201229321 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明是關於藉由金屬與含有有機化合物的電解液 之電解反應（electrolytic react ion)生成有機金屬化 合物（organometal 1 ic compound)之電解生成裝置 . (electrolysis device)。 [先前技術] [0002] 隨著數位家電或半導體照明等的電子領域的發展’ 0 化合物半導體的需要今後越發令人期待。化合物半導體 材料之一的氮化鎵（GaN)被應用於發光二極體 (LED:Light Emitting Diode)或雷射二極體 (LD:Laser Diode)等的發光元件（light emitting device) ’ 或者場效電晶體（FET:Field Effect Transistor)或高電子遷移率電晶體（HEMT: High Electron Mobility Transistor)等的電子元件。但 疋’氮化鎵的基板價格高《因此，當製造包含氮化鎵的 〇 電子70件時，例如藉由使用有機金屬化合物之三曱基鎵 (TMG:trimethyiganium)等的有機金屬化學氣相沉積 法（M0CVD法：Meta卜Organic Chemical Vapor201229321 VI. Description of the Invention: [Technical Field] [0001] The present invention relates to electrolysis of an organometallic compound (organometal 1 ic compound) by electrolytic reaction of a metal with an electrolyte containing an organic compound Generating device. (electrolysis device). [Prior Art] [0002] With the development of electronic fields such as digital home appliances or semiconductor lighting, the demand for compound semiconductors is expected to become more and more promising in the future. Gallium nitride (GaN), one of the compound semiconductor materials, is applied to a light emitting device such as a light emitting diode (LED: Light Emitting Diode) or a laser diode (LD: Laser Diode). An electronic component such as a FET (Field Effect Transistor) or a high electron mobility transistor (HEMT: High Electron Mobility Transistor). However, the substrate of 氮化' gallium nitride is expensive. Therefore, when 70 〇 electrons including gallium nitride are fabricated, for example, an organometallic chemical vapor phase such as trimethygium (TMG) using an organometallic compound is used. Deposition method (M0CVD method: Meta Bu Organic Chemical Vapor
Deposition咖化“）在藍寶石基板（sapphire SUbStrate)之上形成氮化鎵層，在其上製作各種元件。 此處若舉發光二極體為例的話，則氮化鎵的品質會給 予發光二極體的亮度與可靠度（reliability)決定性的 影響。因此，來自半導體製造業者對成為氣化鎵的原料 的二曱基鎵要求高純度的品質。 _ 迄今一般三甲基鎵是使鹵化鎵（gallium halide) 1001472#單編號A0101 第3頁/共22頁 1013043898-0 201229321 與烧基紹（alkylaluminium)反應而生成（例如參照專利 文獻1)。依照專利文獻1，在1，3，5-三甲苯 (mesitylene)的存在下使三氯化鎵（gal 1 ium trichloride)與三甲基銘（trimethylaluminuin)反應 ，合成三f基鎵。 另一方面，藉由將金屬鎵與格任亞化合物（格任亞試 劑（Grignard reagent))電解並使其反應，生成三曱基 鎵的方法也已知（例如參照專利文獻2)。依照專利文獻2 ’首先在電解槽中使格任亞化合物與極性非質子性 (polar aprotic)液體之乙醚（diethyl ether)與金屬 鎵反應，得到三甲基鎵-乙醚加成物 (TMGE:trimethylgal1ium diethyl ether adduct) 。接著’以揮發性低的二異戊醚（(jiiSOpentyi ether·) 置換三甲基鎵-乙域加成物中的乙鍵。然後，由三曱基鎵 -二異戊醚加成物使二異戊醚解離，當作三甲基鎵。格任 亞化合物'乙醚及金屬鎵的電解反應是對具備鉑陰極與 鎵池消耗陽極的電解槽施加1〇〇V的電壓而執行。 [專利文獻1]曰本國特開2006-342101號公報 [專利文獻2]曰本國特開眧59_47388號公報 【發明内容】 [0003] 但是，在上述的先前技術存在幾個問題。在專利文 獻1中雖然使用齒化鎵及烧基紹當作三甲基鎵的原料但 。亥等原料有處理上應留意的點。鹵化鎵因吸濕性 (hygr〇scopicity)高，故很難長期間維持品質。若以 吸濕的狀態的齒化鎵當作原料使用的話，則因與燒基銘 …的反應性不佳，故三曱基鎵的產率（yield)降低。= 10014724#單編號A〇101 第4頁/共22頁 " 1013043 201229321 因烧基銘為自發著火性物質（spontaneous-ignitable substance)，故處理上特別需要慎重。再者，因烧基銘 本身需在高溫高壓條件下生成，故不太適合穩定的生產 、大量的生產。 另一方面，在專利文獻2中因在生成三曱基鎵時，以 金屬鎵與格任亞化合物當作原料，故原料品質比較穩定 ，處理也容易。而且，因電解反應可在較低溫（50~60°C) 且常壓下進行，故可容易進行製造。 如此，記載於專利文獻2之進行金屬鎵與格任亞化合 物的電解反應的製造方法比專利文獻1所代表之進行鹵化 鎵與烷基鋁的反應的情形還具有許多優點。 但是，專利文獻2的製造方法在進行工業的製造上有 問題。在該文獻中如上述，為了進行電解反應，使用具 備鉑陰極與鎵池消耗陽極的電解槽，但藉由該電解槽有 效地且大量地生成高品質的三甲基鎵在現實上很困難。 依照該文獻，該電解生成裝置中的鉑陰極的面積只不過 是lcm2。鎵池消耗陽極也被記載為20〜40g左右。因此， 當以該電解槽進行電解反應時，三甲基鎵的前驅物 (precursor)之三甲基鎵-乙醚加成物的生成量非常少， 為了以工業的規模製造三甲基鎵無論如何也達不到。 而且，電解反應通常在電極間的區域很活潑，而在 離開電極的區域則不太進行反應。因此，在電解反應中 需對電解槽或電極的構造下功夫。此點，專利文獻2因不 以電解槽或電極的構造為課題，故針對設法用以使電解 反應均勻化（homogenization)完全未觸及。但是，現 實問題若電解反應不均勻（heterogeneous)，則因在同 1001472#^^ A〇101 第5頁/共22頁 1013043898-0 201229321 一電解液中產生成分的偏差的情形，與在各別的電解液 中組成或生成量產生個別差異（i nd i v i dua 1 difference)的情形，結果無法有效地生成高品質的三 曱基鎵。 而且，在專利文獻2中當想增加三甲基鎵的生成量時 ，不得不加大電解槽的尺寸並增加電解液及熔融金屬的 供給量。其結果，裝置的製造、維持成本就會增大。而 且，當實施按比例增大（scale up)時，一旦反應開始的 話，該反應就會長期間連續地進行，故反應的控制變得 困難。因此，對按比例增大時的三甲基鎵的製造被要求 更慎重的操作。 如此在現狀中，安全且穩定地生成高品質的有機金 屬化合物之電解生成裝置尚未被開發。本發明是鑑於上 述問題點所進行的創作，其目的為著眼於反應物為液體（ 亦即含有有機化合物的電解液及熔融金屬），提供適合工 業上生成三曱基鎵所代表的有機金屬化合物之電解生成 裝置。 為了解決上述課題之與本發明有關的電解生成裝置 的特徵構成在於： 一種電解生成裝置，藉由金屬與含有有機化合物的 電解液之電解反應生成有機金屬化合物，包含： 以前述金屬在熔點以上的溫度熔融，以熔融金屬的 狀態被導入，並且被供給前述電解液之配設陽極及陰極 的電解槽；以及 儲存前述電解液之儲存槽， 在前述電解槽的内部中，前述陽極及前述陰極各自 1001472#單編號 A〇101 第6頁/共22頁 1013043898-0 201229321 被配置成與前述熔融金屬及前述電解液接觸的狀態， 在前述電解槽與前述儲存槽之間前述電解液被循環 如在上述課題所述的，當使用習知的電解生成裝置 生成有機金屬化合物時，電解反應容易變成不均勻，因 此有機金屬化合物的效率的生成困難，也影響生成物 (product)的品質。而且，為了增加有機金屬化合物的 生成量，需要按比例增大的實施，除了成本面的問題外 ，安全性的問題也被擔心。此乃因電解反應一旦開始的 話，則之後就很難增減電解液的量或使電解液移動。 關於在工業上進行製造，為了安全且穩定地生成高 品質的有機金屬化合物，考慮使金屬與適量的電解液反 應很有效。若進行這種反應，則不浪費且平穩地使金屬 與電解液的反應進行成為可能。 因此，本發明者們專心致力檢討的結果，發現在電 解生成裝置中，藉由除了電解槽之外另外配設儲存槽， 在該儲存槽與電解槽之間使電解液循環，使金屬與電解 液的反應均勻且穩定地進行，其結果可有效且大量地生 成高品質的有機金屬化合物。 在本構成的電解生成裝置中，在電解槽與儲存槽之 間使電解液循環。因可藉由適量地調整電解液的循環量 ，將電解液必要的份供給至電解槽，故與無儲存槽的電 解生成裝置比較，可有效且確實地使電解反應產生。其 結果，有機金屬化合物的品質穩定，生成量也增大。而 且，因可藉由將無助於電解反應的電解液儲存於儲存槽 ，使電解槽小型化，故可在電解槽内充分地使電解反應 1QQ14724f單編號A0101 第7頁/共22頁 1013043898-0 201229321 進行。而且，因電解槽在設備之中價格較高，使電解槽 小型化大大地貢獻於裝置全體的維持成本的削減。 而且，在習知的電解槽中因位置離開電極，故存在 反應成為不充分的液體部分，惟因在本構成中電解液在 循環，故攪拌被充分進行，不產生未反應液。然後，藉 由重複電解液的循環，使得電解液全體的反應更進一步 被均勻化，可有效地得到高品質的有機金屬化合物。此 外，若調整電解液的循環量，則自反應開始後控制反應 變的容易，可生成安全且高品質的有機金屬化合物。 在與本發明有關的電解生成裝置中，前述陽極及前 述陰極各自完全浸潰於前述熔融金屬及前述電解液，而 在前述電解槽的深度方向中被疊層配置，前述陰極離開 前述炫融金屬的液面較佳。 在本構成的電解生成裝置中，因陽極與陰極在電解 槽的深度方向中被疊層配置，故可有效地利用電解槽的 形狀而配置兩電極。例如即使是較淺一些的電解槽，也 能藉由疊層配置仿照電解槽的底面的形狀的電極，供給 對電解槽的容量足夠的電能，故熔融金屬與電解液的反 應更被促進。其結果，有機金屬化合物的品質及生成量 更提高，可有效地進行工業的製造。此外，若為疊層配 置電極的構成，則即使是在深度方向中更進一步縮小電 解槽的尺寸的情形，也能不變更該電極的構造而原封不 動地使用，故在設備成本面也有利。 在與本發明有關的電解生成裝置中，前述陰極與前 述溶融金屬的液面的間隙（clearance)被設定於5~10mm 較佳。 臟4724#單編號删1 第8頁/共22頁 1013043898-0 201229321 在本構成的電解生成裝置中，藉由令陰極與熔融金 屬的液面的間隙的下限值為5mm，可一邊確實地防止電極 間的短路，一邊進行有機金屬化合物的工業的製造。另 一方面，藉由令陰極與熔融金屬的液面的間隙的上限值 為10關，可確實地製造高品質的有機金屬化合物。 在與本發明有關的電解生成裝置中，前述金屬為鎵 ，前述電解液為格任亞化合物的乙醚溶液，前述有機金 屬化合物為院基鎵-乙趟加成物較佳。 