JPH06287011A - Method for synthesizing silane difluoride and its purification - Google Patents
Method for synthesizing silane difluoride and its purificationInfo
- Publication number
- JPH06287011A JPH06287011A JP7388993A JP7388993A JPH06287011A JP H06287011 A JPH06287011 A JP H06287011A JP 7388993 A JP7388993 A JP 7388993A JP 7388993 A JP7388993 A JP 7388993A JP H06287011 A JPH06287011 A JP H06287011A
- Authority
- JP
- Japan
- Prior art keywords
- silane
- hydrogen chloride
- dichloride
- difluoride
- reaction
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は半導体、電子、光学材料
の製造用原料として有用な二フッ化シランの合成法およ
びその精製法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for synthesizing difluorinated silane which is useful as a raw material for producing semiconductors, electronic materials and optical materials, and a method for purifying the same.
【０００２】[0002]
【従来の技術】二フッ化シランは、一般に、適当な固体
状の金属フッ化物を用いて二塩化シランの塩素とフッ素
のハロゲン置換反応を行わせることにより得られる。こ
の際使用される金属フッ化物としてはＳｂＦ3 、ＺｎＦ
2 、ＳｎＦ4 等があり、これら固体状のフッ化物と二塩
化シランを反応させる方法としては、フッ化物充填層に
二塩化シランをガス状で通過させる方法が一般的であ
る。しかしながらこの方法では、反応収率及び純度が満
足できるほど高いものではなく、現在では、これら固体
状金属フッ化物を適当な有機溶媒に懸濁させて二塩化シ
ランと反応させる方法が広く知られている（特開昭61-2
32215 号、特開昭61-151016 号、特開昭63-201013
号）。2. Description of the Related Art Silane difluoride is generally obtained by carrying out a halogen substitution reaction of chlorine and fluorine of silane dichloride using a suitable solid metal fluoride. The metal fluoride used at this time is SbF 3 , ZnF
2 , SnF 4, etc., and as a method of reacting these solid fluorides with silane dichloride, a method of passing silane dichloride in a gaseous state through the fluoride-filled layer is generally used. However, in this method, the reaction yield and purity are not sufficiently high, and at present, a method of suspending these solid metal fluorides in a suitable organic solvent and reacting them with silane dichloride is widely known. (Japanese Patent Laid-Open No. 61-2
32215, JP 61-151016, JP 63-201013
issue).
【０００３】[0003]
【発明が解決しようとする問題点】従来法により二フッ
化シランを得る場合、次に示す問題点がある。 二フッ化シランの製造に使用される金属フッ化物は高
価であり、反応によって副生する金属塩化物の回収、再
生が必要である。また比較的安価な金属フッ化物を一過
的に使用する場合でも副生する金属塩化物が有害物質で
あるものが多く、廃棄には除害処理が必要である。[Problems to be Solved by the Invention] When difluorosilane is obtained by the conventional method, there are the following problems. The metal fluoride used for the production of difluorosilane is expensive, and it is necessary to recover and regenerate the metal chloride by-produced by the reaction. Further, even when a relatively inexpensive metal fluoride is temporarily used, the metal chloride produced as a by-product is a harmful substance in many cases, and therefore a detoxification treatment is required for disposal.
【０００４】従来法によって二フッ化シランを製造す
る場合、反応系に水分が存在すると三フッ化シラン、四
フッ化珪素の如き多フッ化物が副生し、製品純度を低下
させるため、反応系からの脱水が重要となるが、二フッ
化シランの製造に使用される金属フッ化物は吸湿性を示
す物質が多く、脱水精製が必要である。When difluorosilane is produced by the conventional method, when water is present in the reaction system, polyfluorides such as trifluorosilane and silicon tetrafluoride are by-produced and the product purity is lowered. Although dehydration from water is important, many metal fluorides used in the production of difluorosilane have hygroscopic properties, and thus require dehydration purification.
