JPWO2018212007A1 - Method for producing germane electrochemically - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229910000078 germane Inorganic materials 0.000 title claims abstract description 11
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 13
- 150000002291 germanium compounds Chemical class 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 239000004332 silver Substances 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- 229940119177 germanium dioxide Drugs 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910005793 GeO 2 Inorganic materials 0.000 description 7
- 239000012528 membrane Substances 0.000 description 6
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Abstract
隔膜、陽極および銀を含む陰極を有する電気化学セル中で、ゲルマニウム化合物を含む電解液に通電して、陰極においてゲルマンを発生させて、電気化学的にゲルマンを製造する方法。A method for producing germane electrochemically by energizing an electrolytic solution containing a germanium compound in an electrochemical cell having a diaphragm, an anode and a cathode containing silver to generate germane at the cathode.
Description
本発明は、電気化学的にゲルマンを製造する方法に関する。 The present invention relates to a method for electrochemically producing germane.
従来、半導体デバイスの高速化・低消費電力化は、該デバイスの微細化等によって達成されてきたが、さらなる高速化・低消費電力化のための技術として、ＳｉＧｅ基板などの歪シリコンが注目されている。
該ＳｉＧｅ基板を作製する際の原料として、ゲルマン（ＧｅＨ4）が使用されており、ＳｉＧｅ基板の使用の増加に伴い、ＧｅＨ4の使用量も増加すると予想される。Conventionally, high speed and low power consumption of a semiconductor device have been achieved by miniaturization of the device. However, strained silicon such as a SiGe substrate has attracted attention as a technology for further speeding up and lowering power consumption. ing.
Germane (GeH 4 ) is used as a raw material for producing the SiGe substrate, and the use amount of GeH 4 is expected to increase as the use of the SiGe substrate increases.
このようなＧｅＨ4の製造方法として、例えば、特許文献１には、陰極として、Ｃｕ合金またはＳｎ合金を使用することで、ＧｅＨ4を高い電流効率で電気化学的に製造できたことが記載されている。As such a method for producing GeH 4 , for example, Patent Document 1 describes that GeH 4 could be electrochemically produced with high current efficiency by using a Cu alloy or a Sn alloy as a cathode. ing.
また、非特許文献１には、電気化学的にＧｅＨ4を製造する際に用いる陰極として、Ｐｔ、Ｚｎ、Ｔｉ、グラファイト、Ｃｕ、Ｎｉ、Ｃｄ、Ｐｂ、Ｓｎをスクリーニングした結果、ＣｄまたはＣｕが電流効率や汚染等の点で最適であったことが記載されている。Further, Non-Patent Document 1 discloses that as a cathode used when electrochemically producing GeH 4 , as a result of screening Pt, Zn, Ti, graphite, Cu, Ni, Cd, Pb, and Sn, Cd or Cu is obtained. It is described that it was optimal in terms of current efficiency, contamination, and the like.
さらに、非特許文献２には、電気化学的にＧｅＨ4を製造する際に用いる陰極として複数の陰極を調査した結果、陰極としてＨｇを使用した場合に、水素化率が９９％以上になったことを開示している。Further, in Non-Patent Document 2, as a result of investigating a plurality of cathodes as cathodes used for electrochemically producing GeH 4 , when Hg was used as the cathode, the hydrogenation rate was 99% or more. It is disclosed that.
前記文献に記載されているような従来のＧｅＨ4を電気化学的に製造する方法は、例えば、前記特許文献１の実施例で用いている陰極（McMaster-Carr社製の青銅）がメッキやコーティング等で表面にだけ有効な元素を存在させるといった方法を適用し難いことや、前記非特許文献２で用いている陰極（Ｈｇ）の毒性が高いなどの理由により、工業的にＧｅＨ4を製造する方法としては不向きであった。The conventional method for electrochemically producing GeH 4 as described in the above-mentioned literature is based on, for example, plating or coating a cathode (a bronze made by McMaster-Carr) used in an example of the above-mentioned Patent Literature 1. GeH 4 is manufactured industrially because it is difficult to apply a method of allowing an effective element to exist only on the surface, and the toxicity of the cathode (Hg) used in Non-Patent Document 2 is high. It was unsuitable as a method.
本発明の一実施形態は、ＧｅＨ4を電気化学的に製造する方法として工業的に有利な方法を提供する。One embodiment of the present invention to provide an industrially advantageous method as a method for producing a GeH 4 electrochemically.
