TWI499557B - Method for the treatment and/or recycling of cutting slurries - Google Patents
Method for the treatment and/or recycling of cutting slurries Download PDFInfo
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- TWI499557B TWI499557B TW102130393A TW102130393A TWI499557B TW I499557 B TWI499557 B TW I499557B TW 102130393 A TW102130393 A TW 102130393A TW 102130393 A TW102130393 A TW 102130393A TW I499557 B TWI499557 B TW I499557B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28D—WORKING STONE OR STONE-LIKE MATERIALS
- B28D5/00—Fine working of gems, jewels, crystals, e.g. of semiconductor material; apparatus or devices therefor
- B28D5/0058—Accessories specially adapted for use with machines for fine working of gems, jewels, crystals, e.g. of semiconductor material
- B28D5/007—Use, recovery or regeneration of abrasive mediums
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B57/00—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
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- C—CHEMISTRY; METALLURGY
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Description
本發明係關於一種機械分離法過程中用於處理及/或回收切割漿料，特別指半導體材料之方法。該切割漿料含有由半導體材料所製成之顆粒以及碳化矽及/或鑽石微粒。根據本發明之方法，建議一種兩階段處理及/或回收法，其中於第一步驟中，於溫度低於半導體材料之熔點進行漿料處理以及，在第二步驟中，以高於半導體材料熔點之溫度處理獲得自第一步驟之產物。至少於第一步驟及/或第二步驟過程中，將該漿料導入一氣流內及/或流經及/或被氣體所包圍。 The present invention relates to a method for treating and/or recovering a cutting slurry, particularly a semiconductor material, during a mechanical separation process. The cutting slurry contains particles made of a semiconductor material and tantalum carbide and/or diamond particles. According to the method of the present invention, a two-stage treatment and/or recovery method is proposed, wherein in the first step, the slurry treatment is carried out at a temperature lower than the melting point of the semiconductor material and, in the second step, at a higher temperature than the melting point of the semiconductor material The temperature treatment was obtained from the product of the first step. At least during the first step and/or the second step, the slurry is introduced into a gas stream and/or passed through and/or surrounded by a gas.
生產用於製造太陽能電池或其他微電子組件之單及多晶矽片，被稱為晶圓，首先需要一種用於生產大量矽晶重量高達1,000kg之製程。接著，從生長單和多晶矽容積結晶切割下具有100μm至1,000μm厚度之矽晶圓。根據其所使用之分離法，當秤取矽晶材料時，將會耗損約50%之矽晶材料。 The production of single and polycrystalline wafers for the fabrication of solar cells or other microelectronic components, referred to as wafers, first requires a process for producing a large number of twin crystals up to 1,000 kg. Next, a tantalum wafer having a thickness of 100 μm to 1,000 μm was cut from the growth order and polycrystalline germanium volume. Depending on the separation method used, when the twinned material is weighed, about 50% of the twinned material will be consumed.
目前可根據現行技術經由一線鋸切割法(以分散碳化矽沙礫或鑽石線)或相應濕式分離法藉由內孔鋸或類似物從分離液晶材料形成晶圓。 Wafers can now be formed from separate liquid crystal materials by a wire saw or the like by a wire saw cutting method (to disperse carbonized slag or diamond wire) or a corresponding wet separation method according to the prior art.
分離方法最常見由分離液，其可能為研磨介質、來自線或鋸 片之金屬磨粒以及鋸切矽所產生之混合物廢料。根據現行技術，此混合物可被分離成液相和固相。 Separation methods are most commonly carried out by separating liquids, which may be grinding media, from wires or saws The metal abrasive grains of the sheet and the mixture waste produced by sawing the crucible. According to the current technology, this mixture can be separated into a liquid phase and a solid phase.