【０００５】二塩化シランとフッ化水素との反応によ
って副生する塩化水素は二フッ化シランと沸点が似通っ
ているため蒸留による除去が困難である。従来法によっ
て二フッ化シランを製造する場合にも、反応系に存在す
る少量の水分のため塩化水素が少量副生するが、二フッ
化シランの利用分野である半導体分野において当該ガス
を使用する際、この塩化水素が半導体製造プロセスに悪
影響を及ぼすことが確認されており塩化水素の除去精製
が必要である。Hydrogen chloride, which is a by-product of the reaction of silane dichloride and hydrogen fluoride, has a boiling point similar to that of silane difluoride, and therefore it is difficult to remove it by distillation. Even in the case of producing difluorinated silane by a conventional method, a small amount of water present in the reaction system causes a small amount of hydrogen chloride as a by-product, but the gas is used in the semiconductor field, which is the field of application of difluorinated silane. At this time, it has been confirmed that this hydrogen chloride has an adverse effect on the semiconductor manufacturing process, and it is necessary to remove and purify the hydrogen chloride.
【０００６】本発明は、かかる従来法の問題点を一掃す
るものである。The present invention eliminates the problems of the conventional method.
【０００７】[0007]
【問題点を解決するための手段】本発明は、フッ化水素
と二塩化シランとを直接反応させることを特徴とする二
フッ化シランの合成法、および本合成法によって副生す
る塩化水素を選択的にエーテル中に吸収除去することを
特徴とする二フッ化シランの精製法に関するものであ
る。The present invention is directed to a method for synthesizing silane difluoride, which comprises directly reacting hydrogen fluoride with silane dichloride, and hydrogen chloride produced as a by-product by this synthesis method. The present invention relates to a method for purifying difluorinated silane which is characterized by selectively absorbing and removing it in ether.
【０００８】本発明によれば、フッ素化剤に安価なフッ
化水素を用いることにより、高価な金属フッ化物を使用
することなく二フッ化シランを従来法とほぼ同等の純度
で合成することができ副生する塩化水素は二フッ化シラ
ンと分離除去した後、アルカリとの反応によって簡単に
除害できる。また、フッ化水素は通常、数ｐｐｍ〜数百
ｐｐｍの水分を含有するが、この程度の水分では多フッ
化物の副生に影響はない。According to the present invention, by using inexpensive hydrogen fluoride as the fluorinating agent, difluorinated silane can be synthesized with almost the same purity as the conventional method without using an expensive metal fluoride. Hydrogen chloride produced as a by-product can be easily removed by separation with difluorosilane and then reaction with an alkali. Further, hydrogen fluoride usually contains several ppm to several hundred ppm of water, but this amount of water does not affect the by-product of polyfluoride.
【０００９】本発明においてフッ化水素と二塩化シラン
を反応させる場合には、二塩化シランを理論反応当量よ
り過剰の状態で反応させるべきである。すなわち、フッ
化水素と二塩化シランはモル比２：１の割合で反応し二
フッ化シラン１モルと塩化水素２モルを生成するが、フ
ッ化水素がこれより過剰となる場合は多フッ化物の生成
による純度低下を引き起こすため二塩化シランを過剰に
する必要がある。When hydrogen fluoride and silane dichloride are reacted in the present invention, the silane dichloride should be reacted in an excess of the theoretical reaction equivalent. That is, hydrogen fluoride and silane dichloride react at a molar ratio of 2: 1 to produce 1 mol of disilane silane and 2 mol of hydrogen chloride, but when hydrogen fluoride is in excess of this, polyfluoride It is necessary to make silane dichloride excessive in order to cause a decrease in purity due to the formation of
【００１０】フッ化水素と二塩化シランのモル比は、
１：１／２より過剰の二塩化シランが反応系に存在する
ことが好ましく、これより小さい場合多フッ化物が生成
し好ましくない。また、二塩化シランが大過剰に存在す
る場合は、反応は進行するが未反応の二塩化シランが大
量に残り、その回収等を考えると効率的ではない。The molar ratio of hydrogen fluoride to silane dichloride is
It is preferable that an excess of 1: 1/2 silane dichloride is present in the reaction system, and if it is smaller than this, polyfluoride is produced, which is not preferable. Further, when the silane dichloride is present in a large excess, the reaction proceeds, but a large amount of unreacted silane dichloride remains, which is not efficient considering the recovery thereof.
