201202138. 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種矽系太陽電池用原料的製造方 法，詳細而言，本發明是有關於一種對在各種石夕加工製程 中產生且被高濃度地金屬污染的矽污泥進行清洗，其後， 於電子束裝置内對其進行真空乾燥而使其熔解，藉此可製 造矽系太陽電池用的熔解原料的矽系太陽電池用原料的製 造方法。 【先前技術】 當製造矽系太陽電池時，將包含矽的塊狀的原料（熔 解原料）投入至坩堝中，使其熔解來鑄造矽碇。其後，藉 由將該矽碇切片而獲得太陽電池用的矽基板。” 曰 然而，作為超大規模積體電路（仞加[肛# SWe Integration，ULSI)等超大型積體元件的形成&_^ 圓是，由對利用丘克拉斯基（Cz〇chralski，cz)法提拉而 成的單晶料實施晶圓加工來製作。具體而言， 破切塊’其後’對魏依次進行研難石的外周研^、 利用線鑛的切片，而獲得多片梦晶圓。然後，對各妙曰圓 施去角、研光、侧、研磨來製造元件形成用:產 中財的外周研辭驟及則步驟等 ^造，面研磨步驟中，亦產生的大 石〜匕所3有的石夕粉被由晶圓加工裝置所產生的lxl〇15 201202138 JOZUUpif atoms/cm以上的Fe、Ni等金屬雜質污染，而使所製造的 太陽電池的性能顯著劣化。而且，由於其性狀為污泥，因 此難以對其進行處理，先前，其大部分未被再次利用而受 到廢棄處理。 另外，作為再次利用自晶圓加工製程中所廢棄的石夕的 先刖技術，已知有例如專利文獻1的「坩堝裝置及使用其 的熔解材料的凝固方法」。該技術是如下的技術：首先於電 子束裝置内對塊狀的廢矽照射電子束而使其熔解，使廢矽 中所含有的雜質（例如磷）蒸發來提高矽的純度。其後， 將熔解雜人錄财’使其翻，藉此麟高純度的石夕 系太陽電池用原料。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開2006_111519號公報 但是，於專利文獻1中，被再次利用的廢矽的性狀是 容易進行處理或容易利用電子束進行熔解的塊。因此，無 法將專文獻1 +所§&載的先前技術直接應用於本發明欲 謀求再，利用⑽污泥。例如，由於lxlGl5 atQms/cm3以 上這-高濃度的Fe、Ni等金屬雜質於真空中不_，因此 難以利用電子束的照射來去除。另外，♦污泥巾含有大量 的水分’若於、轉前;Ϊ；對其崎麟，則存在熔解時蒸氣 爆發（phreatic expi〇si〇n)的可能性。因此，為了避免^产 況’必需使料泥自然乾燥例如i週左右，其結果^ 的再次利用的處理時間變長。 2012021¾ 因此發明者進行努力研究的結果，發現若將利用 或HC1 =石夕污泥的清洗法用作污染石夕污泥中所含有的發粉 的lxio15 atoms/cm3以上的金屬雜質的去除（低濃度化） 方法，且於矽污泥的乾燥中，實施利用了電子束熔解時在 電子束裝置内所確保的lxl〇·3 Pa以下的高真空環境的真 空乾燥，則上述所有的問題均得到解決，從而完成本發明。 【發明内容】 本發明的目的在於提供一種可於短時間内自在各種石夕 加工製程中產生、且被高濃度地金屬污染的矽污泥，製造 石夕系太陽電池用的熔解原料的矽系太陽電池用原料的製造 方法。 技術方案1所述之發明是一種矽系太陽電池用原料的 製造方法’其利用可去除金屬雜質的清洗液對在矽加工製 程中產生、且包含上述金屬雜質的污染濃度為lxl〇1S atoms/cm3以上的矽粉的矽污泥進行清洗，藉此使上述矽粉 的上述金屬雜質低濃度化，然後將清洗後的上述矽污泥投 入至電子束裝置的真空腔室中，對上述矽污泥進行真空乾 燥，然後將真空乾燥後的上述矽污泥連續地投入至上述電 子束裝置之中，配置於較上述真空腔室更下游的熔解腔室 中，於其中對上述真空乾燥後的矽污泥照射電子束，藉此 使該真空乾燥後的石夕污泥溶解而製成熔解石夕，繼而，將該 熔解矽投入至成型用的坩堝中，對上述熔解矽進行冷卻而 使其凝固’藉此製成石夕系太陽電池用原料。。 根據技術方案1所述之發明，首先，利用可去除金屬 6 201202138 JSJUUpif 雜質的清洗液對在石夕加工製程令產生的石夕污泥進行清洗。 藉此，可自矽污泥中的矽粉中去除預定量的金屬雜質，而 使石夕粉的金屬雜質量（金屬污染量）降低至未滿IxlO15 atoms/cm3為止。若為該濃度，則可獲得優質的矽系太陽電 池用原料。 繼而，將清洗後的梦污泥投入至電子束裝置的真空腔 室中，於其中對矽污泥進行真空乾燥。藉此，與例如使矽 污泥歷時1週左右而自然錢的情況相比，⑪污泥的再生 時間縮短。將真空乾燥後的石夕污泥移至溶解腔室中，於其 中對石夕污泥照射電子束，而製成。其後，藉由將該 熔解石夕投人至成咖騎财來使其凝固，從而製成石夕系 太陽電池用原料。 所明「石夕系太陽電池用原料」，是指單晶石夕系太陽電池 的原料、多晶衫太陽電池的原料、非晶衫太陽電池的 原料的任一者。 所0污泥’是指錄、雜質、以及水混合成泥狀的 :滓。所谓雜質，是指例如由研削磨石等的磨損所產生的 土:匕，二氧化石夕、剛玉、Cu、Fe、Ni、c〇， 化鎂、塵埃等。 刊 作為矽粉中所含有的金屬雜質，例如可列舉·· Cu、F e、 Νι、Co、氧化鋁、氧化鋇、氧化鎂等。 e 。作為伴隨石夕污泥的產生的石夕加工製程，例如 =峡或多晶錢的切塊、磨石㈣塊的外周 研削、利用研削磨石的魏的定向平面加工或凹口加工: 201202138 矽晶圓的去角、矽晶圓的研光等各步驟。另外，亦包括對 元件形成後的晶圓所實施的背面研磨步驟。 石夕污泥的固體成分的平均粒徑為0.1 μιη〜1〇 。於 大量地產生矽污泥的錠的外周研削步驟、元件製造者的背201202138. VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a raw material for a lanthanide solar cell, and more particularly, the present invention relates to a process for producing various ceramsite processes. The ruthenium sludge contaminated with a high-concentration metal is washed, and then dried in a vacuum apparatus to be melted in an electron beam apparatus, whereby a raw material for a lanthanide solar cell which is a melting raw material for a lanthanide solar cell can be produced. Manufacturing method. [Prior Art] When a lanthanide solar cell is produced, a bulky raw material (melting material) containing ruthenium is put into a crucible, and melted to cast ruthenium. Thereafter, the crucible substrate for the solar cell was obtained by slicing the crucible.曰 , 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛 肛The single crystal material made by Fatila is processed by wafer processing. Specifically, the broken block is 'after', and Wei is successively researched and studied in the outer stone of the stone, and the slice of the line is used to obtain multiple dreams. Wafer. Then, the corners, the light, the side, and the grinding are used to form the components for the formation of the wafers: the peripheral research and the steps of the production, and the large stone produced in the surface grinding step. ～ 石 3 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 Since the trait is sludge, it is difficult to treat it. Most of it has not been reused and was disposed of. In addition, as a re-use of the shovel technology abandoned in the wafer processing process, For example, Patent Document 1 The crucible device and the method of solidifying the molten material using the same. This technique is a technique in which a block-shaped waste sputum is irradiated with an electron beam in an electron beam device to be melted, and impurities (e.g., phosphorus) contained in the ruthenium are evaporated to increase the purity of ruthenium. Thereafter, the melting of the miscellaneous person is recorded and turned over, thereby using the high-purity stone solar cell raw material. [PATENT DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2006-111519. However, in Patent Document 1, the properties of the used waste that are reused are easily processed or easily melted by an electron beam. Piece. Therefore, it is not possible to directly apply the prior art contained in the document 1 + § & directly to the present invention, and to use (10) sludge. For example, since lxlGl5 at Qms/cm3 does not contain metal impurities such as Fe or Ni in a vacuum, it is difficult to remove by electron beam irradiation. In addition, the ♦ sludge towel contains a large amount of water 'if it is before, before turning; Ϊ; for its sirloin, there is a possibility of vapor explosion (phreatic expi〇si〇n) during melting. Therefore, in order to avoid the "production", it is necessary to naturally dry the slurry, for example, about one week, and the processing time for reusing the result becomes long. 20120213⁄4 Therefore, as a result of the intensive study, the inventors have found that the use of the cleaning method using HC1 or Shixia sludge is used as the removal of metal impurities of lxio15 atoms/cm3 or more of pollen contained in the sludge. The concentration method), and in the drying of the sludge, the vacuum drying in a high vacuum environment of 1×10 〇·3 Pa or less secured in the electron beam apparatus during electron beam melting is performed, and all the above problems are obtained. Solved to complete the present invention. SUMMARY OF THE INVENTION An object of the present invention is to provide a bismuth system capable of producing a melting raw material for a Shih-tsu solar cell, which can be produced in a short time by various shovel processing processes and contaminated with a high concentration of metal. A method for producing a raw material for a solar cell. The invention according to claim 1 is a method for producing a raw material for a lanthanide-based solar cell, which uses a cleaning liquid capable of removing metal impurities to generate a contamination concentration in the ruthenium processing process and contains the above-mentioned metal impurities: lxl 〇 1S atoms / Cleaning the sludge of the tantalum powder of cm3 or more, thereby lowering the concentration of the metal impurities of the tantalum powder, and then putting the washed sludge into the vacuum chamber of the electron beam apparatus to smear the stain The mud is vacuum dried, and then the vacuum dried sludge is continuously introduced into the electron beam apparatus, and is disposed in a melting chamber further downstream than the vacuum chamber, and the vacuum dried sputum is placed therein. The sludge is irradiated with an electron beam, thereby dissolving the vacuum dried Schistos sludge to form a melting stone, and then the molten crucible is introduced into a crucible for molding, and the molten crucible is cooled and solidified. 'This is used to make raw materials for Shi Xi solar cells. . According to the invention of the first aspect, first, the Shixia sludge produced in the Shishi processing process is cleaned by using a cleaning liquid capable of removing the metal 6 201202138 JSJUUpif impurity. Thereby, a predetermined amount of metal impurities can be removed from the tantalum powder in the sludge, and the metal impurity amount (metal contamination amount) of the Shishi powder can be reduced to less than IxlO15 atoms/cm3. If it is this concentration, a high-quality raw material for the lanthanide solar cell can be obtained. Then, the washed dream sludge was placed in a vacuum chamber of the electron beam apparatus, and the sludge was vacuum dried therein. As a result, the regeneration time of the sludge 11 is shortened compared with the case where the sludge is naturally used for about one week. The vacuum dried bamboo waste sludge was transferred to a dissolution chamber, and an electron beam was irradiated to the Shixia sludge to prepare an electron beam. Thereafter, the molten stone was thrown into a coffee to make it solidified, thereby preparing a raw material for