在光電技術領域中，目前製造係使用碳化矽沙礫為主線鋸法。此方法中，係使用120~160μm厚鋼線，其藉由研磨介質被濕潤。該藉由研磨介質係由切削顆粒和一般高黏度載液所組成。該切削顆粒必需具有大於二氧化矽之硬度和一般由碳化矽(SiC)或鑽石微粒所構成，以及具有研磨介質30~50%容積比之體積比例。一般係使用聚乙二醇(PEG)作為載液，但亦可使用油和水。在切割過程中，研磨介質線鋸通過矽塊。此因而可切除該矽。其所產生之矽顆粒與研磨介質相混合。該載液、碳化矽或鑽石微粒以及矽微粒所構成之混合物被稱為「漿料」。此外，該漿料滲雜有主要為鐵、銅和鉻之金屬雜質，但亦含有來自用過線鋸之其他金屬以及來自由石墨、玻璃或黏附切割時固定用矽膠管柱之特殊陶瓷所組成載液，以及來自黏著劑之顆粒。 In the field of optoelectronic technology, the current manufacturing system uses carbonized slag gravel as the main line saw method. In this method, a 120-160 μm thick steel wire is used, which is wetted by the grinding medium. The grinding medium consists of cutting particles and a generally high viscosity carrier liquid. The cutting particles must have a hardness greater than that of cerium oxide and generally consist of tantalum carbide (SiC) or diamond particles, and have a volume ratio of 30 to 50% by volume of the grinding medium. Polyethylene glycol (PEG) is generally used as the carrier liquid, but oil and water can also be used. During the cutting process, the abrasive media saw passes through the block. This can thus cut off the defect. The ruthenium particles produced therefrom are mixed with the grinding media. The mixture of the carrier liquid, the ruthenium carbide or the diamond particles and the ruthenium particles is referred to as a "slurry". In addition, the slurry is impregnated with metal impurities mainly composed of iron, copper and chromium, but also contains other metals from used wire saws and special ceramics from graphite, glass or fixed rubber cylinders for adhesive cutting. Carrier liquid, as well as particles from the adhesive.
現行技術係回收PEG以及較大(>5μm)之碳化矽或鑽石微粒。由於從矽顆粒中進一步分離碳化矽或鑽石微粒既無效率又不經濟，因此目前係丟棄研磨過細之碳化矽或鑽石和矽顆粒。文獻中已述及化學純化法(T.Y.Wang、Y.C.Lin、C.Y.Tai、C.C.Fei、M.Y.Tseng和C.W.Lan，從光電應用之切損漿液廢料中回收氧化矽，Progress in Photovoltaics,Research and Application 2009，17：155；163；V.Provent,E.和Brize,B.、Drevet,F.Coustier和E.Flahaut，第26版EUPVSEC之鑽石線切割：有關矽切割回收，2011，1965~1968)、離心不同密度及/或於1470℃以上高溫處理溶劑內之「漿料」(T.Y.Wang、Y.C.Lin、C.Y.Tai、C.C.Fei、M.Y.Tseng和C.W.Lan，從 光電應用之切損漿液廢料中回收矽，Progress in Photovoltaics,Research and Application 2009，17：155,163)。然而無法借助其從矽相中有效分離該碳化矽顆粒。此外，從漿料開始，無法在熔融矽相中完全轉化該矽顆粒因而亦無法回收該昂貴之矽原材料。 The current technology is the recovery of PEG and larger (>5 μm) tantalum carbide or diamond particles. Since further separation of niobium carbide or diamond particles from niobium particles is neither efficient nor economical, it is currently discarding finely ground niobium carbide or diamond and niobium particles. Chemical purification methods (TYWang, YCLin, CYTai, CCFei, MYTseng, and CWLan have been described in the literature to recover cerium oxide from cut-off slurry waste from photovoltaic applications, Progress in Photovoltaics, Research and Application 2009, 17 :155;163;V.Provent,E. and Brize,B.,Drevet,F.Coustier and E.Flahaut,26th edition of EUPVSEC diamond wire cutting: related to 矽 cutting recovery, 2011, 1965~1968), different centrifugation Density and / or "slurry" in the solvent at high temperatures above 1470 ° C (TYWang, YCLin, CYTai, CCFei, MYTseng and CWLan, from Recycling of cut-off slurry waste for photovoltaic applications, Progress in Photovoltaics, Research and Application 2009, 17: 155, 163). However, it is not possible to effectively separate the niobium carbide particles from the haze phase. Further, starting from the slurry, the ruthenium particles cannot be completely converted in the molten ruthenium phase and the expensive ruthenium raw material cannot be recovered.