【００１１】反応温度は１０〜１００℃が好ましく、最
適には３０〜５０℃が好ましい。反応温度が高温になる
と、反応が激しくなり、多フッ化物を生成するため好ま
しくない。また、低温の場合は、反応速度が遅くなり、
過剰の二塩化シランだけでなくフッ化水素も一部未反応
となって残り、このフッ化水素が生成した二フッ化シラ
ンと再度反応して多フッ化物となる傾向にあり好ましく
ない。The reaction temperature is preferably 10 to 100 ° C, most preferably 30 to 50 ° C. When the reaction temperature is high, the reaction becomes violent and polyfluoride is produced, which is not preferable. Also, if the temperature is low, the reaction speed becomes slower,
Not only the excess silane dichloride but also hydrogen fluoride partially remains unreacted, and this hydrogen fluoride tends to react again with the generated difluorosilane to form a polyfluoride, which is not preferable.
【００１２】フッ化水素と二塩化シランを反応させる方
法には液体二塩化シラン中に固体あるいは液体フッ化水
素を滴下させる方法、液体二塩化シラン中に適当なキャ
リアーガスによりフッ化水素を気体状でバブリングさせ
る方法、二塩化シランとフッ化水素を気体で反応させる
方法があるが、前二者による方法は低温反応であり操作
及び制御が容易でなく現実的ではないため、後者による
方法が好ましい。更に、後者による反応では回分式およ
び流通式の反応形式があるが、回分式では生成した二フ
ッ化シランが再度フッ化水素に曝されて多フッ化物とな
る傾向にあり純度低下を引き起こすため流通式が好まし
い。As a method of reacting hydrogen fluoride with silane dichloride, a method of dropping solid or liquid hydrogen fluoride into liquid dichloride silane, or a method in which hydrogen fluoride is vaporized into liquid dichloride silane with an appropriate carrier gas There is a method of bubbling with, and a method of reacting silane dichloride and hydrogen fluoride in a gas, but the method of the former two is a low temperature reaction and the operation and control are not easy and impractical, so the method of the latter is preferable. . Further, the latter reaction has a batch type and a flow type, but in the batch type, the generated difluorinated silane tends to be exposed again to hydrogen fluoride to become a polyfluoride, which causes a decrease in purity and causes a flow. The formula is preferred.
【００１３】本発明において塩化水素を含む二フッ化シ
ランから塩化水素のみを選択的に除去するために用いら
れるエーテルには、ジエチルエーテル、イソプロピルエ
ーテル、ｎ−ジブチルエーテル、ジフェニルエーテル等
が使用できるが、これらエーテル類は揮発性が高く、二
フッ化シランに同伴すると除去が困難となるため可能な
限り蒸気圧の低いエーテルを使用する必要がある。具体
的には、ｎ−ジブチルエーテル、ジフェニルエーテル等
があるが、室温付近でハンドリングの容易なｎ−ジブチ
ルエーテルが好ましい。塩化水素をエーテルに吸収させ
る場合、低温ほど吸収性能が向上するが、二フッ化シラ
ンも同様に吸収量が増大していくため適正な温度を選択
する必要がある。ｎ−ジブチルエーテルでは、−２０〜
２０℃程度が適している。また、塩化水素を吸収した後
のエーテルは、沸点付近で還流熱処理をすることにより
塩化水素と分離、再生が可能であり、再利用ができる。In the present invention, diethyl ether, isopropyl ether, n-dibutyl ether, diphenyl ether and the like can be used as the ether used for selectively removing only hydrogen chloride from the difluorosilane containing hydrogen chloride. Since these ethers have high volatility and are difficult to remove when they are entrained in the difluorosilane, it is necessary to use ethers having a vapor pressure as low as possible. Specifically, there are n-dibutyl ether, diphenyl ether and the like, but n-dibutyl ether, which is easy to handle at around room temperature, is preferable. In the case of absorbing hydrogen chloride in ether, the lower the temperature, the better the absorption performance, but since the absorption amount of difluorinated silane also increases, it is necessary to select an appropriate temperature. With n-dibutyl ether, -20 to
About 20 ° C is suitable. Further, after absorbing hydrogen chloride, the ether can be separated from hydrogen chloride and regenerated by performing a heat treatment under reflux at around the boiling point, and can be reused.