the solar cell. The "material for the solar cell of the solar cell" is used to refer to any of the raw materials of the single crystal solar cell, the raw material of the polycrystalline silicon solar cell, and the raw material of the amorphous shirt solar cell. The 0 sludge 'is recorded, impurities, and water mixed into a mud: 滓. The term "impurity" refers to, for example, soil generated by abrasion of a grinding stone or the like: cerium, cerium oxide, corundum, Cu, Fe, Ni, c, magnesium, dust, and the like. As the metal impurities contained in the tantalum powder, for example, Cu, Fe, Ν, Co, alumina, cerium oxide, magnesium oxide, or the like can be given. e. As a processing process for the production of Shixia sludge, for example, the edging of the gorge or polycrystalline money, the peripheral grinding of the grindstone (four) block, the directional plane machining or the notch processing of the Wei grinding stone: 201202138 矽Various steps such as chamfering of the wafer and polishing of the wafer. In addition, a back grinding step is performed on the wafer after the element is formed. The average particle size of the solid component of Shixia sludge is 0.1 μιη~1〇. The outer peripheral grinding step of the ingot which produces a large amount of sludge, and the back of the component manufacturer
面研磨步驟令，進行使用粗磨石的粗研削與使用細磨石S 精研削，因此平均粒徑成為粗研削中所產生的尺寸的 μιη 〜10 μιη 〇 作為可去除金屬雜質的清洗液，對應於金屬雜質，例 如可採用 HF、HF/H202、Hca、Η01/ϋ202、ΗΜΝΘ3、HF/ 臭氧等。 清洗前的矽污泥的矽粉中所含有的金屬雜質濃度為超 過梦系太陽電池的規格值的at〇ms/cm3以上，具體 而言為 lxl016atoms/cm3〜lxl〇19atoms/cm3。 清洗後的石夕污泥的矽粉中所含有的金屬雜質濃度未滿 lxlO15 atoms/cm3，具體而言為 lxl〇i3 at〇ins/cin3〜ΐχ10ΐ4 atoms/cm3。 一般利用淋洗液來對清洗後的矽污泥進行淋洗。作為 淋洗液’例如可採用純水或超純水。所謂純水，是指藉由 物理處理或化學處理來去除雜質的純度高的水。具體而 言’可採用 1 ΜΩ-cm〜1〇 ΜΩχιη 或 1.0 pS/cm〜0.1 pS/cm 的水。所謂超純水，是指水中所含有的雜質的量例如為〇 〇1 pg/L以下的水。 電子束裝置包括：真空腔室，其與真空泵連通，對清 洗後的石夕污泥進行真空乾燥；熔解腔室，其配置於真空腔 8 201202138 jo^uupif 室的下游 二eun两廿具芏乾綵後的矽污泥的爐床，·電 子搶，其被收納於熔解腔室中，且對已投入至爐床中的 空乾燥後的石夕污泥照射電子束，而使其熔解；成型用的掛 堝，其自爐床注入熔解矽；以及固化用腔室，其配置於 解腔室的下游’且收納有坩堝。再者，於電子束装置的 部空間，因由真空果所產生的負塵力的作用，不僅真空腔 室真空化’其他空間區域亦真空化。另外，於真空 熔解腔室之間，亦可設置收納有暫時儲存真空乾燥後的石夕 污泥的儲存料斗的暫時儲存腔室。 真4=束運轉時’首先將清洗後的石夕污泥投入至 真工腔至中’其後，利用真空栗使真空腔室内真空化 『〇=行真亩空乾燥。此時，亦可將真空腔室内加熱至 腔室㈣真錄職_污泥連續投入 子中自電子搶對真空乾燥後的碎污泥照射電 η广解♦。制，將熔解雜人輯财，對其 订戶 使其凝固’從而獲得㈣太陽電池用原料的錠。 解腔;；？;空乾燥後術泥連續地投入至Ζ 至熔解腔燥後的石夕污泥於真空環境下投人 至中而不朝電子束裝置外取出。 空度泥的熔解條件，例如可列舉真 .1 Pa、加熱溫度為15〇〇°C。 ’例如可採用銅製糊或石墨製掛禍等。 烙解原料^出Γ夕石定於粉碎後’成為石夕系太陽電池的 其後，將姆解原料投人至例如多晶㈣太陽 20120213$ 電池用的錠鑄造裝置中，使其熔解來鑄造多晶矽碇。對鑄 造後的多晶石夕碗進行晶圓加工，並利用預定的方法形成ΡΝ 接合’藉此製成梦系太陽電池。 技術方案2所述之發明是如技術方案1所述之矽系太 陽電池用原料的製造方法’其中上述矽粉的金屬污染物為 Fe及Νι中的至少一個，上述清洗液為HF、HF/H2〇2、HC1、 HC1/H202、HFmN〇3、HF/臭氧的單體或該些的組合。 技術方案2所述之發明中的矽粉的金屬污染物可僅為 Fe，亦可僅為Ni ’亦可為pe&Ni兩者。 清洗液可僅為HF，亦可僅為HF/H2〇2，亦可僅為Ηα， 亦可僅為HCl/H2〇2’亦可僅為HF/HN03、HF/臭氧。或者， 亦可為該些的兩種或三者以上的組合。其中，最佳的清洗 液是HF。若為HF，則Fe的去除能力高，不具有對於矽 的蝕刻作用。 技術方案3所述之發明是如技術方案丨或技術方案2 所述之石夕系太陽電池用原料的製造方法，其中於上述真空 腔室中，配置有收納上述清洗後的矽污泥的污泥容器，且 該污泥容器於上述真空腔室内被加熱至l5(rc〜3〇(Γ(：。 根據技術方案3所述之發明’於真空腔室内的污泥容 器中收納清洗後的矽污泥，其後，於真空腔室内將污泥容 器加熱至150°C〜300°C，因此乾燥時間變短。 作為污泥容器的加熱方法，例如可採用：加熱器加熱、 紅外線加熱等。 右污泥容器的加熱溫度未滿150°C，則石夕污泥的乾燥 201202138 需要長時間。另外’若超過3〇〇°c，則必需增大加熱所需 的電力，而變得不經濟。 [發明的效果] 根據技術方案1所述之發明，利用可去除金屬雜質的 清洗液對在矽加工製程中產生的矽污泥進行清洗，因此可 使矽污泥中高濃度地含有的金屬雜質減少至未滿1 Χίο15 atoms/cm3為止。藉此，可獲得優質的矽系太陽電池用原 料’進而獲得優質的矽系太陽電池。 另外，關於清洗後的碎污》尼，由於在電子束裝置的真 空腔室内對矽污泥進行真空乾燥，因此與例如使^污泥歷 時1週左右而自然乾燥的情況相比，矽污泥的再生時間縮 短。其後，對真空乾燥後的矽污泥照射電子束，將所獲得 的溶解雜人至職巾，對錢行冷卻而使其凝固，從而 獲得矽系太陽電池用原料的錠。 如以上般，可於短時間内自在各種矽加工製程中產 生、且被高濃度地金>1污染㈣污泥，製切系太陽電池 用的熔解原料。 根據技術方案3所述之發明，於真空腔室内的污、尼容 器中收納清洗後的矽污泥，其後，於真空腔室内將污泥容 器加熱至15(TC〜300°C，因此乾燥時間變短。彳4 為讓本發明之上述和其他目的、賴和優點能更明顯 ^下下文特舉較佳實施例，魏合所_式，作詳細說 【實施方式】 201202138 以下’對本發明的實例進行具體說明。 [實例] 參照圖1的流程圖’對本發明的實例1的矽系太陽電 池用原料的製造方法進行說明。 首先’使用包含電磁鎮造爐的鑄模（鍵鑄造裝置），缚 造比電阻為1 n.cm〜2 Q.cm的多晶矽破。繼而，一面以 30升/分對多晶矽碇供給包含純水的切削液（水溫為 22°C)’ 一面將作為最終固化部分的多晶矽碇的頂部（上端 部）切斷成所需的大小。由於是最終固化部分，因此有時 後端板片的金屬雜質（Fe、Ni等）的濃度為丨x丨〇 i5 at〇ms/em3 以上。 於去除端板時及切塊時，產生大量的矽污泥。此處所 謂矽污泥，是指粒徑（粒度分布）的平均為2 μιη〜3 μιη 的石夕私、雜質、以及純水成為泥狀的渣渾。所謂雜質，是 指例如由研削磨石等的磨損所產生的氧化鋁、二氧化矽、 剛玉、Cu、Fe、Ni、Co、氧化鎖、氧化鎭、塵埃等。其中， 由Fe、Ni等金屬雜質所產生的矽污泥（矽粉）的污染濃度 為與端板片相同程度的lxl〇15atoms/cm3以上。 v、又 繼而，使用圖2之⑷〜2之(d)及圖3所示的抽吸果方 式的清洗裝置對矽污泥進行清洗。 如2之(a)~2之⑷及圖3所示，抽吸栗方式的清洗裝 置10具有與附有抽吸栗的排氣管魏，且上端面開口的未 圖示的抽吸槽。於抽吸槽的上端部，以阻塞上述開口的方 式載置有底板為格子狀的支撐托盤u (圖2之(^)。