Ο [0004]Deposition coffee"" forms a gallium nitride layer on a sapphire substrate (sapphire SUbStrate), on which various components are fabricated. Here, if a light-emitting diode is taken as an example, the quality of gallium nitride is given to the light-emitting diode. The brightness and reliability have a decisive influence. Therefore, the semiconductor manufacturer has a high purity quality for the gallium-based gallium which is a raw material for gallium hydride. _ To date, trimethylgallium is a gallium halide (gallium halide). 1001472#Single number A0101 Page 3/22 pages 1013043898-0 201229321 It is produced by reaction with alkylaluminium (for example, refer to Patent Document 1). According to Patent Document 1, in 1,3,5-trimethylbenzene ( In the presence of mesitylene, gallium trichloride (gal 1 ium trichloride) is reacted with trimethylaluminuin to synthesize trif-based gallium. On the other hand, by using metal gallium and gemenar compounds (Ge Renya) A method in which a reagent (Grignard reagent) is electrolyzed and reacted to form trimethyl gallium is also known (for example, refer to Patent Document 2). According to Patent Document 2, first, in the electrolytic cell, Grenada is combined. Reacting with a polar aprotic liquid diethyl ether and metal gallium to obtain a trimethylgallium-diethyl ether adduct (TMGE: trimethylgal1ium diethyl ether adduct) followed by 'low volatility Ether ((jiiSOpentyi ether) replaces the ethyl bond in the trimethylgallium-B domain adduct. Then, the di-amyl ether is dissociated from the trimethylgallium-diisoamyl ether adduct as trimethyl The electrolysis reaction of the gallium and the metal gallium is carried out by applying a voltage of 1 〇〇V to an electrolytic cell having a platinum cathode and a gallium cell consuming anode. [Patent Document 1] 曰 National Patent Publication No. 2006-342101 [Patent Document 2] Japanese Laid-Open Patent Publication No. 59-47388 [Draft] [0003] However, there are several problems in the above-described prior art. In Patent Document 1, although gallium galvanizing and sintering are used as three The raw material of methyl gallium, however, should be noted in the processing of raw materials such as hai. Since gallium halide has high hygroscopicity, it is difficult to maintain quality for a long period of time. If it is used as a raw material, it will be used as a base... The reactivity is not good, so the yield of tris-gallium is reduced. = 10014724#单单A〇101 Page 4 of 22 " 1013043 201229321 Spontaneous ignition material (spontaneous-ignitable) Substance), so it is particularly necessary to be cautious in handling. Furthermore, since the base is required to be produced under high temperature and high pressure conditions, it is not suitable for stable production and mass production. On the other hand, in Patent Document 2, since gallium metal and grenium compounds are used as raw materials in the formation of trimethyl gallium, the quality of the raw materials is relatively stable and handling is easy. Further, since the electrolysis reaction can be carried out at a relatively low temperature (50 to 60 ° C) and at a normal pressure, it can be easily produced. As described above, the production method for performing the electrolytic reaction of the metal gallium and the gemenite compound described in Patent Document 2 has many advantages as compared with the case where the reaction of the gallium halide and the aluminum alkyl is carried out as represented by Patent Document 1. However, the manufacturing method of Patent Document 2 has a problem in industrial production. As described above, in this document, in order to carry out an electrolytic reaction, an electrolytic cell having a platinum cathode and a gallium cell consuming anode is used. However, it is practically difficult to efficiently and stably produce high-quality trimethylgallium by the electrolytic cell. According to this document, the area of the platinum cathode in the electrolysis generating apparatus is only lcm2. The anode of the gallium cell is also described as being about 20 to 40 g. Therefore, when the electrolytic reaction is carried out in the electrolytic cell, the amount of the trimethylgallium-diethyl ether adduct of the precursor of trimethylgallium is very small, in order to manufacture trimethylgallium on an industrial scale anyway. Also not reach. Moreover, the electrolysis reaction is usually very active in the region between the electrodes, and is less reactive in the region away from the electrode. Therefore, it is necessary to work on the structure of the electrolytic cell or the electrode in the electrolytic reaction. In this regard, in Patent Document 2, since the structure of the electrolytic cell or the electrode is not a problem, it has been tried to make the electrolysis reaction homogenization completely untouched. However, if the actual reaction is heterogeneous, the deviation of the composition in the electrolyte is the same as that in the 1001472#^^ A〇101 page 5/22 page 1013043898-0 201229321 In the case where the composition or the amount of the electrolyte in the electrolyte is different (i nd ivi dua 1 difference), the result is that the high-quality trimethyl gallium cannot be efficiently produced. Further, in Patent Document 2, when it is desired to increase the amount of formation of trimethylgallium, it is necessary to increase the size of the electrolytic cell and increase the supply amount of the electrolytic solution and the molten metal. As a result, the manufacturing and maintenance costs of the device increase. Further, when scale-up is carried out, once the reaction is started, the reaction proceeds continuously for a long period of time, so that control of the reaction becomes difficult. Therefore, the manufacture of trimethylgallium when scaled up is required to be handled with greater care. Thus, in the current state of the art, an electrolysis apparatus for efficiently and stably producing