根據漿料純化之現行技術，若碳化矽/矽混合物之滲合物內或高達100%進行單或多晶矽獨特凝固特性之標準晶體生長條件，則可形成粉體但非熔融相之凝聚物。因此，含於碳化矽/矽混合物內矽相之單純「熔出」並非不可能。 According to the current art of slurry purification, agglomerates of a powder but a non-melt phase can be formed if the standard crystal growth conditions of the unique solidification characteristics of mono or polycrystalline germanium are carried out in the permeate of the niobium carbide/niobium mixture or up to 100%. Therefore, the simple "melting" of the ruthenium phase contained in the ruthenium carbide/ruthenium mixture is not impossible.
目前之挑戰為經由一循環迴路從產生之廢料中回收昂貴矽，並且將其再次供應至實際結晶生長過程，以及因此明顯降低其生產成本。 The current challenge is to recover expensive helium from the produced waste via a recycle loop and supply it again to the actual crystal growth process, and thus significantly reduce its production costs.
因此，本發明係提供一種儘可能地從含有半導體材料之切割漿料中回收半導體材料之方法。明確而言，該方法必需為簡單可行並且具有高產輸量。 Accordingly, the present invention provides a method of recovering semiconductor material from a cutting slurry containing a semiconductor material as much as possible. In particular, the method must be simple and feasible and have a high yield.
藉由本申請專利範圍第1項之特徵可達到此目標，其各自附屬項代表其所衍生出之優點。 This object is achieved by the features of item 1 of the scope of the patent application, the respective sub-items of which represent the advantages derived therefrom.
根據本發明，因而係指出一種用於處理及/或回收切割漿料之方法，該切割漿料含有由半導體材料所製成之顆粒。切割漿料於空氣中或儲存條件下，無可避免地在半導體材料形成之顆粒上會形成一些氧化膜，因此這些半導體材料之氧化物至少會於部分區域產生表面氧化膜。此外，含於作為磨料之漿料內含有碳化矽及/或鑽石微粒之切割漿料，而因此 成為該半導體材料於切割過程中之雜質。 According to the present invention, there is thus indicated a method for treating and/or recovering a cutting slurry containing particles made of a semiconductor material. When the cutting slurry is in air or under storage conditions, some oxide film is inevitably formed on the particles formed of the semiconductor material, and therefore the oxide of these semiconductor materials generates a surface oxide film at least in a partial region. Further, it is contained in a slurry containing barium carbide and/or diamond particles in a slurry as an abrasive, and thus Become an impurity in the semiconductor material during the cutting process.
根據本發明之方法，包括下列步驟：a)在第一步驟中，於溫度低於半導體材料之熔點進行漿料處理，以及b)在第二步驟中，以於或高於半導體材料熔點之溫度處理獲得自第一步驟之產物，獲得半導體材料之熔體，以及c)接著，冷卻該熔體直至固化或至少一部分熔融態內半導體材料之熔體被分離。 The method according to the invention comprises the steps of: a) performing a slurry treatment at a temperature below the melting point of the semiconductor material in the first step, and b) a temperature at or above the melting point of the semiconductor material in the second step The product obtained from the first step is treated to obtain a melt of the semiconductor material, and c) the melt is subsequently cooled until the melt of the semiconductor material is solidified or at least partially molten.
至少於第一步驟過程中將該漿料導入一氣體流，及/或流經及/或被氣體所包圍。此外，於第二步驟中依照先前所述方法使該漿料接觸氣體流。 The slurry is introduced into a gas stream at least during the first step, and/or flows through and/or is surrounded by a gas. Further, the slurry is contacted with the gas stream in a second step in accordance with the methods previously described.
