JPH11209103A - Refining method for monogermane - Google Patents
Refining method for monogermaneInfo
- Publication number
- JPH11209103A JPH11209103A JP1434398A JP1434398A JPH11209103A JP H11209103 A JPH11209103 A JP H11209103A JP 1434398 A JP1434398 A JP 1434398A JP 1434398 A JP1434398 A JP 1434398A JP H11209103 A JPH11209103 A JP H11209103A
- Authority
- JP
- Japan
- Prior art keywords
- monogermane
- vessel
- low
- container
- solidified
- 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
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052986 germanium hydride Inorganic materials 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims description 28
- 238000007670 refining Methods 0.000 title 1
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 238000009835 boiling Methods 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000007711 solidification Methods 0.000 description 12
- 230000008023 solidification Effects 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910000078 germane Inorganic materials 0.000 description 10
- 239000003507 refrigerant Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940119177 germanium dioxide Drugs 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- -1 ammonium halide Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VXGHASBVNMHGDI-UHFFFAOYSA-N digermane Chemical compound [Ge][Ge] VXGHASBVNMHGDI-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- SCCCLDWUZODEKG-UHFFFAOYSA-N germanide Chemical compound [GeH3-] SCCCLDWUZODEKG-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はモノゲルマンの精製
方法に関する。より詳しくは、モノゲルマン中に含まれ
る水素（Ｈ２）、窒素（Ｎ２）、一酸化炭素（ＣＯ）、
などの低沸点成分を除去し、電子材料、太陽電池素子等
の材料として使用されうる高純度のモノゲルマンを安全
かつ効率よく製造する方法に関する。The present invention relates to a method for purifying monogermane. More specifically, hydrogen (H 2 ), nitrogen (N 2 ), carbon monoxide (CO),
The present invention relates to a method for safely and efficiently producing high-purity monogermane which can be used as a material for an electronic material, a solar cell element, or the like by removing low boiling components such as the above.
【０００２】[0002]
【従来の技術】モノゲルマンは主としてアモルファスシ
リコンゲルマニウム薄膜の原料として使用されている。
これはアモルファスシリコン薄膜より長波長側の光の吸
収効率が高いという特性があるため、今後長波長光の変
換効率の高い太陽電池や長波長光感度の高い感光ドラム
の開発が進むにつれ、モノゲルマンの需要も著しく伸び
てくるものと期待されている。このため、アモルファス
シリコンゲルマニウム薄膜の原料として使用できるよう
な高純度モノゲルマンが要求されている。ゲルマンの製
造は、古くは１９００年代の初頭にその報告があるが、
本格的に研究が始まったのは１９２０年代以降である。2. Description of the Related Art Monogermane is mainly used as a raw material for amorphous silicon germanium thin films.
This has the property that the absorption efficiency of light on the long wavelength side is higher than that of amorphous silicon thin films.Therefore, as the development of solar cells with high conversion efficiency for long wavelength light and photosensitive drums with high long wavelength light sensitivity progresses, Monogerman The demand for is expected to increase significantly. Therefore, high-purity monogermane that can be used as a raw material of an amorphous silicon germanium thin film is required. Germanic production was reported in the early 1900s,
Research began in earnest after the 1920s.