【００１４】[0014]
【実施例】以下、本発明を実施例により詳細に説明す
る。 実施例１〜５ 攪拌機付４ｌ反応器内に二塩化シランを所定圧力吹き込
み、続いてフッ化水素を導入して回分式に反応させ、こ
の生成ガスをエタノール−ドライアイストラップ（−７
４℃）により未反応ガスを取り除いた後、ガスクロマト
グラフィーにより測定した。この結果を表１に示す。EXAMPLES The present invention will be described in detail below with reference to examples. Examples 1 to 5 Silane dichloride was blown into a 4 l reactor equipped with a stirrer at a predetermined pressure, and then hydrogen fluoride was introduced for batchwise reaction, and the produced gas was mixed with ethanol-dry ice trap (-7
After removing unreacted gas at 4 ° C.), measurement was performed by gas chromatography. The results are shown in Table 1.
【００１５】[0015]
【表１】 [Table 1]
【００１６】実施例６〜１０ 流通式反応管（１／２インチ×５００L ）にて所定流量
の二塩化シランとフッ化水素を大気圧下で混合反応さ
せ、この生成ガスをエタノール−ドライアイストラップ
（−７４℃）により未反応ガスを取り除き、３時間捕集
したガスについてガスクロマトグラフィーにより測定し
た。この結果を表２に示す。Examples 6 to 10 Silane dichloride at a predetermined flow rate and hydrogen fluoride were mixed and reacted under atmospheric pressure in a flow-type reaction tube (1/2 inch × 500 L ), and the produced gas was mixed with ethanol-dry eye. The unreacted gas was removed with a strap (-74 ° C), and the gas collected for 3 hours was measured by gas chromatography. The results are shown in Table 2.
【００１７】[0017]
【表２】 [Table 2]
【００１８】実施例１１〜１６ 攪拌機付３ｌトラップ内に、ゼオライトにより充分脱水
したｎ−ジブチルエーテル２ｌ（液温：０℃）を仕込
み、実施例１および実施例６〜１０で合成したガスを吹
き込んだ。この操作により得られたガスの組成をそれぞ
れ表３に示す。精製後のガス中の塩化水素は、ＦＴ−Ｉ
Ｒによる定量の結果３０ｐｐｍ未満であった。ジフロロ
シランの回収率は約７０％であった。Examples 11 to 16 In a 3 l trap equipped with a stirrer, 2 l of n-dibutyl ether (liquid temperature: 0 ° C.) sufficiently dehydrated with zeolite was charged, and the gas synthesized in Examples 1 and 6 to 10 was blown. It is. The composition of the gas obtained by this operation is shown in Table 3. Hydrogen chloride in the purified gas is FT-I.
The result of quantification by R was less than 30 ppm. The recovery rate of difluorosilane was about 70%.