本発明者は、前記課題を解決すべく鋭意検討した結果、下記製造方法等によれば、前記課題を解決できることを見出し、本発明を完成するに至った。
本発明の構成例は以下の通りである。As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the following manufacturing method and the like, and have completed the present invention.
The configuration example of the present invention is as follows.
［１］ 隔膜、陽極および銀を含む陰極を有する電気化学セル中で、ゲルマニウム化合物を含む電解液に通電して、陰極においてゲルマンを発生させて、電気化学的にゲルマンを製造する方法。 [1] A method for producing germane electrochemically by energizing an electrolytic solution containing a germanium compound in an electrochemical cell having a diaphragm, an anode and a cathode containing silver to generate germane at the cathode.
［２］ 前記電解液が、二酸化ゲルマニウムとイオン性物質とを含む電解液である、［１］に記載の製造方法。
［３］ 前記イオン性物質が、水酸化カリウムまたは水酸化ナトリウムである、［２］に記載の製造方法。
［４］ 前記イオン性物質が水酸化カリウムであり、前記電解液中の水酸化カリウムの濃度が１〜８ｍｏｌ／Ｌである、［２］または［３］に記載の製造方法。[2] The method according to [1], wherein the electrolytic solution is an electrolytic solution containing germanium dioxide and an ionic substance.
[3] The production method according to [2], wherein the ionic substance is potassium hydroxide or sodium hydroxide.
[4] The method according to [2] or [3], wherein the ionic substance is potassium hydroxide, and the concentration of potassium hydroxide in the electrolyte is 1 to 8 mol / L.
［５］ 前記通電の際の陰極の電流密度が３０〜５００ｍＡ／ｃｍ2である、［１］〜［４］のいずれかに記載の製造方法。
［６］ 前記ゲルマンを発生させる際の反応温度が５〜１００℃である、［１］〜［５］のいずれかに記載の製造方法。[5] The production method according to any one of [1] to [4], wherein the current density of the cathode at the time of energization is 30 to 500 mA / cm 2 .
[6] The production method according to any one of [1] to [5], wherein a reaction temperature at which the germane is generated is 5 to 100 ° C.
本発明の一実施形態によれば、工業的に有利な方法、特に高い電流効率でＧｅＨ4を電気化学的に製造することができる。According to an embodiment of the present invention, GeH 4 can be electrochemically produced with an industrially advantageous method, particularly with high current efficiency.
≪電気化学的にＧｅＨ4を製造する方法≫
本発明の一実施形態に係る電気化学的にＧｅＨ4を製造する方法（以下「本方法」ともいう。）は、隔膜、陽極および銀を含む陰極を有する電気化学セル中で、ゲルマニウム化合物を含む電解液に通電して、陰極においてＧｅＨ4を発生させて、電気化学的にＧｅＨ4を製造する。
本方法によれば、工業的に有利な方法、特に高い電流効率でＧｅＨ4を電気化学的に製造することができる。従って、本方法で得られたＧｅＨ4を用いることで、ＳｉＧｅ基板を工業的に有利に製造することもできる。<< Method of producing GeH 4 electrochemically >>
A method for electrochemically producing GeH 4 according to an embodiment of the present invention (hereinafter also referred to as “the present method”) includes a germanium compound in an electrochemical cell having a diaphragm, an anode, and a cathode containing silver. The electrolyte is energized to generate GeH 4 at the cathode, thereby producing GeH 4 electrochemically.
According to this method, GeH 4 can be electrochemically produced with an industrially advantageous method, particularly with high current efficiency. Therefore, by using GeH 4 obtained by the present method, a SiGe substrate can be industrially advantageously produced.
このような工業的な反応としては、例えば、電解液容量が５００〜２５００Ｌで、セル数が３０〜１５０個、使用する電流が１００〜３００Ａといったような規模の反応が挙げられる。 As such an industrial reaction, for example, a reaction having a volume of 500 to 2500 L, a number of cells of 30 to 150, and a current of 100 to 300 A is used.
本方法によれば、好ましくは１０〜９０％、より好ましくは１２〜４０％の電流効率でＧｅＨ4を製造することができる。
なお、前記電流効率は、具体的には、下記実施例に記載の方法で測定することができる。According to this method, GeH 4 can be produced with a current efficiency of preferably 10 to 90%, more preferably 12 to 40%.
The current efficiency can be specifically measured by the method described in the following example.