【０００３】これまでのゲルマン生成反応の型式は大き
く次の３つに分類される。 １）マグネシウムゲルマナイド（＝Ｍｇ２Ｇｅ）と酸も
しくはハロゲン化アンモニウムの反応 例えば、Krans、Carney, J.Am.Chem.Soc.; vol.56, P765
(1934) ２）四塩化ゲルマニウム（＝ＧｅＣｌ４）と水素化剤と
の反応 例えば、Finholt、Bond, J.Am.Chem.Soc.; vol.69, P269
2 (1947) ３）二酸化ゲルマニウム（＝ＧｅＯ２）と水素化剤との
反応 例えば、Piper、Wilson, J.Inorg.Nucl.Chem.; vol.4, P
22 (1957)[0003] The types of Germane-forming reactions so far are roughly classified into the following three types. 1) Reaction of magnesium germanide (= Mg 2 Ge) with acid or ammonium halide For example, Krans, Carney, J. Am. Chem. Soc .; vol. 56, P765
(1934) 2) Reaction of germanium tetrachloride (= GeCl 4 ) with hydrogenating agent For example, Finholt, Bond, J. Am. Chem. Soc .; vol. 69, P269
2 (1947) 3) Reaction of germanium dioxide (= GeO 2 ) with hydrogenating agent For example, Piper, Wilson, J. Inorg. Nucl. Chem .; vol. 4, P
22 (1957)
【０００４】上記何れの方法を採用しても製造されたモ
ノゲルマンを主成分として含むガスを製造することがで
きる。しかしながら、本発明者らが得られた粗ゲルマン
ガス中の不純物について種々検討を行ったところ、反応
原料や条件によってその種類や量は多少ことなるが、殆
どの場合二酸化炭素（ＣＯ２）、や一酸化炭素（Ｃ
Ｏ）、水素（Ｈ２）、メタンエタン等の炭化水素類、Ｓ
Ｏ２やＨ２Ｓ含有硫黄化合物、ＨＣｌ等が含まれている
ことがわかった。また当然のことながら、Ｈｅや、Ｎ２
を、キャリアガスとした場合には、これを不純物として
含有することになる。Either of the above methods can produce a gas containing the produced monogermane as a main component. However, the present inventors have conducted various studies on the impurities in the obtained crude germane gas, and found that the type and amount vary depending on the reaction raw materials and conditions, but in most cases, carbon dioxide (CO 2 ), Carbon monoxide (C
O), hydrogen (H 2 ), hydrocarbons such as methaneethane, S
It was found that O 2 and H 2 S-containing sulfur compounds, HCl and the like were contained. Of course, He and N 2
Is used as a carrier gas, this is contained as an impurity.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、これま
で、モノゲルマン中の不純物の除去、精製に関する報告
は、全くなされていない。このため本発明者らが鋭意検
討行ったところ、上記モノゲルマン中の不純物のうち、
二酸化炭素、炭化水素類、含有硫黄化合物等は固体酸と
接触することにより、効率的に吸着除去できることを見
出し、この方法を特願平９−３３５８５５号公報に開示
した。しかしながらＨ２やＨｅ、Ｎ２等の低沸点成分は
一般に吸着では十分に分離除去を行うことができない。
このため目的の分離を行うためには深冷蒸留操作が必要
となるが、モノゲルマンは発火性であり、かつ自己分解
性があり、取り扱いが極めて難しい物質であるため蒸留
のような緊雑な操作はできるかぎり避けたい。本発明の
目的は前述低沸点成分の不純物を効率よく分離し、かつ
安全に高純度モノゲルマンを得る方法を提供することに
ある。However, there have been no reports on the removal and purification of impurities in monogermane. For this reason, the present inventors conducted extensive studies, and found that among the impurities in the monogermane,
It has been found that carbon dioxide, hydrocarbons, contained sulfur compounds and the like can be efficiently adsorbed and removed by contact with a solid acid, and this method was disclosed in Japanese Patent Application No. 9-335855. However, low-boiling components such as H 2 , He, and N 2 cannot generally be sufficiently separated and removed by adsorption.
Therefore, a cryogenic distillation operation is required to perform the intended separation.However, monogermane is ignitable, self-decomposing, and extremely difficult to handle. I want to avoid operations as much as possible. An object of the present invention is to provide a method for efficiently separating impurities of the above-mentioned low-boiling components and safely obtaining high-purity monogermane.