於支 12The surface polishing step is performed by rough grinding using coarse grindstone and fine grinding with fine grindstone S. Therefore, the average particle diameter is μιη to 10 μηη 尺寸 which is the size of the rough grinding, and is used as a cleaning liquid for removing metal impurities. As the metal impurities, for example, HF, HF/H202, Hca, Η01/ϋ202, ΗΜΝΘ3, HF/ozone, or the like can be used. The concentration of the metal impurities contained in the tantalum powder of the sludge before washing is at least ms/cm3 or more of the specification value of the dream solar cell, specifically, lxl016atoms/cm3 to lxl〇19 atoms/cm3. The concentration of the metal impurities contained in the tantalum powder of the washed Shixi sludge is less than lxlO15 atoms/cm3, specifically lxl〇i3 at〇ins/cin3~ΐχ10ΐ4 atoms/cm3. The eluent is generally used to rinse the washed sludge. As the eluent, for example, pure water or ultrapure water can be used. The term "pure water" refers to water of high purity which is removed by physical treatment or chemical treatment. Specifically, water of 1 ΜΩ-cm~1〇 ΜΩχιη or 1.0 pS/cm~0.1 pS/cm can be used. The ultrapure water means that the amount of impurities contained in the water is, for example, 〇 1 pg/L or less. The electron beam device comprises: a vacuum chamber communicating with the vacuum pump, vacuum drying the cleaned Shishi sludge; a melting chamber disposed in the vacuum chamber 8 201202138 jo^uupif chamber downstream two eun two cookware drying The hearth of the sludge after the coloring, the electronic grab, is stored in the melting chamber, and irradiates the electron beam to the air-dried Shi Xi sludge that has been put into the hearth, and melts it; The hanging raft is injected from the hearth into the melting enthalpy; and the curing chamber is disposed downstream of the eliminating chamber and contains enthalpy. Further, in the space of the electron beam apparatus, not only the vacuum chamber is vacuumed but also the other space regions are vacuumed by the action of the negative dust generated by the vacuum fruit. Further, a temporary storage chamber for storing a storage hopper for temporarily storing the vacuum dried Zeishi sludge may be provided between the vacuum melting chambers. True 4=When the beam is running, 'The first time the cleaned Shishi sludge is put into the real chamber to the middle', then the vacuum chamber is used to vacuum the vacuum chamber. At this time, the vacuum chamber can also be heated to the chamber (4). The record is continuously recorded. The sludge is continuously injected into the sub-electron to illuminate the crushed sludge after vacuum drying. The system will melt the miscellaneous people and make it solidified by the subscribers to obtain (4) ingots for the solar cell raw materials. Solution cavity;;? After the air drying, the mud is continuously poured into the 夕 至 熔 至 至 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥 污泥The melting conditions of the void mud include, for example, true .1 Pa and a heating temperature of 15 °C. For example, a copper paste or a graphite can be used. After the smashing of the raw material, the sputum stone is set to become the Shishi solar cell, and then the raw material is poured into an ingot casting device for, for example, a polycrystalline (four) solar 20120213$ battery, which is melted and cast. Polycrystalline germanium. Wafer processing is performed on the cast polycrystalline stone bowl, and a 接合 joint is formed by a predetermined method to thereby form a dream solar cell. The invention of claim 2 is the method for producing a raw material for a lanthanide-based solar cell according to claim 1, wherein the metal contaminant of the bismuth powder is at least one of Fe and Ν, and the cleaning liquid is HF, HF/ H2〇2, HC1, HC1/H202, HFmN〇3, HF/ozone monomer or a combination of these. The metal contaminant of the tantalum powder in the invention described in claim 2 may be only Fe, or only Ni ' or both of pe & Ni. The cleaning solution may be only HF, or only HF/H2〇2, or only Ηα, or only HCl/H2〇2' or only HF/HN03, HF/ozone. Alternatively, it may be a combination of two or more of these. Among them, the best cleaning solution is HF. In the case of HF, Fe has a high removal ability and does not have an etching effect on ruthenium. The invention of claim 3, wherein the vacuum chamber is provided with a stain for storing the washed sludge a mud container, and the sludge