high-quality organic metal compounds has not been developed. The present invention has been made in view of the above problems, and an object thereof is to provide an organometallic compound which is suitable for industrially producing trimethyl gallium by a liquid (that is, an electrolyte containing an organic compound and a molten metal). Electrolytic generating device. In order to solve the above-described problems, an electrolytic production apparatus according to the present invention is characterized in that an electrolytic production apparatus generates an organometallic compound by electrolytic reaction of a metal with an electrolytic solution containing an organic compound, and includes: the metal is at a melting point or higher. The temperature is melted, introduced into the molten metal, and supplied to the electrolytic cell in which the anode and the cathode are disposed; and the storage tank storing the electrolyte; in the inside of the electrolytic cell, the anode and the cathode are respectively 1001472#单号A〇101 Page 6/22 pages 1013043898-0 201229321 In a state of being in contact with the molten metal and the foregoing electrolyte, the electrolyte is circulated between the electrolytic cell and the storage tank. In the above-mentioned problem, when an organic metal compound is produced by a conventional electrolytic production apparatus, the electrolytic reaction is likely to become uneven, and therefore the production of the efficiency of the organometallic compound is difficult, and the quality of the product is also affected. Further, in order to increase the amount of formation of the organometallic compound, a scale-up implementation is required, and in addition to the problem of cost, the problem of safety is also worried. This is because once the electrolysis reaction is started, it is difficult to increase or decrease the amount of the electrolyte or move the electrolyte. In order to manufacture industrially, in order to produce a high-quality organometallic compound safely and stably, it is effective to react a metal with an appropriate amount of electrolyte. When such a reaction is carried out, it is possible to carry out the reaction of the metal and the electrolyte smoothly without wasting and smoothly. Therefore, the present inventors focused on the results of the review and found that in the electrolytic generation device, by additionally providing a storage tank in addition to the electrolytic cell, the electrolyte is circulated between the storage tank and the electrolytic cell to cause metal and electrolysis. The reaction of the liquid proceeds uniformly and stably, and as a result, a high-quality organometallic compound can be efficiently and largely produced. In the electrolytic production apparatus of the present configuration, the electrolytic solution is circulated between the electrolytic cell and the storage tank. Since the necessary amount of the electrolytic solution can be supplied to the electrolytic cell by appropriately adjusting the circulation amount of the electrolytic solution, the electrolytic reaction can be efficiently and surely produced as compared with the electrolytic generating device without the storage tank. As a result, the quality of the organometallic compound is stabilized and the amount of formation is also increased. Further, since the electrolytic solution can be miniaturized by storing the electrolytic solution which does not contribute to the electrolytic reaction in the storage tank, the electrolytic reaction can be sufficiently made in the electrolytic cell 1QQ14724f, single number A0101, page 7 / total 22 pages 1013043898- 0 201229321 Conducted. Further, since the electrolytic cell is expensive in the equipment, the miniaturization of the electrolytic cell greatly contributes to the reduction of the maintenance cost of the entire apparatus. Further, in the conventional electrolytic cell, since the electrode is separated from the electrode due to the position, the reaction is insufficient, and since the electrolytic solution is circulated in the present configuration, the stirring is sufficiently performed, and no unreacted liquid is generated. Then, by repeating the circulation of the electrolytic solution, the reaction of the entire electrolytic solution is further uniformized, and a high-quality organometallic compound can be efficiently obtained. Further, when the circulation amount of the electrolytic solution is adjusted, it is easy to control the reaction from the start of the reaction, and a safe and high-quality organometallic compound can be produced. In the electrolytic production apparatus according to the present invention, the anode and the cathode are each completely impregnated with the molten metal and the electrolytic solution, and are stacked in a depth direction of the electrolytic cell, and the cathode is separated from the molten metal. The liquid level is preferred. In the electrolytic production apparatus of the present configuration, since the anode and the cathode are stacked in the depth direction of the electrolytic cell, the electrodes can be effectively disposed by the shape of the electrolytic cell. For example, even in a shallower electrolytic cell, it is possible to supply electric energy sufficient for the capacity of the electrolytic cell by laminating an electrode which is patterned in the shape of the bottom surface of the electrolytic cell, so that the reaction between the molten metal and the electrolytic solution is further promoted. As a result, the quality and amount of the organometallic compound are further improved, and industrial production can be efficiently performed. Further, in the case of the configuration in which the electrodes are