＜電気化学セル＞
前記電気化学セルとしては、隔膜、陽極および前記陰極を有すれば特に制限されず、従来公知のセルを用いることができる。
該セルとしては、具体的には、陽極を含む陽極室と、陰極を含む陰極室とを隔膜を用いて隔てたセル等が挙げられる。<Electrochemical cell>
The electrochemical cell is not particularly limited as long as it has a diaphragm, an anode, and the cathode, and a conventionally known cell can be used.
Specific examples of the cell include a cell in which an anode chamber including an anode and a cathode chamber including a cathode are separated using a diaphragm.
＜陰極＞
前記陰極は、Ａｇを含めば特に制限されない。
該陰極は、金属Ａｇからなる電極やＡｇを主成分とするＡｇ基合金からなる電極であってもよいし、金属ＡｇまたはＡｇ合金をメッキまたはコーティングした電極であってもよい。
前記メッキまたはコーティングした電極としては、Ｎｉ等の基材に金属ＡｇまたはＡｇ合金をメッキまたはコーティングした電極等が挙げられる。
これらの中でも、金属Ａｇは高価であるため、コストの面からは、金属ＡｇまたはＡｇ合金をメッキまたはコーティングした電極であることが好ましい。<Cathode>
The cathode is not particularly limited as long as Ag is included.
The cathode may be an electrode made of metal Ag, an electrode made of an Ag-based alloy containing Ag as a main component, or an electrode plated or coated with metal Ag or an Ag alloy.
Examples of the plated or coated electrode include an electrode in which a metal such as Ni is plated or coated with metal Ag or an Ag alloy.
Among them, metal Ag is expensive, and therefore, from the viewpoint of cost, it is preferable to use an electrode plated or coated with metal Ag or an Ag alloy.
前記陰極の形状は特に制限されず、板状、柱状、中空状等のいずれであってもよい。
また、前記陰極の大きさ、表面積等も特に制限されない。The shape of the cathode is not particularly limited, and may be any one of a plate shape, a column shape, a hollow shape, and the like.
Further, the size, surface area and the like of the cathode are not particularly limited.
＜陽極＞
前記陽極としては、特に制限されず、電気化学的にＧｅＨ4を製造する際に従来用いられてきた陽極を用いればよいが、ＮｉおよびＰｔ等の導電性金属からなる電極、該導電性金属を主成分とする合金からなる電極等が好ましく、コストの面から、Ｎｉからなる電極が好ましい。
また、前記陽極は、陰極と同様に、前記導電性金属または該金属を含む合金をメッキまたはコーティングした電極を使用してもよい。
前記陽極の形状、大きさ、表面積等も、前記陰極と同様に特に制限されない。<Anode>
The anode is not particularly limited, and may be an anode conventionally used when electrochemically producing GeH 4. An electrode made of a conductive metal such as Ni and Pt may be used as the anode. An electrode made of an alloy as a main component is preferable, and an electrode made of Ni is preferable in terms of cost.
The anode may be an electrode formed by plating or coating the conductive metal or an alloy containing the metal, similarly to the cathode.
The shape, size, surface area and the like of the anode are not particularly limited as well as the cathode.
＜隔膜＞
前記隔膜としては、特に制限されず、電気化学セルに従来用いられてきた、陽極室と陰極室とを隔てることが可能な隔膜を用いればよい。
このような隔膜としては、種々の電解質膜や多孔質膜を用いることができる。
電解質膜としては、高分子電解質膜、例えばイオン交換固体高分子電解質膜、具体的には、ＮＡＦＩＯＮ（登録商標）１１５、１１７、ＮＲＥ−２１２（シグマアルドリッチ社製）等が挙げられる。
多孔質膜としては、多孔質ガラス、多孔質アルミナ、多孔質チタニア等の多孔質セラミックス、多孔質ポリエチレン、多孔質プロピレン等の多孔質ポリマー等を用いることができる。<Diaphragm>
The diaphragm is not particularly limited, and any diaphragm conventionally used in an electrochemical cell and capable of separating an anode compartment and a cathode compartment may be used.
Various electrolyte membranes and porous membranes can be used as such a diaphragm.
Examples of the electrolyte membrane include a polymer electrolyte membrane, for example, an ion-exchange solid polymer electrolyte membrane, specifically, NAFION (registered trademark) 115, 117, NRE-212 (manufactured by Sigma-Aldrich) and the like.
As the porous membrane, porous ceramics such as porous glass, porous alumina and porous titania, and porous polymers such as porous polyethylene and porous propylene can be used.