container is heated in the vacuum chamber to l5 (rc~3〇(Γ.. According to the invention of claim 3), the cleaned crucible is stored in a sludge container in a vacuum chamber. After the sludge is heated in the vacuum chamber to 150 ° C to 300 ° C in the vacuum chamber, the drying time is shortened. As the heating method of the sludge container, for example, heater heating, infrared heating, or the like can be employed. If the heating temperature of the right sludge container is less than 150 ° C, the drying of the Shi Xi sludge will take a long time. In addition, if it exceeds 3 ° C, it is necessary to increase the power required for heating and become uneconomical. [Effects of the Invention] According to the invention of claim 1, the mash sludge generated in the mash processing process is cleaned by the cleaning liquid capable of removing metal impurities, so that the metal impurities contained in the slag sludge can be contained at a high concentration. cut back In the case of less than 1 Χίο15 atoms/cm3, it is possible to obtain high-quality raw materials for lanthanide solar cells, and to obtain high-quality lanthanide solar cells. Since the sludge is vacuum-dried in the chamber, the regeneration time of the sludge is shortened compared to the case where the sludge is naturally dried for about one week, and then the vacuum-dried sludge is irradiated with electrons. The bundle of the obtained miscellaneous person to the job towel is cooled and solidified to obtain the ingot of the raw material for the tantalum solar cell. As described above, it can be produced in various processing processes in a short time. In addition, the high-concentration gold >1 is contaminated with (4) sludge, and the molten material for the solar cell is cut. According to the invention of claim 3, the cleaned sludge is stored in the sewage and the niche in the vacuum chamber. Thereafter, the sludge container is heated to 15 (TC to 300 ° C in the vacuum chamber, so the drying time becomes shorter. 彳 4 is to make the above and other objects, advantages and advantages of the present invention more obvious. Lift BEST MODE FOR CARRYING OUT THE INVENTION [Embodiment] [2012] The following is a detailed description of an example of the present invention. [Examples] Referring to the flowchart of Fig. 1, the raw materials for the lanthanide solar cell of Example 1 of the present invention are described. The manufacturing method will be described. First, using a mold (key casting device) including an electromagnetic ballast furnace, a polycrystalline rupture having a specific resistance of 1 n.cm to 2 Q.cm is imposed. Then, a polycrystalline bismuth is 30 liter/min.碇 Supply a cutting fluid containing pure water (water temperature is 22 ° C)' On one side, cut the top (upper end) of the polycrystalline crucible as the final solidified portion to the desired size. Because it is the final solidified part, sometimes it is later The concentration of metal impurities (Fe, Ni, etc.) of the end plate is 丨x丨〇i5 at 〇ms/em3 or more. When the end plates are removed and diced, a large amount of sludge is produced. The term "sludge sludge" as used herein refers to a slag that has an average particle size (particle size distribution) of 2 μιη to 3 μιη, and an impurity, and pure water. The term "impurity" means, for example, alumina, cerium oxide, corundum, Cu, Fe, Ni, Co, oxidized lock, cerium oxide, dust, or the like which is produced by abrasion of a grinding stone or the like. Among them, the contamination concentration of the mash sludge (powder powder) caused by metal impurities such as Fe or Ni is lxl 〇 15 atoms/cm 3 or more which is the same as that of the end plate piece. v. Further, the sludge is washed using the suction type cleaning device shown in (4) to (2) of Fig. 2 and the suction fruit type shown in Fig. 3. As shown in Fig. 2 (a) to (4) and Fig. 3, the suction pump type cleaning device 10 has a suction groove (not shown) that is open to the upper end surface of the exhaust pipe with the suction pump. At the upper end portion of the suction groove, a support tray u having a bottom plate in a lattice shape is placed in a manner to block the opening (Fig. 2 (^).