stacked, even if the size of the electrolytic cell is further reduced in the depth direction, the structure of the electrode can be used without changing the structure of the electrode, which is advantageous in terms of equipment cost. In the electrolytic production apparatus according to the present invention, it is preferable that the clearance of the liquid surface of the cathode and the molten metal is set to 5 to 10 mm. Dirty 4724# single number deletion 1 page 8 / total 22 page 1013043898-0 201229321 In the electrolytic generation device of the present configuration, the lower limit of the gap between the cathode and the molten metal is 5 mm, and it is possible to surely Industrial production of organometallic compounds is carried out while preventing short circuits between the electrodes. On the other hand, by setting the upper limit of the gap between the cathode and the molten metal to 10, the high-quality organometallic compound can be reliably produced. In the electrolytic production apparatus according to the present invention, the metal is gallium, the electrolytic solution is a diethyl ether solution of a Gebyan compound, and the organic metal compound is preferably a gallium-acetonitrile adduct. Ο [0004]
若為本構成的電解生成裝置，則因金屬為鎵，電解 液為格任亞化合物的乙醚溶液，故工業上可製造高品質 的院基鎵-乙謎加成物。 【實施方式】 根據圖面說明與本發明的電解生成裝置有關的實施 形態。但是，本發明無意被限定於記載於在以下說明的 實施形態或圖面的構成。 圖1是顯示與本發明的電解生成裝置100有關的電解 槽10的全體構造之斜視圖。圖2是圖1所示的電解槽10之 分解斜視圖。而且，圖3是顯示本發明的實施例，電解生 成裝置100與其後段的處理裝置之全體構成圖。 在與本發明有關的電解生成裝置1〇〇中，藉由金屬與 含有有機化合物的電解液的電解反應生成有機金屬化合 物。在本實施形態中，金屬使用鎵（Ga)，有機化合物使 用格任亞化合物（CH3MgI)。鎵是在加溫到熔點（約29. 7 °C)以上的溫度的熔融金屬的狀態下使用。格任亞化合物 是在溶解於溶媒之乙醚（Et2〇)的狀態下當作電解液使用 1001472#單編號 A_ 第9頁/共22頁 1013043898-0 201229321 電解生成裝置100主要的構成包含電解槽10與儲存 槽20。在電解槽10的内部配設有用以使電解反應進行的 陽極50及陰極60。陽極50配置於與滯留於電解槽10的底 部的鎵始終接觸的位置。陰極60在電解槽10内浸潰於流 動於鎵的上方的電解液中而被配置。除了電解槽10之外 另外配設有儲存槽20，儲存槽20儲存供給至電解槽10的 電解液，並且反應後的電解液由電解槽10返回。電解槽 10與儲存槽20之間透過兩條送液管30a、30b連接，據此 ，形成流體迴路30。藉由使配設於流體迴路30的途中的 循環泵40動作，電解液循環於電解槽10與儲存槽20之間 〇 此處，使用圖1及圖2說明電解槽10的詳細的構成。 電解槽10是由下部塊（lower block)ll、陽極配置塊12 、中間塊1 3、陰極配置塊14及上部塊（upper block) 15 構成。 下部塊11構成電解槽10的底板，支撐供給至電解槽 10内的熔融鎵及電解液的重量。由於下部塊11與熔融鎵 直接接觸，故構成材料使用不與熔融鎵反應且下部塊11 自身也不劣化的财腐餘性材料（corros ion res i stan t material)(例如氟樹脂（fluororesin)(聚四氟乙烯 :polytetrafluoroethylene)等））° 陽極配置塊12被疊層於下部塊11之上，在電解槽10 内配置陽極50而發揮功能。在陽極配置塊12於上下方向 形成有陽極配置用的第一框部12a，更於側面形成有連著 第一框部12a的第一孔部12b。陽極50是由鈦製的網狀板 (mesh plate)50a與鈦製的陽極導線50b構成，在將陽 臟472#單編號謝01 第10頁/共22頁 1013043898-0 201229321 極50固定於陽極配置塊12時，一邊將陽極導線5〇b插通於 第一孔部12b ’ 一邊將網狀板50a嵌合於第一框部12a。 據此，陽極50與陽極配置塊12—體化。當需使陽極5〇的 固定更堅固時’可更進一步進行螺絲固定等◊由於陽極 配置塊12也與炼融鎵直接接觸，故構成材料使用不與炫 融鎵反應且陽極配置塊12自身也不劣化的耐腐蝕性材料（ 例如氟樹脂（聚四氟乙烯等））。 中間塊13被疊層於陽極配置塊12之上，確實使上述 Ο 的陽極50與後述的陰極60分離而發揮功能。陽極50被配 置成與炫融鎵接觸的狀態。因此，當熔融鎵與電解液的 界面紊亂時’往往會發生短路等的故障。因此，在中間 塊13設有空間部13a，以便包爵鎵與電解液的界面。據此 ’錄與電解液的界面穩定，陰極6〇不會接觸鎵。中間塊 13的厚度設定為陰極6〇與鎵的液面的間隙成為5 1〇咖左 右較佳°藉由令陰極6〇與鎵的液面的間隙的下限值為5mm ’可一邊確實地防止電極間的短路，一邊進行三曱基鎵_ 乙喊加成物（TMGE)的工業的製造。另一方面，藉由令陰 極60與鎵的液面的間隙的上限值為10mm，可確實地製造 ° 質的二曱基嫁-乙謎加成物。可令空間部13a的形狀 為與上述的第—框部12a及後述的第二框部14a同形狀。 但是’使空間部13a比第一框部12a及第二框部14a小一 些也有效。此情形，因中間塊13當作陽極5〇及陰極60的 壓緊構件而發揮功能，故構造更穩定。由於中間塊13與 熔融鎵及電解液直接接觸，故構成材料使用不與熔融鎵 及電解液反應且中間塊13自身也不劣化的耐腐蝕性材料（ __單_:氟樹脂（聚讀乙稀等）） 1013043898-0 第11頁/共22頁 201229321 陰極配置塊14被疊層於中間塊13之上，在電解槽10 内配置陰極60而發揮功能。在陰極配置塊14於上下方向 形成有陰極配置用的第二框部148，更於侧面形成有連著 第—框部14a的第二孔部14b。陰極60是由鈦製的網狀板 6〇a與妖製的陰極導線6〇b構成在將陰極固定於陰極 配置塊14時，一邊將陰極導線6〇b插通於第二孔部以匕， 邊將網狀板60a嵌合於第二框部14&。據此，陰極6〇與 陰極配置塊14 —體化。當需使陰極6〇的固定更堅固時， 可更進一步進行螺絲固定等。由於陰極配置塊14與電解 液直接接觸’故構成材料使用不與電解液反應且陰極配 置塊14自身也不劣化的耐腐蝕性材料（例如氟樹脂（聚四 氟乙烯等））。 上部塊15被疊層於陰極配置塊14之上，構成電解槽 的頂板（top plate)。由於上部塊15與電解液直接接 觸，故構成材料使用不與電解液反應且上部塊15自身也 不劣化的耐腐蝕性材料（例如氟樹脂（聚四氟乙烯等））。 藉由以上的下部塊Π、陽極配置塊12 '中間塊13、 陰極配置塊14及上部塊15依此順序由下方開始疊層配置 ，可構成具備内部空間的電解槽1〇。疊層後，各塊藉由 螺絲固定等的機械的接合而被固定較佳，惟藉由利用接 著劑等的化學的接合也無妨。由於各塊的疊層配置的結 果’陽極50與陰極60在電解槽1〇的深度方向中被疊層配 置，因此可有效地利用電解槽1〇的形狀而配置兩電極。 例如即使是較淺-些的電解槽1〇，也能藉由疊層配置仿 照電解槽1 0的底面的形狀的電極，供給對電解槽丨〇的容 10014724^ 1013043898-0 ΐ足夠的電能，故鎵與電解液的反應更被促進。其結果 Α0101 第12頁/共22頁 201229321 ，三曱基鎵-乙醚加成物的品質及生成量更提高，可有效 地進行工業的製造。此外，若為疊層配置電極的構成， 則即使是在深度方向中更進一步縮小電解槽ίο的尺寸的 情形，也能不變更該電極的構造而原封不動地使用，故 在設備成本面也有利。 在電解槽10的内部空間中如上述，藉由使熔融鎵與 電解液電解反應，進行有機金屬化合物之三甲基鎵-乙醚 加成物的生成。此處，在電解槽10配設有熔融鎵被導入 的鎵導入部1 0a，及留住導入到内部空間的鎵之栓1 Ob。 Ο i 而且，同時在電解槽ίο配設有電解液被導入的電解液導 入部10c，及電解液被排出的電解液排出部10d。如由圖2 理解的，鎵導入部10a遍及上部塊15、陰極配置塊14、中 間塊13及陽極配置塊12配設成管狀，在陽極配置塊12的 内部中連接於第一框部12a而成為彎頭構造（elbow structure)。而且，在本實施形態的電解槽10中，在對 鎵導入部10a成點對稱的位置也遍及上部塊15、陰極配置 塊14、中間塊13及陽極配置塊12配設有與鎵導入部10a ❹ 同樣的管狀構造。但是，上部塊15的管部被堵塞而成為 栓10b。因此，被導入到内部空間的鎵僅在電解反應中被 消耗。除此之外無鎵減少的因素。電解液導入部10c在與 鎵導入部10a並排的位置，由上部塊15遍及陰極配置塊14 配設成管狀，在陰極配置塊14的内部中連接於第二框部 14a而成為彎頭構造。電解液排出部10(1在對電解液導入 部10c成點對稱的位置遍及上部塊15到陰極配置塊14配設 成管狀，在陰極配置塊14的内部中連接於第二框部14a而 成為彎頭構造。使用於電解反應的電解液藉由循環泵40 10014724#單編號 A〇101 帛 13 頁 / 共 22 頁 1013043898-0 201229321 被由儲存槽20供給，通過電解液導入部10c並遍及陰极6〇 的網狀板60a及中間塊13的空間部13a，或者在被由電解 液排出部10d排出後，返回到儲存槽2〇。該電解液的循環 繼續到電解反應結束為止。 在本發明中因藉由適量地調整電解液的循環量，可 僅將必要份的電解液供給至電解槽1〇，故與無儲存槽 的電解生成裝置比較，有效且確實地使電解反應產生成 為可能。其結果，三甲基鎵-乙醚加成物的品質穩定，生 成量也增大。而且，因可藉由將無助於電解反應的電解 液儲存於儲存槽20，使電解槽1〇小型化，故可在電解槽 10内充分地使電解反應進行。而且，因電解槽在設備 之中價格較高’使電解槽小型化大大地貢獻裝置全體的 維持成本的削減。 而且，在習知的電解槽中因位置離開電極，故存在 反應成為不充分的液體部分，惟因在本構成中電解液在 循環，故攪拌被充分進行’不產生未反應液。然後，藉 由重複電解液的循環，使得電解液全體的反應更進一步 被均勻化，可有效地得到高品質的有機金屬化合物。此 外，若調整電解液的循環量，則自反應開始後控制反應 變的容易，可生成安全且高品質的有機金屬化合物。 [實施例] 使用具備上述的電解槽10及儲存槽20的電解生成裝 置生成了二甲基鎵-乙鍵加成物（TMGE)。而’且，由所 得到的三甲基鎵-乙醚加成物生成了最終目地之高純度的 三甲基鎵（TMG)。參照圖3 ’以下說明該等化合物的生成 程序當作實施例。 _472#單編號A0101 第14頁/共22頁 1013043898-0 201229321 〈電解程序〉 電解反應的製備是在儲存槽20準備格任亞化合物的 乙醚溶液當作電解液。將熔融狀態的鎵導入電解槽10， 陽極50一達到成為鎵的液面下的規定量，就使循環泵40 動作並由儲存槽2〇經由送液管3〇a將電解液導入電解槽1〇 。溢流（overflow)出電解槽1〇的電解液由送液管30b返 回到儲存槽20。在該狀態下對陽極50及陰極6〇施加電壓 。外加電壓（applied v〇itage)約30V(電流密度為 2A/dm2)。反應溫度約4〇°c。此時，在乙醚的存在下鎵與 格任亞化合物反應，生成三甲基鎵—乙醚加成物。包含三 甲基鎵-乙醚加成物的電解液返回到儲存槽2〇。 〈分餾程序〉 在儲存槽20的電解液除了未反應的格任亞化合物及 乙_外’也包含有副生成物（by-pr〇duct)之埃化錯 (Mgl2)(magnesium iodide)及在生成格任亞化合物的 階段使用的峨曱统（CH3I)( methyl iodide)。因此將含 有該等各成分的電解液分餾（分餾程序）。逐漸使電解液 升溫，最終加溫到180°C。