【０００６】[0006]
【課題を解決するための手段】本発明者らが、粗ゲルマ
ンガス中の上記低沸点成分の除去方法について鋭意検討
を行ったところ、モノゲルマンを容器内で冷却固化した
後該容器を真空排気すれば極めて効率よく上記不純物が
除去できる事を見出し、本発明を完成するに至ったもの
である。Means for Solving the Problems The present inventors have conducted intensive studies on a method for removing the low-boiling components from the crude germane gas. After the monogermane was cooled and solidified in the vessel, the vessel was evacuated. The inventors have found that the impurities can be removed very efficiently if they do so, and have completed the present invention.
【０００７】即ち、本発明は低沸点成分を主たる不純物
として含有するモノゲルマンを容器内で冷却し、固化し
た状態で、該容器内を真空排気すること、または低沸点
成分を主たる不純物として含有するモノゲルマンを容器
内で冷却し、固化した状態で、該容器内を真空排気した
後モノゲルマンを容器内で気化せしめ、再度冷却し、固
化した状態で容器内を真空排気することを特徴とするモ
ノゲルマンの精製方法に関する。 〔発明の詳細な説明〕That is, according to the present invention, monogermane containing a low-boiling component as a main impurity is cooled and solidified in a vessel, and the inside of the vessel is evacuated, or the low-boiling component is contained as a main impurity. The monogerman is cooled in the container, and in a solidified state, the inside of the container is evacuated after vacuum evacuation, the monogerman is vaporized in the container, cooled again, and the container is evacuated in the solidified state. The present invention relates to a method for purifying monogermane. [Detailed description of the invention]
【０００８】以下、本発明を詳細に説明する。一般に反
応で生成するモノゲルマン中には前述のごとく、高次ゲ
ルマンであるジゲルマン（Ｇｅ２Ｈ６）、トリゲルマン
（Ｇｅ３Ｈ８）、また、炭化水素類（ＴＨＣ）、二酸化
炭素（ＣＯ２）などの不純物が混入するが、本発明の方
法ではこれらの高沸点成分を直接対象としておらず、低
沸点成分を対象とする発明である。本発明にいう低沸点
成分とは、モノゲルマンに対する相対揮発度の高い成分
であり、厳密にはモノゲルマンの融点である−１６５℃
以下に常圧の沸点を有する成分と定義する。具体的に
は、Ｎ２、Ｈｅ、Ｈ２、Ｏ２、ＣＯ等が挙げられる。低
沸点成分を主たる不純物し含有するモノゲルマンの製法
には特に限定はなく、前述に挙げた例のごとき反応を好
適に採用できる。しかしながら、反応を行うに際しては
取り扱いの容易で安価な物質を使用することが好ましい
ことは言うまでもなく、大気中でＨＣｌミストを生成す
るような四塩化ゲルマニウムや高価な金属ゲルマニウム
を使用するよりも、二酸化ゲルマニウムと水素化剤とを
反応させる方法がより好ましい。Hereinafter, the present invention will be described in detail. In general, monogermanes formed by the reaction include higher-order germanes such as digermane (Ge 2 H 6 ) and trigermane (Ge 3 H 8 ), hydrocarbons (THC), and carbon dioxide (CO 2 ), as described above. )), But the method of the present invention does not directly target these high-boiling components, but rather the low-boiling components. The low boiling point component referred to in the present invention is a component having a high relative volatility to monogermane, and strictly speaking, a melting point of monogermane of -165 ° C.
Hereinafter, it is defined as a component having a normal boiling point. Specific examples include N 2 , He, H 2 , O 2 , CO, and the like. There is no particular limitation on the method for producing monogermane containing low-boiling components as main impurities, and the reaction as in the above-mentioned examples can be suitably employed. However, it is needless to say that it is preferable to use an easy-to-handle and inexpensive substance when performing the reaction. A method of reacting germanium with a hydrogenating agent is more preferable.