驚奇地發現，在步驟a)及/或b)所述條件下，該半導體材料之表面氧化膜，其含有半導體材料之氧化物，能與碳化矽或鑽石之碳反應。該半導體材料之氧化物因而發生形成初步半導體金屬和一氧化碳及/或二氧化碳之還原反應。因而可利用氣流移除形成之揮發性物質。 Surprisingly, it has been found that under the conditions of steps a) and/or b), the surface oxide film of the semiconductor material, which contains an oxide of a semiconductor material, can react with carbon of tantalum carbide or diamond. The oxide of the semiconductor material thus undergoes a reduction reaction that forms a preliminary semiconducting metal and carbon monoxide and/or carbon dioxide. The resulting volatile material can thus be removed using a gas stream.
另外，已驚奇地發現顆粒雜質積聚於第二步驟中產生漿料熔體，以及亦於其後殘留熔體在冷卻和固化期間之金屬邊緣區域。形成金屬渣(regulus)因此具有-存在顆粒雜質之下-一純化半導體材料組成之核心以及一融合成顆粒狀雜質之邊緣區域。此類雜質，其內可能含有例如在根據本發明方法中步驟a)和b)中選定條件下之碳化矽或鑽石微粒，無法與半導體金屬顆粒之氧化物膜表面上半導體金屬氧化物以及來自用於切割法中線鋸磨耗之金屬微粒完全地反應。 In addition, it has been surprisingly found that particulate impurities accumulate in the second step to produce a slurry melt, and also in the metal edge regions of the residual melt during cooling and solidification thereafter. The formation of metal rusts thus has - under the presence of particulate impurities - a core of purified semiconductor material composition and an edge region fused into particulate impurities. Such impurities, which may contain, for example, niobium carbide or diamond particles under selected conditions in steps a) and b) of the method according to the invention, incapable of contacting the semiconducting metal oxide on the surface of the oxide film of the semiconducting metal particles and from In the cutting method, the metal particles worn by the wire saw completely react.
本發明一較佳具體實施例因此提供於熔體固化後被機械或 濕式化學蝕刻法(etched wet-chemically)所分離固體結晶之邊緣區域。 A preferred embodiment of the invention is thus provided after the melt is cured by mechanical or The edge region of the solid crystal separated by wet-etched wet-chemically.
根據發明者之驚奇發現，藉由分離邊緣區域可獲得含於切割漿料內大部分之純化半導體材料，而因此藉由分離該邊緣區域，亦可分離邊緣區域內於熔體固化期間所積聚之顆粒雜質。該獲得半導體材料具有高純度，並且可被再利用。 According to the surprise of the inventors, a large portion of the purified semiconductor material contained in the dicing slurry can be obtained by separating the edge regions, and thus by separating the edge regions, it is also possible to separate the edge regions to accumulate during the solidification of the melt. Particulate impurities. The obtained semiconductor material has high purity and can be reused.
該邊緣區域之分離可受機械性地影響，例如藉由舉例如鋸切及/或銼磨等，但亦可藉由現行技術中已知相關蝕刻法。該分離因而在基本上由純化半導體材料所組成之固化金屬渣核心區域被暴露以及含於邊緣區域內雜質被分離時才開始。 The separation of the edge regions can be mechanically affected, such as by, for example, sawing and/or honing, but can also be by known etching methods known in the art. This separation thus begins when the solidified slag core region consisting essentially of the purified semiconductor material is exposed and the impurities contained in the edge region are separated.
或者，其同樣可例如藉由傾倒法分離半導體材料之至少一部分獲得熔體，而因此獲得純化半導體材料。固化之進行可藉由例如於單獨坩堝/瓶內之分離。 Alternatively, it is likewise possible to obtain a melt by separating at least a part of the semiconductor material by a pouring method, thereby obtaining a purified semiconductor material. Curing can be carried out by, for example, separation in a separate crucible/bottle.
施加於第一步驟中方法之較佳溫度範圍因而在500至1,500°C，更佳為900至1,100℃。 The preferred temperature range for the method applied in the first step is thus from 500 to 1,500 ° C, more preferably from 900 to 1,100 ° C.
施加於第二步驟之較佳溫度因而在1,000至2,000℃之範圍，更佳為1,400至1,600℃。 The preferred temperature applied to the second step is thus in the range of 1,000 to 2,000 ° C, more preferably 1,400 to 1,600 ° C.