201202138^ JO^rW^piI 推托盤11中’可取出地收納有孔徑為1 μιη〜30 μπι的金 屬網製的過濾容器12。 於’胃洗污泥時，首先，將矽污泥a與HF清洗液（HF 潰度為〇.5%〜5%) b投入至過濾、容器12中，使用未圖示 的螺旋^式的攪拌裝置，以使石夕污泥a於HF清洗液b中 刀，的方式If拌預定時間。再者，HF清洗液b的投入量是 石夕污泥a的投人量的1G倍左右。藉此，自梦污泥&中的石夕 私中將Fe、Νι等金屬雜質溶解去除，使石夕粉的例如&、 价的污染量降低至未滿lxl〇14at_/cm3為止。 、繼而’使上述抽吸栗運作來將抽吸槽内負壓化，通過 過遽容器12的底板的孔及續托盤u的底板的孔，抽吸 HF清洗液來進行矽污泥a的脫水（圖2之(的）。 繼而’將包含超純水的淋洗液c注入至過 中（圖2之(c))，同樣地使抽吸泵運作來將抽吸“槽内負壓 化’然後強制地使淋洗液c通過脫水後的石夕污泥圖2 束將録通水健4複財次數，—污泥a的 於清洗（包含淋洗）後，將過滤容器^ 11中取出，使其反⑽料洗後时污泥（含m盤 al自過濾容器12中排出（圖3)。 马2ϋ/〇/) 其後，將以上述方柄獲得的清洗㈣ 至圖4所示的電子束裝置2G中，於其中依二 =空乾燥、熔融及固化。以下，對電子束二 13 201202138 如圖4所示’電子束裝置20包括：真空腔室21，其 配置於裝置最上游（上段）；暫時儲存腔室22，其暫時儲 存於真空腔室21内被真空乾燥的矽污泥a2;熔解腔室23, 其於將經暫時儲存的石夕污泥a2移至爐床30後，在爐床30 上照射電子束來製成熔解矽a3 ;以及排出腔室25，其收納 有供自熔解腔室23所排出的炫解石夕a3注入的掛禍24。真 空腔室21與暫時儲存腔室22及熔解腔室23是沿著電子束 裝置20内的矽污泥al〜a3的流向而大致水平地連續配 置。另外，最下游（最下段）的排出腔室25配設於熔解腔 室23的正下方。 於真空腔室21中，配設有使真空腔室21的内部空間 變成〇·〇1 Pa的真空狀態的真空泵26、以及接收自裝置外 投入至真空腔室21中的矽污泥al的污泥容器27。污泥容 器27中内置有未圖示的加熱器，若載置清洗後的污泥，則 可加熱至3〇(TC。另外，於暫時儲存腔室μ中收納有真空 乾燥後的碎污泥a2的暫時儲存料斗28。於暫時儲存料斗 28的底。卩’①置有將所儲存的^夕污泥每次以預定量向 炫解腔室23切出的切出裝置29。於溶解腔室23中，配設 有接收由切出裝置29所切出的石夕污泥a2的爐床3〇，以及 配置於爐床3G的上方’對爐床3()内_污泥照射電子 束來製成溶_a3的—對電子搶3卜另外，排出腔室Μ 的内部空間被分成三個平台，即待機平台W、轉石夕的注 入平台S2及冷卻溶解石夕的冷卻平台S3，於各平纟si〜平 口 S3中配⑶有可於平台間移動的石英製的掛網^。 201202138 將清洗後的矽污泥al自真空腔室21的原料投入口投 入至污泥容器27中。其後，關閉原料投入口，使真空泵 26運作，進而加熱至30(TC。使真空腔室21，甚至電 裝置20的整個内部空間變成〇 〇lpa的真空度。藉此，於 内將污泥容器27中所收納的清洗後的妙污泥真 二乾燥。其結果，與例如使矽污泥al 乾燥的情況相比，可縮短倾以的乾燥時 == 紐矽污泥a的再生時間。 將真空乾燥後的矽污泥a2投入至暫時儲存腔室22 的暫時儲存料斗28中。其後，使切出裝置29運作，藉此 自暫時儲存料斗28的底部，將真空乾燥後的石夕污泥心每 以預定量切出至熔解腔室23⑽爐床％中。於炫融腔 中二自2個電子搶31對爐床3〇内的石夕污泥^照射 電子束，藉此矽污泥a2被加熱至2〇〇〇°c〜25〇(rc而成為 炫解發a3。 其後，爐床30内的熔解矽a3自爐床3〇的上緣向下 流，並被注入至配置於排出腔室25的注入平△ s2中的坩 堝24中。當於掛堝24中僅儲存預定量的熔融;夕a3後^亥 坩堝24被朝冷卻平台S3搬出，且於注入平台幻中自待 機平台S1搬入新的掛禍24。於冷卻平台幻中溶解石夕 a3得到冷卻而固化，成為石夕碇！。其後，將石夕碗工自掛禍 24中取出’繼而實施粉碎成所需的大小等後續處理，藉此 製成由Fe、Ni等的金屬雜質所產生的污染度小的優質^矽 糸太陽電池用原料。 15 201202138 此處，針對實際上於矽加工製程中產生且包含矽粉 矽污泥，測定HF清洗後實施臭氧清洗的情況下（試驗例7 / 與並非如此的情況下（比較例1)的矽粉中的Fe、Ni及 Co的含量並進行比較。HF清洗的條件是HF : h2〇二p 10 (體積比）’臭氧清洗的條件是濃度為2〇 ppm，清洗時 間為5分鐘。 '守 矽粉中的各金屬雜質的測定方法於試驗例丨的情況 下，首先於HF清洗後對矽粉進行臭氧清洗，將矽粉 至電子束裝置中使其轉’然後對其進行冷卻、固化來製 作試驗體。針對該試驗體，利用ICp_MS (ICP質量分析穿 置，Thermo Fisher Scientific股份有限公司製造 ELEMENT2)測定各金屬雜質的含量。另一方面，於比較 例1的情況下，將未清洗的矽粉直接投入至電子束裝置 中，同樣地製作試驗體，然後利用ICP_MS測定試驗體的 各金屬雜質的含量。再者，熔解矽的具體的製作條件依據 實例1。 其結果，於比較例1的情況下，試驗體中的Fe的含量 為 3xl017 atoms/cm3 ’ Ni 的含量為 5xl016 atoms/cm3，C〇 的含量為5χ1016 atoms/cm3。相對於此，於試驗例1的情況 下’試驗體中的Fe、Ni及Co的各含量均未滿lxlO!5 atoms/cm3。 [產業上之可利用性] 本發明作為將例如目前為止使用較困難的矽污泥有效 地用於太陽電池用的原料的技術而有用。 16 201202138 —雖然本發明已以較佳實施例揭露如上，然其並非用以 限^本發明’任何熟習此技藝者，在不脫離本發明之精神 和範圍内，當可作些許之更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 圖1是表示本發明的實例1的矽系太陽電池用原料的 製造方法的流程圖。 圖2之(a)是表示本發明的實例1的矽系太陽電池用原 料的製造方法中，矽污泥的清洗過濾中的狀態的縱剖面 圖。圖2之(b)是表示本發明的實例1的矽系太陽電池用原 料的製造方法中，矽污泥的清洗過濾後的狀態的縱剖面 圖。圖2之(c)是表示本發明的實例1的矽系太陽電池用原 料的製造方法中，矽污泥的淋洗中的狀態的縱剖面圖。圖 2之W)是表示本發明的實例1的矽系太陽電池用原料的製 造方法中，矽污泥的淋洗液的脫水狀態的縱剖面圖。 圖3是表示本發明的實例1的矽系太陽電池用原料的 製造方法中，淋洗後的矽污泥的排出狀態的縱剖面圖。 圖4是表示本發明的實例1的矽系太陽電池用原料的 製造方法中所使用的電子束裝置的整體構成圖。 【主要元件符號說明】 io :清洗裝置 U:支撐托盤 U:過濾容器 2〇 :電子束裝置 17 201202138α 21 :真空腔室 22 :暫時儲存腔室 23 :熔解腔室/熔融腔室 24 :坩堝 25 :排出腔室 26 ··真空泵 27 :污泥容器 28 :暫時儲存料斗 29 :切出裝置 30 :爐床 31 :電子槍 a : >5夕污泥 al :清洗後的矽污泥 a2 :真空乾燥後的矽污泥 a3 :炫解石夕 b : HF清洗液（清洗液） c :淋洗液 I :石夕石定 51 :待機平台 52 :注入平台 53 :冷卻平台 18201202138^ JO^rW^piI In the push tray 11, a filter container 12 made of a metal mesh having a hole diameter of 1 μm to 30 μm is accommodated. When the sludge is washed by the stomach, first, the sludge a and the HF cleaning solution (HF 5% to 5%) are put into the filtration and the container 12, and a spiral type (not shown) is used. The stirring device is used to make the Shixi sludge a in the HF cleaning solution b, and the method If is mixed for a predetermined time. In addition, the input amount of the HF cleaning solution b is about 1 G times the amount of the investment of the Shishan sludge a. In this way, the metal impurities such as Fe and Νι are dissolved and removed in the self-dream sludge & in the Shi Xi private, so that the amount of contamination of the Shishi powder, for example, is reduced to less than lxl 〇 14 at_/cm 3 . Then, the suction pump is operated to negatively pressurize the suction tank, and the HF cleaning liquid is sucked by the hole of the bottom plate of the container 12 and the hole of the bottom plate of the tray u to perform dehydration of the sludge a. (Fig. 2). Then, the eluent c containing ultrapure water is injected into the middle (Fig. 2 (c)), and the suction pump is operated to suction the suction in the tank. 