【０００９】このようにして生成したガス中には先に述
べたように、不純物として低沸成分以外に高次ゲルマン
や炭化水素、ＣＯ２等を含むが、事前に後者の成分を吸
着等の方法で除去してもよいしそのまま本発明を遂行し
てもよい。次に本発明の本質を述べる。モノゲルマンの
凝固点は常圧下で−１６５℃であり、この温度で固化す
る。本発明ではモノゲルマンが固化した状態で雰囲気を
真空排気する。この操作により、この温度で蒸気圧を有
する低沸点成分を除去することができる。As described above, the gas thus generated contains higher-order germane, hydrocarbons, CO 2 , and the like as impurities in addition to low-boiling components. It may be removed by a method or the present invention may be performed as it is. Next, the essence of the present invention will be described. The freezing point of monogermane is -165 ° C under normal pressure and solidifies at this temperature. In the present invention, the atmosphere is evacuated while the monogerman is solidified. By this operation, a low-boiling component having a vapor pressure at this temperature can be removed.
【００１０】モノゲルマンの冷却固化のために使用する
冷媒としては特に限定するものではないがコスト的には
液体窒素を使用するのが最も有利である。また排気用の
ポンプも特に限定しないが、モノゲルマンの物性を考え
るとオイルの混入を避けるべきであり真空排気はダイヤ
フラム式の真空ポンプが好ましい。The refrigerant used for cooling and solidifying monogermane is not particularly limited, but liquid nitrogen is most advantageous in terms of cost. The pump for evacuation is not particularly limited. However, considering the physical properties of monogermane, mixing of oil should be avoided, and the vacuum evacuation is preferably a diaphragm-type vacuum pump.
【００１１】また、真空排気時間は、容器の容量、処理
すべきモノゲルマンの充填量、低沸点成分の含有量、真
空ポンプの排気能力などによって異なるので一概に断定
出来ないが、概ね３〜３０分、好ましくは５〜２０分程
度の間で実施する。その際の容器内圧力は好ましくは１
０Ｔｏｒｒ以下、より好ましくは５Ｔｏｒｒ以下、最も
好ましくは２Ｔｏｒｒ以下になるまで排気を行う。この
理由は１０Ｔｏｒｒを超えると低沸成分を除去すること
はできるが高純度のモノゲルマンを得ることはできな
い。また、真空排気を終えたモノゲルマンを一旦ガス化
せしめ再度固化して真空排気すると更に低沸成分が効率
的に除去されることを本発明者らは実験的に確認した。
おそらく最初にモノゲルマンが固化する際に低沸成分を
とりこんで固化しているため一旦ガス化する効果があら
われるものと推定している。The vacuum evacuation time cannot be determined unconditionally because it varies depending on the capacity of the container, the filling amount of monogermane to be treated, the content of low-boiling components, and the evacuation capacity of the vacuum pump. Minutes, preferably about 5 to 20 minutes. The pressure in the vessel at that time is preferably 1
Exhaust is performed until the pressure becomes 0 Torr or less, more preferably 5 Torr or less, and most preferably 2 Torr or less. The reason is that if it exceeds 10 Torr, low boiling components can be removed, but high-purity monogermane cannot be obtained. In addition, the present inventors have experimentally confirmed that low-boiling components are more efficiently removed when the monogermane, which has been evacuated, is once gasified, solidified again, and evacuated, to further efficiently remove low-boiling components.
It is presumed that the effect of gasification once appears because monogermane solidifies by taking in low-boiling components when it first solidifies.
【００１２】かくして真空排気が終了すると、容器は密
閉したまま冷媒浴より取り出し、常温に戻して充填され
ているモノゲルマンを気化する。以上一連の操作で
Ｈ２、Ｎ ２、ＣＯなどの低沸点成分が除去された高純度
のモノゲルマンを得る事が出来るのである。尚、この様
にして得られた高純度モノゲルマンを、所望により、再
度本発明を繰り返す事によって、上記低沸点成分が更に
除去され、極めて高純度とすることも可能である。When the evacuation is completed, the container is closed.