本発明の一実施形態では、隔膜により、電気化学セルを陽極室と陰極室とに分けるため、陽極で発生するＯ2ガスと陰極で発生するＧｅＨ4とを混合させず、それぞれの電極室の独立した出口から取り出すことができる。
Ｏ2ガスとＧｅＨ4とが混合すると、Ｏ2ガスとＧｅＨ4とが反応して、ＧｅＨ4の収率が低下する傾向にある。In one embodiment of the present invention, the diaphragm separates the electrochemical cell into an anode chamber and a cathode chamber, so that O 2 gas generated at the anode and GeH 4 generated at the cathode are not mixed, and the respective electrode chambers are not mixed. Can be taken out of a separate exit.
When the O 2 gas and GeH 4 are mixed, the O 2 gas and GeH 4 react with each other, and the yield of GeH 4 tends to decrease.
＜ゲルマニウム化合物を含む電解液＞
本方法では、ゲルマニウム化合物を含む電解液からＧｅＨ4を製造する。
該電解液は、好ましくは水溶液である。<Electrolyte containing germanium compound>
In this method, GeH 4 is produced from an electrolytic solution containing a germanium compound.
The electrolyte is preferably an aqueous solution.
前記ゲルマニウム化合物としては、ＧｅＯ2が好ましい。
前記電解液中のＧｅＯ2の濃度は、高い方が反応速度が速くなり、効率的にＧｅＨ4を合成できるため、溶媒、好ましくは水に対する飽和濃度にすることが好ましい。GeO 2 is preferable as the germanium compound.
The higher the concentration of GeO 2 in the electrolytic solution is, the higher the reaction rate becomes and the more efficient the synthesis of GeH 4 can be.
前記電解液は、電解液の導電性を向上させ、ＧｅＯ2の水への溶解性を促進させるために、イオン性物質を含むことが好ましい。
該イオン性物質としては、電気化学に用いられる従来公知のイオン性物質を用いることができるが、前記効果に優れる等の点から、ＫＯＨまたはＮａＯＨが好ましい。これらの中でも、ＫＯＨ水溶液は、ＮａＯＨ水溶液に比べより導電性に優れるため、ＫＯＨが好ましい。The electrolyte preferably contains an ionic substance in order to improve the conductivity of the electrolyte and promote the solubility of GeO 2 in water.
As the ionic substance, a conventionally known ionic substance used in electrochemistry can be used, but KOH or NaOH is preferable from the viewpoint of excellent effects. Among these, KOH aqueous solution is more preferable than NaOH aqueous solution, and thus KOH is preferable.
前記電解液中のＫＯＨの濃度は、好ましくは１〜８ｍｏｌ／Ｌ、より好ましくは２〜５ｍｏｌ／Ｌである。
ＫＯＨの濃度が前記範囲にあると、ＧｅＯ2濃度の高い電解液を容易に得ることができ、高い電流効率でＧｅＨ4を効率的に製造することができる。
ＫＯＨの濃度が前記範囲の下限未満であると、電解液の導電性が低くなる傾向にあり、ＧｅＨ4の製造に高電圧が必要になる場合があり、また、ＧｅＯ2の水への溶解量が低下する傾向にあり、反応効率が低下する場合がある。一方、ＫＯＨの濃度が前記範囲の上限を超えると、電極やセルの材質として耐食性の高い材質が必要になる傾向にあり、装置のコストが高くなる場合がある。The concentration of KOH in the electrolytic solution is preferably 1 to 8 mol / L, more preferably 2 to 5 mol / L.
When the concentration of KOH is in the above range, an electrolyte having a high GeO 2 concentration can be easily obtained, and GeH 4 can be efficiently produced with high current efficiency.
If the concentration of KOH is less than the lower limit of the above range, the conductivity of the electrolytic solution tends to be low, a high voltage may be required for the production of GeH 4 , and the amount of GeO 2 dissolved in water And the reaction efficiency may decrease. On the other hand, when the concentration of KOH exceeds the upper limit of the above range, a material having high corrosion resistance tends to be required as a material of the electrode or the cell, which may increase the cost of the apparatus.
＜反応条件＞
本方法において、ＧｅＨ4を製造する際（前記通電の際）の陰極の単位面積当たりの電流の大きさ（電流密度）は、反応速度に優れ、高い電流効率でＧｅＨ4を製造できる等の点から、好ましくは３０〜５００ｍＡ／ｃｍ2、より好ましくは５０〜４００ｍＡ／ｃｍ2である。
電流密度が前記範囲にあると、単位時間当たりのＧｅＨ4の発生速度や反応効率を低下させることなく、水の電気分解による水素ガスの発生量を適度に制御することもできる。<Reaction conditions>
In the present method, the magnitude (current density) of the current per unit area of the cathode when producing GeH 4 (at the time of energization) is such that GeH 4 can be produced with high reaction efficiency and high current efficiency. Therefore, it is preferably 30 to 500 mA / cm 2 , more preferably 50 to 400 mA / cm 2 .