'Then then forcibly let the eluent c pass through the dehydrated Shixi sludge. Figure 2 will record the number of times of water recovery 4, after the sludge a is cleaned (including rinsing), the filter container will be 11 Take out the sludge (the m disk a is discharged from the filter container 12 (Fig. 3) after the reverse (10) material washing. Horse 2ϋ/〇/) Thereafter, the cleaning obtained by the above square handle (4) to Fig. 4 In the electron beam device 2G shown, it is dried, melted, and solidified in accordance with the second = empty. Hereinafter, the electron beam 2 13 201202138 as shown in FIG. 4, the electron beam device 20 includes a vacuum chamber 21, which is disposed at the most Upstream (upper section); temporary storage chamber 22 temporarily stored in vacuum chamber 21 vacuum dried sludge a2; melting chamber 23, which will be temporarily After the stored Shishi sludge a2 is moved to the hearth 30, an electron beam is irradiated on the hearth 30 to form a melting crucible a3; and a discharge chamber 25 containing the loose stone discharged from the melting chamber 23. In the evening, the vacuum chamber 21, the temporary storage chamber 22, and the melting chamber 23 are arranged substantially horizontally along the flow direction of the sludges a1 to a3 in the electron beam apparatus 20. The downstream (lowermost) discharge chamber 25 is disposed directly below the melting chamber 23. In the vacuum chamber 21, a vacuum pump is provided in which the internal space of the vacuum chamber 21 is changed to a vacuum state of 〇·〇1 Pa. 26. A sludge container 27 that receives the sludge sludge a that is supplied to the vacuum chamber 21 from outside the apparatus. A heater (not shown) is incorporated in the sludge container 27, and if the sludge after washing is placed, The battery is heated to 3 〇 (TC). The temporary storage hopper 28 of the vacuum-dried sludge a2 is accommodated in the temporary storage chamber μ. The bottom of the hopper 28 is temporarily stored. 卩'1 is stored in the storage compartment. The cutting device 29 cut out from the dazzling chamber 23 by a predetermined amount each time. In the dissolution chamber 23, It is provided with a hearth 3接收 which receives the Shishi sludge a2 cut out by the cutting device 29, and is disposed above the hearth 3G to irradiate an electron beam to the sludge 3 () to form a solution. In addition, the internal space of the discharge chamber 被 is divided into three platforms, namely, the standby platform W, the injection platform S2 of the Shishixi, and the cooling platform S3 of the cooling dissolved Shixi, in each leveling si ～ 平 S 3 3 3 3 石英 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 The raw material is put into the port, and the vacuum pump 26 is operated to be heated to 30 (TC). The vacuum chamber 21, and even the entire internal space of the electric device 20, is made to have a vacuum of 〇lpa. Thereby, the cleaned sludge which is stored in the sludge container 27 is naturally dried. As a result, compared with the case where the sludge sludge a is dried, for example, it is possible to shorten the regeneration time of the depressed sludge == 矽 sludge a. The vacuum dried sludge a sludge a2 is introduced into the temporary storage hopper 28 of the temporary storage chamber 22. Thereafter, the cutting device 29 is operated, whereby the vacuum dried stem stone sludge core is cut out to the melting chamber 23 (10) hearth % by a predetermined amount from the bottom of the temporary storage hopper 28. In the Xingrong cavity, the two electrons grabbed 31 pairs of the stone slag in the 3 炉 of the hearth and irradiated the electron beam, whereby the sludge a2 was heated to 2〇〇〇°c~25〇(rc After that, the melting 矽a3 in the hearth 30 flows downward from the upper edge of the hearth 3〇, and is injected into the crucible 24 disposed in the injection flat Δs2 of the discharge chamber 25. Only a predetermined amount of melting is stored in the hanging raft 24; after the eve a3, the 坩埚 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 A3 is cooled and solidified to become Shi Xiyu!. Thereafter, the Shixi bowl worker is taken out from the hazard 24, and then subjected to subsequent processing such as pulverization to a desired size, thereby producing a metal such as Fe or Ni. High-quality materials for solar cells with low contamination caused by impurities. 