【００１９】[0019]
【表３】 [Table 3]
【００２０】比較例１ 昇華精製した６０〜１００メッシュの三フッ化アンチモ
ン９０ｇとヘプタン３００ｍｌとを水銀シール攪拌機付
５００ｍｌ丸底フラスコに仕込んでフラスコ内の空気を
窒素置換し、０℃にて二塩化シランを１６０ｍｌ／ｍｉ
ｎで吹き込み反応させた。この生成ガスを１時間捕集し
ガスクロマトグラフィーにより測定した結果を表４に示
す。Comparative Example 1 90 g of sublimed and purified 60-100 mesh antimony trifluoride and 300 ml of heptane were placed in a 500 ml round bottom flask equipped with a mercury seal stirrer, the air in the flask was replaced with nitrogen, and dichloride was added at 0 ° C. 160 ml / mi of silane
The reaction was performed by blowing in n. Table 4 shows the results obtained by collecting the generated gas for 1 hour and measuring by gas chromatography.
【００２１】[0021]
【表４】 [Table 4]
【００２２】実施例１７ 実施例１１〜１６と同様の方法で比較例１に示した生成
ガスを精製したところ、塩化水素は３０ｐｐｍ未満とな
った。Example 17 When the produced gas shown in Comparative Example 1 was purified in the same manner as in Examples 11 to 16, hydrogen chloride was less than 30 ppm.
【００２３】[0023]
【発明の効果】従来法は、高価な固体状金属フッ化物等
を用いて製造するため、有害な副生物質が生成し、回
収、再生、廃棄等に問題があったが、本発明は従来にな
い新しい反応経路を用いて二塩化シランから定量的にか
つ簡便で安価に二フッ化シランを得ることができ、また
塩化水素の除去精製によりより純度の高い二フッ化シラ
ンを得ることが可能となる。EFFECTS OF THE INVENTION Since the conventional method is produced using an expensive solid metal fluoride or the like, harmful by-product substances are generated, and there are problems in recovery, regeneration, disposal, etc. It is possible to obtain difluorinated silane quantitatively, conveniently and inexpensively from a dichlorinated silane using a new reaction route that does not exist in the above, and to obtain a higher purity difluorinated silane by removing and purifying hydrogen chloride. Becomes
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小林 義幸 山口県宇部市大字沖宇部5253番地 セント ラル硝子株式会社宇部研究所内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yoshiyuki Kobayashi 5253 Oki Ube, Ube City, Yamaguchi Prefecture Central Glass Co., Ltd. Ube Laboratory
Claims (2)
させることを特徴とする二フッ化シランの合成法。1. A method for synthesizing difluorosilane, which comprises directly reacting hydrogen fluoride with silane dichloride.
ル中に吹き込み、塩化水素のみを選択的に吸収除去する
ことを特徴とする二フッ化シランの精製法。2. A method for purifying difluorinated silane, which comprises blowing difluorinated silane containing hydrogen chloride into ether to selectively absorb and remove only hydrogen chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05073889A JP3107677B2 (en) | 1993-03-31 | 1993-03-31 | Synthesis method of difluorosilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05073889A JP3107677B2 (en) | 1993-03-31 | 1993-03-31 | Synthesis method of difluorosilane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06287011A true JPH06287011A (en) | 1994-10-11 |
| JP3107677B2 JP3107677B2 (en) | 2000-11-13 |
Family
ID=13531236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05073889A Expired - Fee Related JP3107677B2 (en) | 1993-03-31 | 1993-03-31 | Synthesis method of difluorosilane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3107677B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009186197A (en) * | 2008-02-04 | 2009-08-20 | Denki Kagaku Kogyo Kk | Chemical treatment method for chlorosilanes |
-
1993
- 1993-03-31 JP JP05073889A patent/JP3107677B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009186197A (en) * | 2008-02-04 | 2009-08-20 | Denki Kagaku Kogyo Kk | Chemical treatment method for chlorosilanes |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3107677B2 (en) | 2000-11-13 |
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