有機ホスフィン化合物の製造法として
は、有機ハロゲノリン化合物やリンのオキソ酸エステル
を各種の還元剤を用いて還元する方法が一般的に知られ
ている（新実験化学講座第１２巻、ｐ４２１、１９７６
年丸善発行）。As a method for producing the organic phosphine compound, a method of reducing an organic halogenoline compound or an oxo acid ester of phosphorus with various reducing agents is generally known (New Experimental Chemistry Course, Vol. 12, p421, 1976
Published by Nenmaru Zen).
【０００６】[0006]
【発明が解決しようとする課題】上記方法による還元反
応では、還元生成物が複合中間体を形成するため、これ
を塩酸等の酸で加水分解する必要がある。この過程で生
成物の有機ホスフィン化合物が分解し、ハロゲン化アル
キルやハロゲン化アリール等の有機ハロゲン化物が生じ
る。また、有機ハロゲノリン化合物やリンのオキソ酸エ
ステルを合成する際、アルキルあるいはアリール源とし
てハロゲン化アルキルあるいはアリールを使用するが、
これが有機ハロゲノリン化合物やリンのオキソ酸エステ
ル中に混入し、このままアルキルホスフィン中に残留す
る場合がある。一般に、アルキル或いはアリールホスフ
ィンとハロゲン化アルキルとは沸点が近接しているた
め、蒸留等より分離精製することは困難であった。In the reduction reaction according to the above method, the reduction product forms a complex intermediate, and it is necessary to hydrolyze the complex intermediate with an acid such as hydrochloric acid. In this process, the product organic phosphine compound is decomposed to produce an organic halide such as an alkyl halide or an aryl halide. Further, when synthesizing an organic halogenoline compound or an oxo acid ester of phosphorus, a halogenated alkyl or aryl is used as an alkyl or aryl source.
This may be mixed into the organic halogenoline compound or the oxo acid ester of phosphorus, and may remain in the alkylphosphine as it is. Generally, since the boiling points of alkyl or aryl phosphine and alkyl halide are close to each other, it is difficult to separate and purify by distillation or the like.
【０００７】一方、半導体の用途には特に高純度の有機
ホスフィン化合物が要求されるので、生成物中の微量の
有機ハロゲン化物を除去することが求められていた。On the other hand, since a high-purity organic phosphine compound is particularly required for semiconductor applications, it has been required to remove a trace amount of organic halide in the product.
【０００８】本発明は上記課題を解決したもので、本発
明の目的は有機ハロゲン化物等を高度に除去した高純度
の有機ホスフィン化合物を得る方法を提供することにあ
る。The present invention has solved the above problems, and an object of the present invention is to provide a method for obtaining a highly pure organic phosphine compound in which organic halides and the like are highly removed.
【０００９】[0009]
【課題を解決するための手段】本発明の有機ホスフィン
の精製方法は、有機ハロゲン化物を不純物として含有す
る有機ホスフィンを硫酸水溶液で洗浄することにより有
機ハロゲン化物を除去することからなる。The method for purifying an organic phosphine of the present invention comprises removing the organic halide by washing the organic phosphine containing the organic halide as an impurity with an aqueous sulfuric acid solution.
【００１０】本発明は、各種の有機ホスフィン化合物の
精製に適用することができるが、特には、ＭＯＣＶＤ法
等により化合物半導体薄膜を形成する際の原料となるイ
ソプロピル、ｔｅｒｔ−ブチル、フェニル等のモノアル
キル或いはモノアリールホスフィンの精製に好適であ
る。The present invention can be applied to the purification of various organic phosphine compounds, but in particular, mono-monomers such as isopropyl, tert-butyl and phenyl, which are raw materials for forming a compound semiconductor thin film by the MOCVD method or the like. It is suitable for purification of alkyl or monoaryl phosphines.
【００１１】有機ハロゲン化物を不純物として含有する
有機ホスフィン化合物としては、二ハロゲン化亜ホスホ
ニル（ＲＰＸ２）又は二ハロゲン化ホスホニル〔ＲＰ
（Ｏ）Ｘ２〕のような有機ジハロゲノリン化合物、或い
はハロゲン化亜ホスフィニル（Ｒ２ＰＸ）又はハロゲン
化ホスフィニル〔Ｒ２Ｐ（Ｏ）Ｘ〕のような有機モノハ
ロゲノリン化合物、またはとしては、亜ホスホン酸エス
テル〔ＲＰ（ＯＲ’）２〕、ホスホン酸エステル〔ＲＰ
（Ｏ）（ＯＲ’）２〕、亜ホスフィン酸エステル〔Ｒ２
Ｐ（ＯＲ’）〕、ホスフィン酸エステル（Ｒ２Ｐ（Ｏ）
（ＯＲ’）〕等のリンのオキソ酸エステルを、ナトリウ
ム水素化ビス（２−メトキシエトキシ）アルミニウムや
水素化リチウムアルミニウム等の還元剤で還元し、これ
を酸等により加水分解して得られるものを例示できる。
尚、前記化合物においては、特に、Ｒがイソプロピル、
ｔｅｒｔ−ブチル、フェニル等のモノアルキル或いはモ
ノアリール基からなる化合物が好適である。Examples of the organic phosphine compound containing an organic halide as an impurity include phosphonyl dihalide (RPX 2 ) or phosphonyl dihalide [RP
An organic dihalogenoline compound such as (O) X 2 ] or an organic monohalogenoline compound such as phosphinyl halide (R 2 PX) or phosphinyl halide [R 2 P (O) X], or Phosphonate [RP (OR ') 2 ], Phosphonate [RP
(O) (OR ′) 2 ], phosphinic acid ester [R 2
P (OR ′)], phosphinic acid ester (R 2 P (O)
(OR ')] and the like, which are obtained by reducing an oxo acid ester of phosphorus with a reducing agent such as sodium bis (2-methoxyethoxy) aluminum hydride or lithium aluminum hydride, and hydrolyzing this with an acid or the like. Can be illustrated.