15 201202138 Here, in the case where ozone cleaning is performed after the HF cleaning is performed, which is actually generated in the 矽 processing process and contains 矽 矽 ( ( Test Example 7 / The content of Fe, Ni, and Co in the tantalum powder in the case of not being the case (Comparative Example 1) Line comparison. The condition of HF cleaning is HF: h2〇2 p 10 (volume ratio) 'The conditions for ozone cleaning are 2〇ppm and the cleaning time is 5 minutes. 'The determination method of each metal impurity in Shoumu powder is In the case of the test example, first, after the HF cleaning, the tantalum powder was subjected to ozone cleaning, and the tantalum powder was transferred to an electron beam apparatus to be rotated, and then cooled and solidified to prepare a test body. For the test body, ICp_MS was used. (ICP mass spectrometry, ELEMENT 2 manufactured by Thermo Fisher Scientific Co., Ltd.) The content of each metal impurity was measured. On the other hand, in the case of Comparative Example 1, the unwashed tantalum powder was directly introduced into the electron beam apparatus, and the same The test piece was prepared, and the content of each metal impurity in the test piece was measured by ICP_MS. Further, the specific production conditions of the molten ruthenium were based on Example 1. As a result, in the case of Comparative Example 1, the content of Fe in the test piece was determined. The content of 3xl017 atoms/cm3'Ni is 5xl016 atoms/cm3, and the content of C〇 is 5χ1016 atoms/cm3. On the other hand, in the case of Test Example 1, Fe and Ni in the test body. The content of each of Co is less than lxlO!5 atoms/cm3. [Industrial Applicability] The present invention is useful as a technique for effectively using a sludge which has been difficult to use, for example, for use as a raw material for solar cells. 16 201202138 - Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the invention to those skilled in the art, and may be modified and modified without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method of producing a raw material for a lanthanide-based solar cell according to Example 1 of the present invention. Fig. 2 (a) is a longitudinal cross-sectional view showing a state in which the sludge is washed and filtered in the method for producing a bismuth-based solar cell according to the first embodiment of the present invention. Fig. 2 (b) is a vertical cross-sectional view showing a state in which the sludge is washed and filtered in the method for producing a bismuth-based solar cell according to the first embodiment of the present invention. (c) of FIG. 2 is a longitudinal cross-sectional view showing a state in which the sludge is rinsed in the method for producing a bismuth-based solar cell according to the first embodiment of the present invention. Fig. 2(W) is a longitudinal cross-sectional view showing a state in which the eluent of the sludge is dehydrated in the method for producing a raw material for a lanthanide-based solar cell according to Example 1 of the present invention. Fig. 3 is a longitudinal cross-sectional view showing a state in which the sludge after rinsing is discharged in the method for producing a raw material for a lanthanide-based solar cell according to Example 1 of the present invention. Fig. 4 is a view showing the overall configuration of an electron beam apparatus used in a method for producing a raw material for a lanthanide-based solar cell according to Example 1 of the present invention. [Main component symbol description] io: cleaning device U: support tray U: filter container 2: electron beam device 17 201202138α 21 : vacuum chamber 22: temporary storage chamber 23: melting chamber / melting chamber 24: 坩埚 25 : discharge chamber 26 · vacuum pump 27 : sludge container 28 : temporary storage hopper 29 : cutting device 30 : hearth 31 : electron gun a : > 5 mud sludge al : cleaned sludge a2 : vacuum drying After the sludge a3: Hyunjie Shi Xi b: HF cleaning solution (cleaning solution) c: Eluent I: Shi Xi Shi Ding 51: Standby platform 52: Injection platform 53: Cooling platform 18