此外，為了得到最終生成物 (end product)之三曱基鎵，在三甲基鎵-乙醚加成物的 狀態下進行分餾的理由乃因三甲基鎵-乙醚加成物（海點： 約98°C)與碘甲烷（沸點：約43°C)其沸點差距大，兩者的 分離（separation)容易。順便一提，三甲基鎵因沸點約 56°C，當嘗試由沸點約43°C的碘甲烷分離時，三甲基鎵 的產率降低。分餾程序的結果，得到包含三甲基鎵_乙_ 加成物的分餾物（fraction)。但是，該分餾物還包含有 少量的乙醚及蛾曱院。因此，追加乙謎再度進行分館（再 單編號 A0101 第15頁/共22頁 1013043898-0 201229321 分餾程序），完全除去碘甲烷。另一方面，分餾程序後的 殘留物包含有乙醚、格任亞化合物、碘曱烷及碘化鎮。 包含於殘留物的有機金屬化合物藉由水及酸分解，當作 穩定的化合物。因包含於殘留物的碘化合物（iodine compound)有用，故回收碘再利用。 〈單離（iso 1 at ion)程序〉 其次，將被精製的三曱基鎵-乙醚加成物（再分餾物） 移至預先放入異戊鍵（isoarayl ether)的反應槽 (reaction tank)70。以 78°C、30torr 對該溶液進行 減壓蒸餾（reduced pressure distillation)，將三 甲基鎵-乙醚加成物分解成三甲基鎵與乙醚，同時分離出 乙醚。然後，返回到低壓，以168°C使三甲基鎵蒸餾出（ 單離）。 〈精德（rectification)程序〉 所得到的鶴出液（distillate)包含有少量的異戊 謎等。因此’將餾出液導入到精餾塔（rectifying column)80，得到最終生成物之三甲基鎵。蒸餾鍋 (distillation still)内的液溫約90°C。藉由精餾得 到的尚純度的三曱基鎵在無塵室（C1 ean roora)(未圖示） 被填充捆包於容器中。順便一提’在本實施例得到的高 純度三甲基鎵藉由感應耦合電漿質譜儀法 (ICP-MS:Inductively Coupled Plasma Mass Spectrometry)及石墨爐原子吸收光譜儀法 (GFAAS：Grapbite Furnace Atomic Absorption Spectrometry)分析的結果，各種金屬含量（A1、Ca、In the case of the electrolysis apparatus of the present configuration, since the metal is gallium and the electrolytic solution is an ether solution of the Gerenite compound, a high-quality gallium-based puzzle additive can be produced industrially. [Embodiment] An embodiment relating to the electrolytic production apparatus of the present invention will be described based on the drawings. However, the present invention is not intended to be limited to the configurations described in the embodiments or drawings described below. Fig. 1 is a perspective view showing the entire structure of an electrolytic cell 10 relating to the electrolytic production apparatus 100 of the present invention. Fig. 2 is an exploded perspective view of the electrolytic cell 10 shown in Fig. 1. Further, Fig. 3 is a view showing the entire configuration of the electrolytic generation device 100 and the processing device in the subsequent stage, showing an embodiment of the present invention. In the electrolytic production apparatus 1 according to the present invention, an organometallic compound is produced by electrolytic reaction of a metal with an electrolytic solution containing an organic compound. In the present embodiment, gallium (Ga) is used for the metal, and the Gebyan compound (CH3MgI) is used as the organic compound. Gallium is used in a state of molten metal heated to a temperature higher than a melting point (about 29.7 ° C). The Grenium compound is used as an electrolyte in a state of being dissolved in a solvent of diethyl ether (Et2〇). 1001472#单号A_第9页/共22页1013043898-0 201229321 The main structure of the electrolysis device 100 includes the electrolysis cell 10 With the storage tank 20. An anode 50 and a cathode 60 for conducting an electrolysis reaction are disposed inside the electrolytic cell 10. The anode 50 is disposed at a position where it is always in contact with gallium remaining in the bottom of the electrolytic cell 10. The cathode 60 is placed in the electrolytic solution 10 to be immersed in an electrolytic solution flowing above the gallium to be disposed. In addition to the electrolytic cell 10, a storage tank 20 is disposed. The storage tank 20 stores the electrolyte supplied to the electrolytic cell 10, and the electrolytic solution after the reaction is returned from the electrolytic cell 10. The electrolytic cell 10 and the storage tank 20 are connected to each other through the two liquid supply pipes 30a and 30b, whereby the fluid circuit 30 is formed. By operating the circulation pump 40 disposed in the middle of the fluid circuit 30, the electrolytic solution is circulated between the electrolytic cell 10 and the storage tank 20, and the detailed configuration of the electrolytic cell 10 will be described with reference to Figs. 1 and 2 . The electrolytic cell 10 is composed of a lower block 11, an anode block 12, an intermediate block 13, a cathode block 14, and an upper block 15. The lower block 11 constitutes the bottom plate of the electrolytic cell 10, and supports the weight of the molten gallium and the electrolytic solution supplied into the electrolytic cell 10. Since the lower block 11 is in direct contact with the molten gallium, the constituent material uses a corrosion resit material that does not react with the molten gallium and the lower block 11 itself does not deteriorate (for example, fluororesin ( Polytetrafluoroethylene, etc.)) The anode arrangement block 12 is laminated on the lower block 11, and the anode 50 is disposed in the electrolytic cell 10 to function. In the anode block 12, a first frame portion 12a for arranging the anode is formed in the vertical direction, and a first hole portion 12b to which the first frame portion 12a is connected is formed on the side surface. The anode 50 is composed of a mesh plate 50a made of titanium and an anode lead wire 50b made of titanium, and is fixed at the anode of the anode 472# single number Xie 01 page 10 total 22 pages 1013043898-0 201229321 When the block 12 is placed, the mesh plate 50a is fitted into the first frame portion 12a while the anode lead 5b is inserted into the first hole portion 12b'. Accordingly, the anode 50 is integrated with the anode arrangement block 12. When it is necessary to make the fixing of the anode 5 更 stronger, the screw can be further fixed, etc. Since the anode arranging block 12 is also in direct contact with the fused gallium, the constituent material is not used for reacting with the galvanic gallium and the anode arranging block 12 itself is also A corrosion-resistant material that does not deteriorate (for example, a fluororesin (polytetrafluoroethylene, etc.)). The intermediate block 13 is laminated on the anode block 12, and the anode 50 of the above-mentioned crucible is surely separated from the