這些較佳具體實施例中，第二步驟中之溫度因而選擇通常較高於第一步驟中之溫度。 In these preferred embodiments, the temperature in the second step is thus selected to be generally higher than the temperature in the first step.
第一步驟之漿料處理時間較佳為0.1至100小時，更佳為在0.5至30小時；而第二步驟之漿料處理時間較佳為0.5至10小時，更佳為在1至3小時。 The slurry treatment time of the first step is preferably from 0.1 to 100 hours, more preferably from 0.5 to 30 hours; and the slurry treatment time of the second step is preferably from 0.5 to 10 hours, more preferably from 1 to 3 hours. .
此外，為了分離存在於漿料內之任何液體化合物，尤指聚乙 二醇及/或水，若於第一步驟之前預乾燥漿料將有其優勢，其溫度較佳為30至1,000℃，更佳為100至500℃。 In addition, in order to separate any liquid compounds present in the slurry, especially polyethylene The diol and/or water, if pre-dried prior to the first step, has its advantage, preferably at a temperature of from 30 to 1,000 ° C, more preferably from 100 to 500 ° C.
藉由揮發作用物理性地分離其所含揮發性化合物可達到預乾燥之目的；然而，若含碳時一其同樣可選擇碳化溫度揮發含液體化合物；根據初步描述之原則，同樣可利用其後所形成之碳於還原該半導體材料顆粒之氧化物膜表面。 Pre-drying can be achieved by physically separating the volatile compounds contained by volatilization; however, if carbon is contained, it is also possible to volatilize the liquid compound containing carbonization temperature; according to the principle of preliminary description, the same can be used thereafter. The carbon formed is used to reduce the surface of the oxide film of the semiconductor material particles.
預乾燥中之較佳壓力範圍因而為低於500mbar，更佳為低於10mbar，最佳為低於1mbar。 The preferred pressure range in the pre-drying is thus less than 500 mbar, more preferably less than 10 mbar, and most preferably less than 1 mbar.
然而，該預乾燥亦可於第一步驟中同步進行。 However, the pre-drying can also be carried out simultaneously in the first step.
此方法條件中，用利用氣流相對含於漿料內之材料因而較佳為具有化學惰性；尤指含有惰性氣體或由惰性氣體構成之氣流。此態樣之可能稀有氣體舉例為例如氦、氖、氬、氪及/或其混合物，其中以氬為最佳。 In the process conditions, it is preferred to use a gas stream relative to the material contained in the slurry and is therefore preferably chemically inert; in particular, a gas stream comprising or consisting of an inert gas. Examples of possible rare gases are, for example, helium, neon, argon, krypton and/or mixtures thereof, with argon being preferred.
進一步變化為提供被加入該氣流之氫氣，較佳為以0.01至50%體積比之容積比例，更佳為0.1至25%體積比，最佳為0.5至5%體積比。 Further variation is to provide hydrogen gas to be added to the gas stream, preferably in a volume ratio of from 0.01 to 50% by volume, more preferably from 0.1 to 25% by volume, most preferably from 0.5 to 5% by volume.
所利用氫氣同樣被用於還原其所含之半導體材料氧化物。目前，已指出氧化碳化矽之還原反應與所加入之氫成比例。 The hydrogen used is also used to reduce the oxide of the semiconductor material contained therein. At present, it has been pointed out that the reduction reaction of ruthenium carbide is proportional to the hydrogen added.
此外，漿料較佳為流動經過及/或被第一步驟中氣體所包圍，該漿料為成層狀供應以及該氣流通過其各層中至少一表面，該漿料層之厚度較佳為小於5cm，更佳為小於1cm，最佳為小於0.5cm。 In addition, the slurry is preferably flowed through and/or surrounded by a gas in a first step, the slurry being supplied in layers and the gas stream passing through at least one surface of each of the layers, the thickness of the slurry layer preferably being less than 5 cm, more preferably less than 1 cm, most preferably less than 0.5 cm.