When the current density is in the above range, the amount of hydrogen gas generated by the electrolysis of water can be appropriately controlled without lowering the generation rate and reaction efficiency of GeH 4 per unit time.
ＧｅＨ4を製造する際（ＧｅＨ4を発生させる際）の反応温度は、反応速度に優れ、低コストでＧｅＨ4を製造できる等の点から、好ましくは５〜１００℃、より好ましくは１０〜４０℃である。
反応温度が前記範囲にあると、反応効率を低下させることなく、セルの加熱のための電力消費を適度に制御することもできる。The reaction temperature in (when generating the GeH 4) for producing a GeH 4 is excellent in reaction rate, in terms of such can be produced GeH 4 at a low cost, preferably 5 to 100 ° C., more preferably 10 to 40 ° C.
When the reaction temperature is in the above range, the power consumption for heating the cell can be appropriately controlled without lowering the reaction efficiency.
ＧｅＨ4を製造する際の反応雰囲気（陽極室および陰極室の気相部分）は特に制限されないが、不活性ガス雰囲気であることが好ましく、該不活性ガスとしては、窒素ガスが好ましい。The reaction atmosphere (the gas phase portion of the anode chamber and the cathode chamber) for producing GeH 4 is not particularly limited, but is preferably an inert gas atmosphere, and nitrogen gas is preferable as the inert gas.
本方法では、電気化学セル中の前記電解液は、静止させたままでもよいし、撹拌してもよいし、別途他の液槽を設けて循環流通させてもよい。
前記他の液槽を設けて循環流通させた場合、反応液濃度の変化が相対的に小さくなり、電流効率の安定化が期待できるとともに、電極表面のＧｅＯ2濃度が高く保たれ、反応速度の向上が期待できる。このため、電気化学セル中の前記電解液は循環流通させることが好ましい。In this method, the electrolytic solution in the electrochemical cell may be kept stationary, may be stirred, or may be separately circulated and provided with another liquid tank.
When the other liquid tank is provided and circulated, the change in the reaction solution concentration is relatively small, stabilization of the current efficiency can be expected, and the GeO 2 concentration on the electrode surface is kept high, and the reaction speed is reduced. Improvement can be expected. For this reason, it is preferable that the electrolytic solution in the electrochemical cell is circulated and circulated.
＜ＧｅＨ4の製造装置＞
本方法では、前記電気化学セルを用いれば特に制限されないが、該セル以外に、例えば、図１に示すような、電源、測定手段（ＦＴ−ＩＲ、圧力計（ＰＩ）、積算計等）、窒素ガス（Ｎ2）供給路、マスフローコントローラー（ＭＦＣ）、排気路など、従来公知の部材を有する装置を用いることができる。
また、図示しない、前述の循環流路等を有する装置を用いてもよい。<GeH 4 manufacturing equipment>
In the present method, there is no particular limitation as long as the electrochemical cell is used. In addition to the cell, for example, a power source, a measuring means (FT-IR, pressure gauge (PI), integrator, etc.) as shown in FIG. An apparatus having a conventionally known member such as a nitrogen gas (N 2 ) supply path, a mass flow controller (MFC), and an exhaust path can be used.
Further, a device having the above-described circulation flow path and the like (not shown) may be used.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれら実施例に限定されない。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
［実施例１］
以下の材料を用い、図１に示すような、隔膜で陽極室と陰極室とを隔てた塩化ビニル製電気化学セルを作製した。
・陰極：０．５ｃｍ×０．５ｃｍ×厚さ０．５ｍｍのＡｇ板
・陽極：２ｃｍ×２ｃｍ×厚さ０．５ｍｍのＮｉ板
・隔膜：ナフィオン（登録商標） ＮＲＥ−２１２（シグマアルドリッチ社製）
・電解液：４ｍｏｌ／ＬのＫＯＨ水溶液に９０ｇ／Ｌの濃度でＧｅＯ2を溶解させた液体
・陰極室への電解液導入量：１００ｍＬ
・陽極室への電解液導入量：１００ｍＬ
・標準電極：銀−塩化銀電極を陰極に設置[Example 1]
Using the following materials, an electrochemical cell made of vinyl chloride in which an anode chamber and a cathode chamber were separated by a diaphragm as shown in FIG.