Take out from the refrigerant bath with closed, return to normal temperature and fill
To vaporize the monogerman. With a series of operations
H2, N 2High purity with low boiling point components such as CO and CO removed
It is possible to obtain the monogerman. In addition, like this
The high-purity monogermane obtained in
By repeating the present invention, the low boiling point component
It can be removed and made extremely high in purity.
【００１３】[0013]
【実施例】以下、実施例により本発明を具体的に説明す
る。なお二酸化ゲルマニウム、ナトリウムボロハイドラ
イド、水酸化カリウム、硫酸はすべて関東化学社製の試
薬を、水はイオン交換水を使用した。以下、％は重量基
準を表す。 実施例１ 容量１Ｌのガラス製三角フラスコに２.８％の水酸化カ
リウム水溶液５６６ｇを調製し、これに二酸化ゲルマニ
ウム粉末７.９ｇとナトリウムボロハイドライド粉末１
６．５ｇを添加、攪拌、溶解して反応原料水溶液を調製
した。また、他の１Ｌガラス製三角フラスコに２７％の
硫酸水溶液（約３mol／ｌ）を調製した。容量１Ｌで密
閉のできる蓋付のテフロン製反応器に２７％の硫酸水溶
液１５０ｇを仕込んで蓋を閉め、反応原料水溶液供給ラ
イン、温度計、キャリヤ窒素、発生ガス出口ラインを接
続した。反応器はスターラーで攪拌ができるようにし、
また容器ごと温浴に浸して、反応温度を２５〜３５℃に
調節するようにした。The present invention will be described below in detail with reference to examples. Note that germanium dioxide, sodium borohydride, potassium hydroxide, and sulfuric acid all used reagents manufactured by Kanto Chemical Co., and water used was ion-exchanged water. Hereinafter,% represents a weight standard. Example 1 566 g of a 2.8% potassium hydroxide aqueous solution was prepared in a 1 L glass Erlenmeyer flask, and 7.9 g of germanium dioxide powder and sodium borohydride powder 1 were added thereto.
6.5 g was added, stirred and dissolved to prepare a reaction raw material aqueous solution. A 27% aqueous sulfuric acid solution (about 3 mol / l) was prepared in another 1-L glass Erlenmeyer flask. 150 g of a 27% aqueous sulfuric acid solution was charged into a Teflon reactor having a capacity of 1 L and capable of being sealed, and the lid was closed. A reaction raw material aqueous solution supply line, a thermometer, carrier nitrogen, and a generated gas outlet line were connected. The reactor should be stirred with a stirrer,
The reaction vessel was immersed in a warm bath to adjust the reaction temperature to 25 to 35 ° C.
【００１４】また別途、図１に示すモノゲルマンの精製
装置を以下のように前準備した。先ず固化精製用ボンベ
１（容量１５０ｍｌ、材質ＳＵＳ−３１６製）を約１０
０℃に加熱した状態で内圧が１Torr以下に達する迄真空
ポンプ３にて排気した。しかる後、加熱を止め、室温ま
で冷却し、固化精製用ボンベ１を冷媒槽２（冷媒は液体
窒素を使用）中に浸漬して内温が−１９０℃以下になる
まで冷却した。次に、真空ポンプをストップし、Ｈｅガ
スを常圧まで導入した。Separately, a monogerman purification apparatus shown in FIG. 1 was prepared in advance as follows. First, a cylinder 1 for solidification and purification (capacity: 150 ml, made of SUS-316) was prepared for
While heating to 0 ° C., the gas was evacuated by the vacuum pump 3 until the internal pressure reached 1 Torr or less. Thereafter, the heating was stopped, the temperature was cooled to room temperature, and the solidification / purification cylinder 1 was immersed in a refrigerant tank 2 (liquid nitrogen was used as a refrigerant) to cool the internal temperature to -190 ° C or lower. Next, the vacuum pump was stopped, and He gas was introduced to normal pressure.