In the above compound, R is isopropyl,
A compound consisting of a monoalkyl or monoaryl group such as tert-butyl and phenyl is preferable.
【００１２】尚、本発明は、有機ハロゲン化物を不純物
として含有する有機ホスフィン化合物であれば、モノア
ルキル或いはアリール等のモノ体でも、ジアルキル或い
はアリール等のジ体でも、トリアルキル或いはアリール
のトリ体のいずれの有機ホスフィン化合物の精製にも適
用することができる。In the present invention, as long as it is an organic phosphine compound containing an organic halide as an impurity, a mono-form such as monoalkyl or aryl, a di-form such as dialkyl or aryl, or a tri-form of trialkyl or aryl. It can be applied to the purification of any of the organic phosphine compounds.
【００１３】本発明においては、有機ハロゲン化物がい
かなる機構によって硫酸水溶液で除去できるかは不明で
あるが、塩酸水溶液を用いた洗浄では除去できない。In the present invention, it is unclear by what mechanism the organic halide can be removed by the aqueous solution of sulfuric acid, but it cannot be removed by washing with the aqueous solution of hydrochloric acid.
【００１４】この硫酸水溶液での洗浄においては、硫酸
の濃度は特に限定されないが、希酸方が経済的であり、
０．５〜５規定の範囲で適宜選定することがが好まし
い。また有機ホスフィン化合物は、そのままで洗浄して
も良いが、疎水性溶媒に溶かして、溶液とした状態でも
問題はない。使用する硫酸水溶液の量は、混入してくる
有機ハロゲン化物の量にもよるが、一般に、１０００ｐ
ｐｍのオーダーで混入してくる場合、２規定の硫酸を用
いれば、有機ホスフィン化合物と同容量程度の量で十分
である。In the washing with this sulfuric acid aqueous solution, the concentration of sulfuric acid is not particularly limited, but dilute acid is economical.
It is preferable to appropriately select within the range of 0.5 to 5 stipulation. The organic phosphine compound may be washed as it is, but there is no problem even if it is dissolved in a hydrophobic solvent to form a solution. The amount of the sulfuric acid aqueous solution used depends on the amount of the organic halide mixed in, but is generally 1000 p
In the case of mixing in the order of pm, if 2N sulfuric acid is used, the same amount as the organic phosphine compound is sufficient.
【００１５】[0015]
（実施例）３００ｐｐｍのｔｅｒｔ−ブチルクロライド
を含むｔｅｒｔ−ブチルホスフィン２０ｇを３０ｍｌの
ｎ−ジブチルエーテルに希釈し２Ｎの硫酸３０ｍｌを加
え、１時間撹拌した。静置後二層分離し、エーテル層は
２回水洗の後、長さ５０ｃｍの蒸留塔で常圧蒸留を行っ
た。留分中のｔｅｒｔ−ブチルクロライドはガスクロマ
トグラフィー検出下限１０ｐｐｍ程度）を下回った。(Example) 20 g of tert-butylphosphine containing 300 ppm of tert-butyl chloride was diluted with 30 ml of n-dibutyl ether, 30 ml of 2N sulfuric acid was added, and the mixture was stirred for 1 hour. After standing still, two layers were separated, and the ether layer was washed twice with water and then subjected to atmospheric distillation in a distillation column having a length of 50 cm. The tert-butyl chloride in the distillate was below the gas chromatography detection lower limit of about 10 ppm).
【００１６】（比較例）３００ｐｐｍのｔｅｒｔ−ブチ
ルクロライドを含むｔｅｒｔ−ブチルホスフィン２０ｇ
を長さ５０ｃｍの蒸留塔で常圧蒸留した。留分中のｔｅ
ｒｔ−ブチルクロライドは２２０ｐｐｍと少し減少した
程度であった。Comparative Example 20 g of tert-butylphosphine containing 300 ppm of tert-butyl chloride
Was distilled under atmospheric pressure in a distillation column having a length of 50 cm. Te in the fraction
The amount of rt-butyl chloride was slightly reduced to 220 ppm.