或者或另外，於此處同樣可流經氣流之漿料較佳為經由一噴槍或一氣體熔塊(gas frit)被注入該氣流。明確而言，較佳為經由一噴槍或一熔塊將該氣流注入於坩堝內燒結之漿料，該坩堝最佳為附有一透氣罩。 Alternatively or additionally, the slurry which is also permeable to the gas stream here is preferably injected into the gas stream via a spray gun or a gas frit. Specifically, it is preferred to inject the gas stream into the slurry sintered in the crucible via a spray gun or a frit, preferably with a gas permeable cover attached thereto.
根據本發明之方法較佳為於反應鍋例如坩堝內進行，其係形成自具有高達至少1,600℃耐溫性之材料，用於此目的之材料為舉例如具有相對高軟化點或熔點之陶瓷或金屬或合金。此特定坩堝可由例如碳、氧化鋁(Al2O3)、氧化矽(SiO2)、氮化硼(BN)、氮化矽(Si3N4)、鎢和鉑所組成。 The method according to the present invention is preferably carried out in a reaction vessel such as a crucible which is formed from a material having a temperature resistance of at most 1,600 ° C, and the material used for this purpose is, for example, a ceramic having a relatively high softening point or melting point or Metal or alloy. This specific germanium may be composed of, for example, carbon, aluminum oxide (Al 2 O 3 ), cerium oxide (SiO 2 ), boron nitride (BN), tantalum nitride (Si 3 N 4 ), tungsten, and platinum.
可根據本發明方法被加工之較佳半導體材料因而係選自週期表第III、IV和V族及其組合之元素，其尤指矽、鍺、砷化鎵、磷化鎵、砷化銦、磷化銦及/或組合或其混合物。 Preferred semiconductor materials which can be processed in accordance with the method of the present invention are therefore selected from elements of Groups III, IV and V of the Periodic Table and combinations thereof, particularly yttrium, lanthanum, gallium arsenide, gallium phosphide, indium arsenide, Indium phosphide and/or combinations or mixtures thereof.
根據本發明方法之進一步變化為提供相對該漿液固體含量從0.1至60%重量比，較佳為從0.1至50%重量比，最佳為從0.1至40%重量比之碳化矽及/或鑽石微粒。 A further variation of the process according to the invention is to provide a bismuth carbide and/or diamond relative to the solids content of the slurry from 0.1 to 60% by weight, preferably from 0.1 to 50% by weight, most preferably from 0.1 to 40% by weight. particle.
或者或另外，相對各自該漿料之固體含量，由半導體材料與至少部分區域氧化物膜表面所形成顆粒之含量為從99.9至40%重量比，較佳為從99.9至50%重量比，最佳為從99.9至80%重量比。 Alternatively or additionally, the content of particles formed from the semiconductor material and at least a portion of the surface oxide film surface is from 99.9 to 40% by weight, preferably from 99.9 to 50% by weight, most preferably relative to the solid content of the respective slurry. Good from 99.9 to 80% by weight.
在不受限於本發明特定實例參數之下，參考後續圖示、說明及其具體實施例詳細解釋本發明。 The present invention is explained in detail with reference to the following drawings, description, and specific embodiments thereof, without being limited thereto.