cathode 60 to be described later to function. The anode 50 is configured to be in contact with the glaze. Therefore, when the interface between the molten gallium and the electrolytic solution is disordered, a failure such as a short circuit often occurs. Therefore, the intermediate portion 13 is provided with a space portion 13a so as to cover the interface between the gallium and the electrolyte. According to this, the interface between the recording and the electrolyte is stable, and the cathode 6〇 does not contact gallium. The thickness of the intermediate block 13 is set such that the gap between the cathode 6 〇 and the liquid surface of the gallium is about 5 〇 较佳 ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° Industrial production of tris-based gallium _ 喊 加 加 (TMGE) is carried out while preventing short-circuit between electrodes. On the other hand, by setting the upper limit of the gap between the cathode 60 and the liquid surface of gallium to 10 mm, it is possible to reliably produce a ruthenium-based copolymer. The shape of the space portion 13a can be made to have the same shape as the above-described first frame portion 12a and the second frame portion 14a to be described later. However, it is also effective to make the space portion 13a smaller than the first frame portion 12a and the second frame portion 14a. In this case, since the intermediate block 13 functions as a pressing member for the anode 5 and the cathode 60, the structure is more stable. Since the intermediate block 13 is in direct contact with the molten gallium and the electrolytic solution, the constituent material is a corrosion-resistant material that does not react with the molten gallium and the electrolytic solution and the intermediate block 13 itself does not deteriorate ( __单_: fluororesin (poly read B) Thin)) 1013043898-0 Page 11 of 22201229321 The cathode arrangement block 14 is laminated on the intermediate block 13, and the cathode 60 is disposed in the electrolytic cell 10 to function. In the cathode arrangement block 14, a second frame portion 148 for arranging the cathode is formed in the vertical direction, and a second hole portion 14b to which the first frame portion 14a is connected is formed on the side surface. The cathode 60 is composed of a mesh plate 6a made of titanium and a cathode wire 6〇b made of a demon, and when the cathode is fixed to the cathode block 14, the cathode lead 6〇b is inserted into the second hole. The mesh plate 60a is fitted to the second frame portion 14& Accordingly, the cathode 6A is integrated with the cathode arrangement block 14. When it is necessary to make the fixing of the cathode 6〇 stronger, screw fixing or the like can be further performed. Since the cathode arrangement block 14 is in direct contact with the electrolytic solution, the constituent material uses a corrosion-resistant material (for example, a fluororesin (polytetrafluoroethylene, etc.) which does not react with the electrolytic solution and does not deteriorate the cathode arrangement block 14 itself. The upper block 15 is laminated on the cathode block 14 to form a top plate of the cell. Since the upper block 15 is in direct contact with the electrolytic solution, the constituent material is a corrosion-resistant material (for example, a fluororesin (such as polytetrafluoroethylene)) which does not react with the electrolytic solution and does not deteriorate the upper block 15 itself. The lower block, the anode block 12, the intermediate block 13, the cathode block 14, and the upper block 15 are stacked in this order from the bottom in this order, and an electrolytic cell 1b having an internal space can be formed. After the lamination, each of the blocks is preferably fixed by mechanical joining such as screwing, but it is also possible by chemical bonding using an adhesive or the like. Since the results of the lamination arrangement of the respective blocks, the anode 50 and the cathode 60 are laminated in the depth direction of the electrolytic cell 1〇, the electrodes can be effectively disposed by the shape of the electrolytic cell 1〇. For example, even in the case of a shallower electrolytic cell, it is possible to supply sufficient electric energy to the electrolytic cell 容10014724^1013043898-0 by laminating the electrode in the shape of the bottom surface of the electrolytic cell 10. Therefore, the reaction between gallium and electrolyte is promoted. As a result, Α0101, page 12 of 22, 201229321, the triterpene gallium-diethyl ether adduct has improved quality and production, and can be industrially manufactured efficiently. In addition, when the electrode is disposed in a stacked manner, even if the size of the electrolytic cell is further reduced in the depth direction, the structure of the electrode can be used without changing the structure of the electrode, so that it is advantageous in terms of equipment cost. . In the internal space of the electrolytic cell 10, as described above, the formation of the trimethylgallium-diethyl ether adduct of the organometallic compound is carried out by electrolytically reacting the molten gallium with the electrolytic solution. Here, the electrolytic cell 10 is provided with a gallium introduction portion 10a into which molten gallium is introduced, and a plug 1 Ob for retaining gallium introduced into the internal space. Further, at the same time, the electrolytic solution introducing portion 10c into which the electrolytic solution is introduced and the electrolytic solution discharging portion 10d from which the electrolytic solution is discharged are disposed in the electrolytic cell. As understood from FIG. 2, the gallium introduction portion 10a is disposed in a tubular shape over the upper