-Cathode: Ag plate of 0.5cm x 0.5cm x 0.5mm thickness-Anode: Ni plate of 2cm x 2cm x 0.5mm thickness-Diaphragm: Nafion (registered trademark) NRE-212 (manufactured by Sigma-Aldrich) )
・ Electrolyte: A liquid obtained by dissolving GeO 2 at a concentration of 90 g / L in a 4 mol / L KOH aqueous solution ・ Amount of electrolyte introduced into the cathode chamber: 100 mL
・ Amount of electrolyte introduced into anode chamber: 100mL
・ Standard electrode: Silver-silver chloride electrode is installed on the cathode
得られた電気化学セルにおける、陽極室および陰極室の気相部分を窒素ガス（Ｎ2）でパージした後、電源として、北斗電工（株）製Ｈｚ−５０００を用い、−５７ｍＡで１０分間電流を流すことで、電気化学的にＧｅＨ4を製造した。このときの電流密度は、９９ｍＡ／ｃｍ2であった。
なお、電流を流す際に電気化学セルの温度をコントロールしなかったところ、反応温度は１４℃であった。
陰極室の出口ガスを、積算計を用いて測定することで、反応により生じた出口ガス全量（ＧｅＨ4および水素ガスを含むガス）を測定し、ＦＴ−ＩＲを用いることで、出口ガス全量中のＧｅＨ4濃度を測定した。これらの測定結果から、ＧｅＨ4の発生量を算出した。In the obtained electrochemical cell, the gas phase portions of the anode chamber and the cathode chamber were purged with nitrogen gas (N 2 ), and then a current was supplied at −57 mA for 10 minutes using Hz-5000 manufactured by Hokuto Denko Corporation as a power source. Was flowed to electrochemically produce GeH 4 . The current density at this time was 99 mA / cm 2 .
The reaction temperature was 14 ° C. when the temperature of the electrochemical cell was not controlled when applying a current.
By measuring the outlet gas of the cathode chamber using an integrator, the total amount of the outlet gas generated by the reaction (gas containing GeH 4 and hydrogen gas) is measured, and by using FT-IR, the total amount of the outlet gas is measured. Was measured for GeH 4 concentration. From these measurement results, the amount of GeH 4 generated was calculated.
電流を印加してから、０〜１０分の間のＧｅＨ4の発生量と、印加した電流量とから、下記式に基づいて電流効率を算出し、該電流効率を反応時間１０分間の電流効率とした。結果を表１に示す。
電流効率（％）＝［前記発生量（ｍｍｏｌ／ｍｉｎ）のＧｅＨ4が発生するのに相当する電気量（Ｃ／ｍｉｎ）×１０（ｍｉｎ）×１００］／［印加した全電気量（Ｃ／ｍｉｎ）×１０（ｍｉｎ）］The current efficiency is calculated based on the following equation from the amount of GeH 4 generated between 0 and 10 minutes after the current is applied and the amount of the applied current, and the current efficiency is calculated based on the current efficiency for a reaction time of 10 minutes. And Table 1 shows the results.
Current efficiency (%) = [the amount of electricity (C / min) × 10 (min) × 100 corresponding to the generation of GeH 4 of the above-mentioned amount (mmol / min)] / [total amount of electricity applied (C / min) min) × 10 (min)]
［比較例１］
陰極として０．５ｃｍ×０．５ｃｍ×厚さ０．５ｍｍのＣｕ板を使用し、印加する電流を−８５ｍＡで１０分間に変更した以外は実施例１と同様の条件で反応を行った。結果を表１に示す。[Comparative Example 1]
The reaction was carried out under the same conditions as in Example 1 except that a Cu plate of 0.5 cm × 0.5 cm × 0.5 mm thickness was used as the cathode, and the applied current was changed to −85 mA for 10 minutes. Table 1 shows the results.
［比較例２］
陰極として０．５ｃｍ×０．５ｃｍ×厚さ０．５ｍｍのＣｄ板を使用し、印加する電流を−５５ｍＡで１０分間に変更した以外は実施例１と同様の条件で反応を行った。結果を表１に示す。[Comparative Example 2]
The reaction was carried out under the same conditions as in Example 1 except that a Cd plate of 0.5 cm × 0.5 cm × 0.5 mm thick was used as the cathode, and the applied current was changed to −55 mA for 10 minutes. Table 1 shows the results.
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