【００１７】[0017]
【発明の効果】本発明によれば、有機ハロゲン化物を不
純物として含む有機ホスフィン化合物を硫酸水溶液で洗
浄することにより、微量の有機ハロゲン化物を有効に除
去することができ、半導体エピタキシャル膜成長の原料
として有用な高純度の有機ホスフィン化合物を得ること
ができる。According to the present invention, a trace amount of an organic halide can be effectively removed by washing an organic phosphine compound containing an organic halide as an impurity with an aqueous sulfuric acid solution, and a raw material for semiconductor epitaxial film growth. A highly pure organic phosphine compound useful as
Claims (1)
ィン化合物を硫酸水溶液で洗浄することを特徴とする有
機ホスフィン化合物の精製方法。1. A method for purifying an organic phosphine compound, which comprises washing an organic phosphine compound mixed with an organic halide with an aqueous sulfuric acid solution.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3126640A JP2501146B2 (en) | 1991-04-30 | 1991-04-30 | Method for purifying alkylphosphine |
| JP3308307A JP2548856B2 (en) | 1991-10-29 | 1991-10-29 | Method for purifying alkylphosphine |
| US07/874,696 US5284977A (en) | 1991-04-30 | 1992-04-28 | Process for producing high-purity organic phosphine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3308307A JP2548856B2 (en) | 1991-10-29 | 1991-10-29 | Method for purifying alkylphosphine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0649084A true JPH0649084A (en) | 1994-02-22 |
| JP2548856B2 JP2548856B2 (en) | 1996-10-30 |
Family
ID=17979479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3308307A Expired - Lifetime JP2548856B2 (en) | 1991-04-30 | 1991-10-29 | Method for purifying alkylphosphine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2548856B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014113849A1 (en) * | 2013-01-23 | 2014-07-31 | Nahhat Bassil | Support arrangement for motorcycle |
| US9066643B2 (en) | 2006-12-12 | 2015-06-30 | G.B.D. Corp. | Surface cleaning apparatus |
| US9301666B2 (en) | 2006-12-12 | 2016-04-05 | Omachron Intellectual Property Inc. | Surface cleaning apparatus |
| US9591952B2 (en) | 2009-03-11 | 2017-03-14 | Omachron Intellectual Property Inc. | Hand vacuum cleaner with removable dirt chamber |
| US9826868B2 (en) | 2009-03-13 | 2017-11-28 | Omachron Intellectual Property Inc. | Portable surface cleaning apparatus |
| US11124641B2 (en) | 2016-11-30 | 2021-09-21 | Kimberly-Clark Worldwide, Inc. | Thermoplastic injection molded and flushable material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03166257A (en) * | 1989-09-28 | 1991-07-18 | Basf Ag | Impact-resistant modified ther- mally plastic polyurethane- polyester resin for molding and its manufacture |
| JPH04368393A (en) * | 1991-06-12 | 1992-12-21 | Nikko Kyodo Co Ltd | Purification of alkylphosphine |
-
1991
- 1991-10-29 JP JP3308307A patent/JP2548856B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03166257A (en) * | 1989-09-28 | 1991-07-18 | Basf Ag | Impact-resistant modified ther- mally plastic polyurethane- polyester resin for molding and its manufacture |
| JPH04368393A (en) * | 1991-06-12 | 1992-12-21 | Nikko Kyodo Co Ltd | Purification of alkylphosphine |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9095245B2 (en) | 2006-12-12 | 2015-08-04 | G.B.D. Corp. | Surface cleaning apparatus |
| US9066643B2 (en) | 2006-12-12 | 2015-06-30 | G.B.D. Corp. | Surface cleaning apparatus |
| US9078549B2 (en) | 2006-12-12 | 2015-07-14 | G.B.D. Corp. | Surface cleaning apparatus |
| US9084523B2 (en) | 2006-12-12 | 2015-07-21 | G.B.D. Corp. | Surface cleaning apparatus |
| US9084522B2 (en) | 2006-12-12 | 2015-07-21 | G.B.D. Corp. | Surface cleaning apparatus |
| US9084524B2 (en) | 2006-12-12 | 2015-07-21 | G.B.D. Corp. | Surface cleaning apparatus |
| US9119514B2 (en) | 2006-12-12 | 2015-09-01 | G.B.D. Corp. | Surface cleaning apparatus |
| US9301666B2 (en) | 2006-12-12 | 2016-04-05 | Omachron Intellectual Property Inc. | Surface cleaning apparatus |
| US9591952B2 (en) | 2009-03-11 | 2017-03-14 | Omachron Intellectual Property Inc. | Hand vacuum cleaner with removable dirt chamber |
| US10105023B2 (en) | 2009-03-11 | 2018-10-23 | Omachron Intellectual Property Inc. | Hand vacuum cleaner |
| US9826868B2 (en) | 2009-03-13 | 2017-11-28 | Omachron Intellectual Property Inc. | Portable surface cleaning apparatus |
| WO2014113849A1 (en) * | 2013-01-23 | 2014-07-31 | Nahhat Bassil | Support arrangement for motorcycle |
| US11124641B2 (en) | 2016-11-30 | 2021-09-21 | Kimberly-Clark Worldwide, Inc. | Thermoplastic injection molded and flushable material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2548856B2 (en) | 1996-10-30 |
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