明確而言，本發明之方法適合用於處理該所謂切割泥漿之由例如PEG、碳化矽、矽和其他金屬雜質構成之「漿料」，以回收其中所含之矽。因而產生可被相互分離之結晶生長所捨棄液態矽相和殘留固態相。「漿料」之適當處理包含在所述氣流下之特定溫度處理。該溫度處理首先可在例如高至1,000℃之低溫範圍內有效分離該液體和相應揮發性物種。由於易於揮發，因而於低於1巴(bar)壓力下操作有其優勢。此外，根據下列反應方程式該處理可有效進行任何存在氧化矽(氧化物表面或呈SiOx顆粒)與碳化 矽之轉換：2SiO2+SiC→3SiO+CO Specifically, the method of the present invention is suitable for treating a so-called cutting slurry of a "slurry" composed of, for example, PEG, tantalum carbide, niobium and other metallic impurities to recover the niobium contained therein. Thus, a liquid ruthenium phase and a residual solid phase which are separated from each other by crystal growth are produced. Appropriate treatment of the "slurry" is treated at a specific temperature below the gas stream. This temperature treatment can first effectively separate the liquid and corresponding volatile species in a low temperature range of, for example, up to 1,000 °C. Operating at pressures below 1 bar has advantages due to its ease of volatilization. In addition, according to the following reaction equation, the treatment can effectively perform any conversion of cerium oxide (oxide surface or SiO x particles) and lanthanum carbide: 2SiO 2 + SiC → 3 SiO + CO
在氣流作用之下，該從此反應形成之揮發性化合物被輸移。在高溫下產生之其他含金屬化合物亦如同PEG，同樣地從該粉體被移除。藉由該溫度處理以及特定供氣，因而使該仍潮濕之純化漿料形成「漿料粉體」。現在該「漿料粉體」內獲得之矽可藉由製程內進一步界定之處理被轉化成熔融相。 The volatile compounds formed from this reaction are transported under the action of a gas stream. Other metal-containing compounds produced at elevated temperatures, like PEG, are likewise removed from the powder. By this temperature treatment and specific gas supply, the still moist purified slurry is formed into a "slurry powder". The enthalpy obtained in the "slurry powder" can now be converted to a molten phase by a process further defined in the process.
該氣流數量、氣體供應以及氣體組成物於此處扮演一重要角色。為了輸移該揮發性物種，該粉體與氣體接觸表面積必需最大化。在大於1,000℃溫度下於一確定時間間隔(0.5至30小時)加入氫至惰性氣體(0.5~10%)更加影響該矽和碳化矽顆粒表面上氧化物之還原作用。已假設移除碳化矽顆粒表面上之天然氧化物將導致提高存在碳化矽形成揮發性氧化矽和一氧化碳成分之轉換率。因而，亦可減少漿料內存在之碳化矽含量。藉由所示程序，轉化已存在SiOx以及同時減少碳化矽含量，而可熔化漿料內之矽含量。 The amount of gas, gas supply, and gas composition play an important role here. In order to transport the volatile species, the surface area of the powder in contact with the gas must be maximized. The addition of hydrogen to an inert gas (0.5 to 10%) at a defined time interval (0.5 to 30 hours) at a temperature greater than 1,000 °C further affects the reduction of oxides on the surface of the niobium and tantalum carbide particles. It has been hypothesized that removal of the natural oxide on the surface of the tantalum carbide particles will result in an increase in the conversion rate of the formation of volatile niobium oxide and carbon monoxide components in the presence of niobium carbide. Therefore, the amount of niobium carbide present in the slurry can also be reduced. By the procedure shown, the conversion of the already present SiO x and at the same time the reduction of the niobium carbide content, while melting the niobium content in the slurry.
藉由此方法，可有效和經濟地再循環於單和多晶矽晶圓製造中所產生之各種矽基漿料以及回收該昂貴矽原料。 By this method, various sulfonium-based pastes produced in the manufacture of single and polycrystalline silicon wafers can be efficiently and economically recycled and the expensive ruthenium raw materials can be recovered.
1‧‧‧粉體原位處理構造 1‧‧‧ powder in situ treatment structure
2‧‧‧坩堝 2‧‧‧坩埚
3‧‧‧粉體 3‧‧‧ powder
4‧‧‧透氣覆蓋 4‧‧‧ breathable cover
5‧‧‧噴槍 5‧‧‧ spray gun
6‧‧‧氣體 6‧‧‧ gas
圖1a顯示一矽相，圖1b顯示開啟石墨坩堝內部已充滿100%「漿料」粉體之熔化和固化過程後殘留漿料粉體。該「漿料」粉體適合於左側而非右側進行預處理。因此，該矽相應於「漿料粉體」之左側被熔出。 Figure 1a shows a bismuth phase, and Figure 1b shows the residual slurry powder after the melting and solidification process of the 100% "slurry" powder that has been filled inside the graphite crucible. The "slurry" powder is suitable for pretreatment on the left side rather than the right side. Therefore, the crucible is melted corresponding to the left side of the "slurry powder".
圖2顯示用於執行根據本發明方法之一特殊製程構造。 Figure 2 shows a particular process configuration for performing a method in accordance with the present invention.