【００１５】以上のように前準備したゲルマン発生装置
と、精製装置を用い、ゲルマン発生装置より発生した粗
ゲルマンガスを、シリカゲル及びモレキュラシーブと接
触させて高沸点を除去した後、導入配管（配管１３）よ
り固化精製用ボンベ１に通気する為、４時間通気しモノ
ゲルマンを固化した。尚、冷却固化精製中のボンベ内温
度は、−１９０〜−１９５℃で行い、固化精製ボンベ１
の後に、冷却固化ロス分のモノゲルマンを確認する為、
ガスクロマトグラフィーで分析を行えるようにした。４
時間後、モノゲルマンの発生をストップし、容器内にモ
ノゲルマンを固化した状態で、真空ポンプ３を起動し、
容器内気相部に残っている低沸点成分を除去した。上記
操作温度は−１９０〜−１９７℃、真空排気時間は１０
分とした。真空排気終了後、容器を密閉した状態で、冷
媒槽２より容器を取り出し、常温になるまで放置してモ
ノゲルマンを気化した。気化したモノゲルマン中の低沸
点成分をガスクロマトグラフィーにて成分分析した値を
表１に示した。Using the germane generator and the purifier prepared as described above, the crude germane gas generated from the germane generator is brought into contact with silica gel and molecular sieve to remove the high boiling point, and then introduced into the introduction pipe (pipe 13). ) In order to aerate the bomb 1 for solidification and purification, aeration was performed for 4 hours to solidify monogermane. The temperature in the cylinder during the cooling and solidification purification was -190 to -195 ° C,
After, to confirm the monogermane of the cooling solidification loss,
The analysis was made possible by gas chromatography. 4
After a period of time, the generation of monogermane is stopped, and the vacuum pump 3 is started with the monogermane solidified in the container,
Low boiling components remaining in the gas phase in the vessel were removed. The operating temperature is -190 to -197 ° C, and the evacuation time is 10
Minutes. After the evacuation was completed, the container was taken out of the refrigerant tank 2 with the container sealed, and allowed to stand at room temperature to evaporate monogermane. Table 1 shows the values of low-boiling components in the vaporized monogermane, which were analyzed by gas chromatography.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【発明の効果】本発明は、モノゲルマンガス中に含有す
る不純物のうち、二酸化炭素（ＣＯ２）、炭化水素（Ｔ
ＨＣ）を、モレキュラシーブなどの吸着剤を使用する精
製方法で除去した後、水素（Ｈ２）、窒素（Ｎ２）、一
酸化炭素（ＣＯ）等を主たる不純物成分として含有する
モノゲルマンを、容器内で温度−１９７℃以下で冷却固
化した後、容器内を、１Ｔｏｒｒ以下まで真空排気する
という、極めて簡単な精製方法である。本発明の方法を
採用すれば、安全に、かつ高純度のモノゲルマンが得る
ことができる。以上を総合して考えると、本発明の効果
は大きいと考える。According to the present invention, carbon monoxide (CO 2 ) and hydrocarbon (T
HC) is removed by a purification method using an adsorbent such as molecular sieve, and then monogermane containing hydrogen (H 2 ), nitrogen (N 2 ), carbon monoxide (CO), etc. as main impurity components is placed in a container. This is a very simple purification method in which after cooling and solidifying at a temperature of −197 ° C. or less in a vessel, the inside of the vessel is evacuated to 1 Torr or less. By employing the method of the present invention, monogermane of high purity can be obtained safely and safely. Considering all the above, the effect of the present invention is considered to be great.
【００１８】[0018]
【図１】 本発明のモノゲルマンを精製する概略図FIG. 1 is a schematic diagram for purifying the monogermane of the present invention.