block 15, the cathode arrangement block 14, the intermediate block 13, and the anode arrangement block 12, and is connected to the first frame portion 12a in the interior of the anode arrangement block 12 Become an elbow structure. Further, in the electrolytic cell 10 of the present embodiment, the gallium introduction portion 10a is disposed over the upper block 15, the cathode arrangement block 14, the intermediate block 13, and the anode arrangement block 12 at a point symmetrical with respect to the gallium introduction portion 10a. ❹ The same tubular structure. However, the tube portion of the upper block 15 is blocked to become the plug 10b. Therefore, gallium introduced into the internal space is consumed only in the electrolytic reaction. In addition to this, there is no factor of gallium reduction. The electrolyte introduction portion 10c is disposed in a tubular shape over the cathode arrangement block 14 at a position parallel to the gallium introduction portion 10a, and is connected to the second frame portion 14a inside the cathode arrangement block 14 to have an elbow structure. The electrolyte discharge portion 10 (1 is disposed in a tubular shape at a point symmetrical with respect to the electrolyte introduction portion 10c throughout the upper block 15 to the cathode arrangement block 14, and is connected to the second frame portion 14a in the inside of the cathode arrangement block 14 to become Elbow structure. The electrolyte used for the electrolysis reaction is supplied from the storage tank 20 through the circulation pump 40 10014724# single number A 〇 101 帛 13 pages / total 22 pages 1013043898-0 201229321, and passes through the electrolyte introduction portion 10c and over the yin The mesh portion 60a of the pole 6 and the space portion 13a of the intermediate block 13 are returned to the storage tank 2 after being discharged from the electrolyte discharge portion 10d. The circulation of the electrolyte continues until the completion of the electrolytic reaction. In the invention, by appropriately adjusting the circulation amount of the electrolytic solution, only a necessary portion of the electrolytic solution can be supplied to the electrolytic cell 1 〇, so that the electrolytic reaction can be efficiently and surely produced as compared with the electrolytic generation device without the storage tank. As a result, the quality of the trimethylgallium-diethyl ether adduct is stable, and the amount of production is also increased. Moreover, since the electrolytic solution which does not contribute to the electrolysis reaction can be stored in the storage tank 20, the electrolytic cell 1 is made small. , The electrolytic reaction can be sufficiently carried out in the electrolytic cell 10. Further, since the electrolytic cell is expensive in the equipment, the miniaturization of the electrolytic cell greatly contributes to the reduction of the maintenance cost of the entire device. Moreover, in the conventional electrolytic cell Since the position leaves the electrode, the reaction becomes an insufficient liquid portion. However, since the electrolytic solution is circulated in the present configuration, the stirring is sufficiently performed to "not generate an unreacted liquid. Then, by repeating the circulation of the electrolytic solution, The reaction of the entire electrolyte solution is further uniformized, and a high-quality organometallic compound can be efficiently obtained. Further, when the circulation amount of the electrolytic solution is adjusted, it is easy to control the reaction from the start of the reaction, and it is possible to produce a safe and high-quality product. [Examples] A dimethyl gallium-ethyl bond adduct (TMGE) was produced by using an electrolysis apparatus including the above-described electrolytic cell 10 and storage tank 20, and 'and the obtained trimethyl group The gallium-diethyl ether adduct produces trimethylgallium (TMG) of high purity in the final destination. Referring to Figure 3, the following procedure for the formation of such compounds is described as an implementation. _472#单号A0101 Page 14 of 22 1013043898-0 201229321 <Electrolysis procedure> The electrolysis reaction is prepared by preparing an ether solution of the Grenium compound in the storage tank 20 as an electrolyte. The molten state of gallium is introduced into the electrolysis. In the tank 10, when the anode 50 reaches a predetermined amount below the liquid level of the gallium, the circulation pump 40 is operated, and the electrolyte is introduced into the electrolytic cell 1 through the liquid supply tube 3〇a from the storage tank 2〇. Overflow The electrolytic solution discharged from the electrolytic cell 1 is returned to the storage tank 20 by the liquid supply pipe 30b. In this state, a voltage is applied to the anode 50 and the cathode 6 。. The applied voltage (applied v〇itage) is about 30 V (current density is 2 A/dm 2 ). ). The reaction temperature is about 4 ° C. At this time, gallium is reacted with the genomic compound in the presence of diethyl ether to form a trimethylgallium-diethyl ether adduct. The electrolyte containing the trimethylgallium-diethyl ether adduct is returned to the storage tank 2〇. <Fractionation Procedure> The electrolyte solution in the storage tank 20 contains the by-pr〇duct (Mgl2) (magnesium iodide) in addition to the unreacted Grenium compound and B-external The CH3I (methyl iodide) used in the stage of generating the Grenium compound. Therefore, the electrolyte containing these components is fractionated (fractionation procedure). The electrolyte was gradually warmed and finally warmed to 180 °C. Further, in order to obtain the trimethyl sulfide of the end product, the reason for fractional distillation in the state of trimethylgallium-diethyl ether adduct is due to trimethylgallium-diethyl ether adduct (sea point: about 98 ° C) and methyl iodide (boiling point: about 43 ° C) have a large difference in boiling point, the separation of the two is easy. Incidentally, trimethylgallium has a boiling point of about 56 ° C, and when attempting to separate from methyl iodide having a boiling point of about 43 ° C, the yield of trimethylgallium is lowered. As a result of the fractionation procedure, a fraction containing a trimethylgallium-B-adduct was obtained. However, the fraction also contains a small amount of ether and moth. Therefore, the additional riddles were re-opened (re-single number A0101, page 15 of 22, 1013043898-0 201229321 fractionation procedure) to completely remove methyl iodide. On the other hand, the residue after the fractionation process contains diethyl ether, gemenar compound, iodonium and iodized town. The organometallic compound contained in the residue is decomposed by water and acid to be regarded as a stable compound. Since the iodine compound contained in the residue is useful, iodine is recovered and reused. <iso 1 at ion procedure> Next, the purified trimethyl gallium-diethyl ether adduct (re-fractionation) is transferred to a reaction tank in which an isoarayl ether is previously placed. 70. The solution was reduced pressure distillation at 78 ° C, 30 torr, and the trimethylgallium-diethyl ether adduct was decomposed into trimethylgallium and diethyl ether, and diethyl ether was separated. Then, it was returned to a low pressure, and trimethylgallium was distilled off at 168 ° C (isolation). <Rectification Program> The distillate obtained contains a small amount of isobaric mystery. Therefore, the distillate is introduced into a rectifying column 80 to obtain a final product of trimethylgallium. The liquid temperature in the distillation still is about 90 °C. The trimethyl arsenium of the purity obtained by rectification is packed in a container in a clean room (C1 ean roora) (not shown). By the way, the high-purity trimethylgallium obtained in the present embodiment is inductively coupled plasma mass spectrometry (ICP-MS: Inductively Coupled Plasma Mass Spectrometry) and graphite furnace atomic absorption spectrometry (GFAAS: Grapbite Furnace Atomic Absorption) Spectrometry) results in various metal contents (A1, Ca,
Cd、Cr、Fe、Mg ' Μη、Si、Zn、Cu)為 0· lppm 以下。 1013043898-0 10014724^單編號A〇1〇l 第16頁/共22頁 201229321 本發明的電解生成裝置100因除了採用使電解液循環 的方式外，也採用電極在電解槽10的深度方向中被疊層 配置的方式，故電解反應時的電流效率（current ef f i c i ency )優良。而且，在電解生成裝置100中若由侧 方進行鎵的供給，則疊層電解槽10自身成為可能。其結 果，可擴大電解反應中的有效面積，工業的規模下的三 甲基鎵的生產量確保變得容易。因此，若實施本發明， 高純度的三甲基鎵的工業的製造十分可能。 [0005] 【產業上的可利用性】 本發明的電解生成裝置可在遙晶基板（epitaxial substrate)(GaN、GaAs)、高頻元件（high frequency device)、半導體雷射（semiconductor laser)、高亮度LED(藍色、白色、紫外）等的製造中被 利用。 【圖式簡單說明】 [0006] 圖1是顯示與本發明的電解生成裝置有關的電解槽的 全體構造之斜視圖。 圖2是圖1所示的電解槽之分解斜視圖。 圖3是顯示本發明的實施例，電解生成裝置與其後段 的處理裝置之全體構成圖。 【主要元件符號說明】 [0007] 10:電解槽 1 0 a :鎵導入部 1 Ob :栓 10c :電解液導入部 1001472#單編號歷01 第17頁/共22頁 1013043898-0 201229321 10d :電解液排出部 11:下部塊 12:陽極配置塊 12a·.第一框部 12b:第一孔部 13 :中間塊 13a :空間部 14:陰極配置塊 14a:第二框部 14b:第二孔部 1 5 :上部塊 20:儲存槽 30 :流體迴路 30a、30b :送液管 4 0 :循環栗 50 :陽極 50b:陽極導線 50a:網狀板 60:陰極 70:反應槽 8(h精餾塔 100:電解生成裝置 圆472#單編號廳01 第18頁/共22頁 1013043898-0Cd, Cr, Fe, Mg 'Μη, Si, Zn, Cu) are 0·lppm or less. 1013043898-0 10014724^Single number A〇1〇l Page 16 of 22201229321 The electrolytic generation apparatus 100 of the present invention is also used in the depth direction of the electrolytic cell 10 in addition to the method of circulating the electrolytic solution. Since the lamination is arranged, the current efficiency (current ef ficiency) during the electrolysis reaction is excellent. Further, when the supply of gallium is performed side by side in the electrolysis generating apparatus 100, the lamination of the electrolytic cell 10 itself is possible. As a result, the effective area in the electrolytic reaction can be expanded, and the production amount of trimethylgallium at an industrial scale can be easily secured. Therefore, in the practice of the present invention, industrial manufacture of high purity trimethylgallium is highly possible. [Industrial Applicability] The electrolytic generation device of the present invention can be used in an epitaxial substrate (GaN, GaAs), a high frequency device, a semiconductor laser, and a high It is used in the manufacture of brightness LEDs (blue, white, ultraviolet). BRIEF DESCRIPTION OF THE DRAWINGS [0006] Fig. 1 is a perspective view showing the entire structure of an electrolytic cell relating to an electrolytic production apparatus of the present invention. Figure 2 is an exploded perspective view of the electrolytic cell shown in Figure 1. Fig. 3 is a view showing the overall configuration of an electrolytic generation apparatus and a processing apparatus in a subsequent stage according to an embodiment of the present invention. [Description of main component symbols] [0007] 10: Electrolytic cell 1 0 a : Gallium introduction part 1 Ob : Plug 10c : Electrolyte introduction part 1001472# Single number calendar 01 Page 17 / Total 22 page 1013043898-0 201229321 10d : Electrolysis Liquid discharge portion 11: lower block 12: anode arrangement block 12a. first frame portion 12b: first hole portion 13: intermediate block 13a: space portion 14: cathode arrangement block 14a: second frame portion 14b: second hole portion 1 5 : upper block 20: storage tank 30: fluid circuit 30a, 30b: liquid supply pipe 40: circulating pump 50: anode 50b: anode wire 50a: mesh plate 60: cathode 70: reaction tank 8 (h rectification tower) 100: Electrolytic generating device circle 472# single number hall 01 page 18 / total 22 pages 1013043898-0