１ 固化精製用ボンベ ２ 冷媒槽 ３ 真空ポンプ ４ ガスクロマトグラフィー ５ 圧力計 ６ 温度計 ７ モノゲルマン導入配管 ８ Ｈｅ導入配管 DESCRIPTION OF SYMBOLS 1 Cylinder for solidification / purification 2 Refrigerant tank 3 Vacuum pump 4 Gas chromatography 5 Pressure gauge 6 Thermometer 7 Monogerman introduction pipe 8 He introduction pipe
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年２月１３日[Submission date] February 13, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００９】このようにして生成したガス中には先に述
べたように、不純物として低沸成分以外に高次ゲルマン
や炭化水素、ＣＯ２等を含むが、事前に後者の成分を吸
着等の方法で除去してもよいしそのまま本発明を遂行し
てもよい。次に本発明の本質を述べる。モノゲルマンの
融点は常圧下で−１６５℃であり、この温度で固化す
る。本発明ではモノゲルマンが固化した状態で雰囲気を
真空排気する。この操作により、この温度で蒸気圧を有
する低沸点成分を除去することができる。As described above, the gas thus generated contains higher-order germane, hydrocarbons, CO 2 , and the like as impurities in addition to low-boiling components. It may be removed by a method or the present invention may be performed as it is. Next, the essence of the present invention will be described. Monogerman
The melting point is -165 ° C under normal pressure and solidifies at this temperature. In the present invention, the atmosphere is evacuated while the monogerman is solidified. By this operation, a low-boiling component having a vapor pressure at this temperature can be removed.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１４】また別途、図１に示すモノゲルマンの精製
装置を以下のように前準備した。先ず固化精製用ボンベ
１（容量１５０ｍｌ、材質ＳＵＳ−３１６製）を約１０
０℃に加熱した状態で内圧が１Ｔｏｒｒ以下に達する迄
真空ポンプ３にて排気した。しかる後、加熱を止め、室
温まで冷却し、固化精製用ボンベ１を冷媒槽２（冷媒は
液体窒素を使用）中に浸漬して内温が−１９０℃以下に
なるまで冷却した。次に、真空ポンプ３をストップし、
ＨｅガスをＨｅ導入配管８より常圧まで導入した。Separately, a monogerman purification apparatus shown in FIG. 1 was prepared in advance as follows. First, a cylinder 1 for solidification and purification (capacity: 150 ml, made of SUS-316) was prepared for
While heating to 0 ° C., the gas was evacuated by the vacuum pump 3 until the internal pressure reached 1 Torr or less. Thereafter, the heating was stopped, the temperature was cooled to room temperature, and the solidification / purification cylinder 1 was immersed in a refrigerant tank 2 (liquid nitrogen was used as a refrigerant) to cool the internal temperature to -190 ° C or lower. Next, the vacuum pump 3 is stopped,
He gas was introduced from He introduction pipe 8 to normal pressure.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Correction target item name] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１５】以上のように前準備したゲルマン発生装置
と、精製装置を用い、ゲルマン発生装置より発生した粗
ゲルマンガスを、シリカゲル及びモレキュラシーブと接
触させて高沸点物を除去した後、モノゲルマン導入配管
７より固化精製用ボンベ１に通気する為、４時間通気し
モノゲルマンを固化した。尚、冷却固化精製中のボンベ
内温度は、−１９０〜−１９５℃で行い、固化精製ボン
ベ１の後に、冷却固化ロス分のモノゲルマンを確認する
為、ガスクロマトグラフィーで分析を行えるようにし
た。４時間後、モノゲルマンの発生をストップし、容器
内にモノゲルマンを固化した状態で、真空ポンプ３を起
動し、容器内気相部に残っている低沸点成分を除去し
た。上記操作温度は−１９０〜−１９７℃、真空排気時
間は１０分とした。真空排気終了後、容器を密閉した状
態で、冷媒槽２より容器を取り出し、常温になるまで放
置してモノゲルマンを気化した。気化したモノゲルマン
中の低沸点成分をガスクロマトグラフィーにて成分分析
した値を表１に示した。[0015] and germane generating apparatus prior prepared as above, using the purifier, the crude germane gas generated from germane generator, after removal of the high boilers in contact with silica gel and molecular sieves, monogermane introduction pipe
In order to ventilate the solidification / purification cylinder 1 from Step 7 , the mixture was ventilated for 4 hours to solidify the monogermane. The temperature in the cylinder during the cooling and solidification purification was -190 to -195 ° C., and after the solidification and purification cylinder 1, analysis was performed by gas chromatography to confirm monogermane of the cooling solidification loss. . After 4 hours, the generation of monogermane was stopped, and in a state where the monogermane was solidified in the vessel, the vacuum pump 3 was started to remove low boiling components remaining in the gas phase in the vessel. The operation temperature was -190 to -197 ° C, and the evacuation time was 10 minutes. After the evacuation was completed, the container was taken out of the refrigerant tank 2 with the container sealed, and allowed to stand at room temperature to evaporate monogermane. Table 1 shows the values of low-boiling components in the vaporized monogermane, which were analyzed by gas chromatography.
Claims (6)
するモノゲルマンを容器内で冷却し、固化した状態で、
該容器内を真空排気することを特徴とするモノゲルマン
の精製方法。1. A monogermane containing a low-boiling component as a main impurity is cooled in a container and solidified.
A method for purifying monogermane, comprising evacuating the container.
するモノゲルマンを容器内で冷却し、固化した状態で、
該容器内を真空排気した後モノゲルマンを容器内で気化
せしめ、再度冷却し、固化した状態で容器内を真空排気
することを特徴とするモノゲルマンの精製方法。2. A monogermane containing a low-boiling component as a main impurity is cooled in a container and solidified.
A method for purifying monogermane, comprising evacuating the vessel, evaporating the monogermane in the vessel, cooling again, and evacuating the vessel in a solidified state.
ｏｒｒ以下である請求項１または２記載のモノゲルマン
の精製方法。3. The pressure in the container at the time of evacuation is 10T.
The method for purifying monogermane according to claim 1 or 2, which is at or or lower.
ｒｒ以下である請求項１または２記載のモノゲルマンの
精製方法。4. The pressure in the container at the time of evacuation is 5 To
The method for purifying monogermane according to claim 1 or 2, wherein the rrrr is not more than rr.
ｒｒ以下である請求項１または２記載のモノゲルマンの
精製方法。5. The pressure in the container at the time of evacuation is 2 To
The method for purifying monogermane according to claim 1 or 2, wherein the rrrr is not more than rr.
とも１回以上、１０Ｔｏｒｒ以下とする請求項１または
２記載のモノゲルマンの精製方法。6. The method for purifying monogermane according to claim 1, wherein the pressure in the container at the time of evacuation is at least once and not more than 10 Torr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1434398A JPH11209103A (en) | 1998-01-27 | 1998-01-27 | Refining method for monogermane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1434398A JPH11209103A (en) | 1998-01-27 | 1998-01-27 | Refining method for monogermane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11209103A true JPH11209103A (en) | 1999-08-03 |
Family
ID=11858436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1434398A Pending JPH11209103A (en) | 1998-01-27 | 1998-01-27 | Refining method for monogermane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11209103A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006034802A1 (en) * | 2004-09-29 | 2006-04-06 | Umicore | Process for the production of ge by reduction of geci4, with liquid metal |
-
1998
- 1998-01-27 JP JP1434398A patent/JPH11209103A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006034802A1 (en) * | 2004-09-29 | 2006-04-06 | Umicore | Process for the production of ge by reduction of geci4, with liquid metal |
| US7682593B2 (en) | 2004-09-29 | 2010-03-23 | Umicore | Process for the production of Ge by reduction of GeCl4 with liquid metal |
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