在一管狀爐內進行第一次乾燥和分離步驟後之回收「漿料」粉體處理。選擇溫度範圍在500~1,500℃，更佳為在900~1,100℃。在給定溫度之處理時間為0.5~30小時。粉體係置入具有大縱橫比之坩堝內。其目的係最大化粉體與氣流接觸之表面積。選擇於優勢溫度時能使其維持尺寸安定之坩堝材料。化學反應或機械磨耗時，必需保持低雜質量。該坩堝可由石英玻璃或石墨，但亦可由氮化物所構成。該氣流係流經粉體表面。選擇可使載流氣體和粉體之間不發生反應之氣體。較佳為調整氣流使其不渦旋而升和輸移。此外，應確保粉體上方之揮發性物種迅速地被移除。其所形成氫氣與載流氣體滲合物之濃度範圍在0.01~10%體積比，如上所述，可移除位於矽和碳化矽顆粒上之氧化物。 The "slurry" powder treatment is carried out after the first drying and separation step in a tubular furnace. The temperature range is selected from 500 to 1,500 ° C, more preferably from 900 to 1,100 ° C. The treatment time at a given temperature is 0.5 to 30 hours. The powder system is placed in a crucible having a large aspect ratio. Its purpose is to maximize the surface area of the powder in contact with the gas stream. Choose the material that will maintain the dimensional stability when it is at the dominant temperature. In the case of chemical reactions or mechanical abrasions, it is necessary to maintain a low impurity quality. The crucible may be made of quartz glass or graphite, but may also be composed of nitride. This air flow flows through the surface of the powder. A gas that does not react between the carrier gas and the powder is selected. Preferably, the air flow is adjusted so that it does not vortex and is lifted and transported. In addition, it should be ensured that volatile species above the powder are quickly removed. The concentration of hydrogen and carrier gas gas formed therein ranges from 0.01 to 10% by volume, and as described above, the oxides on the ruthenium and tantalum carbide particles can be removed.
繼氣流下加入氫氣之第一溫度處理之後，該「漿料」粉體可被用於矽晶製造之各種方法中。圖1a顯示熔化和固化過程後石墨坩堝內具有100%「漿料」粉體原來稱取量之熔融矽。 The "slurry" powder can be used in various methods of twinning after the first temperature treatment of adding hydrogen under the gas stream. Figure 1a shows the melting enthalpy of the 100% "slurry" powder in the graphite crucible after the melting and solidification process.
圖1b顯示氣流內無適當溫度處理之相同程序後所獲得結果。 Figure 1b shows the results obtained after the same procedure in the gas stream without proper temperature treatment.
亦可於原位進行粉體之處理，即於「漿料」熔化前之熔化和固化設備內。於具體實施例1所述溫度處理中，為有效輸移該揮發性物種，必需運用下列所述氣體供應概念。 The powder can also be processed in situ, ie in the melting and solidification equipment prior to the melting of the "slurry". In the temperature treatment described in the specific embodiment 1, in order to efficiently transport the volatile species, it is necessary to apply the gas supply concept described below.
載流氣體以及氫氣可經由一噴槍被導入該粉體內，或經由氣體熔塊輸送該粉體。圖2中，繪圖表示以空氣噴槍用於原位處理該粉體之構 造。該空氣噴槍以高溫下具有化學和力學安定性之不透氣材料所組成。根據應用上之類型，可使用例如氧化鋁(Al2O3)、其他陶瓷，亦包括石英玻璃。該氣體經由噴槍被傳送入粉體。為了保護單元部件以避免污染以及降低因粉末渦旋上升而造成***之危險，可視需要使用一透氣覆蓋。由於材料性質該覆蓋可透氣，用於此目的可使用陶瓷材料，亦可使用石墨。此外，該覆蓋上可能具有排氣用之小孔。應考慮所選用覆蓋具有足夠高之溫度(至少400℃)以避免被輸移之氧化矽(SiO)不會造成沈澱而降低其透氣性。因而可有效預處理該「漿料」以及於其後進行矽熔化過程。於是可直接地固化該熔融矽相或以液態形式被傳送入其他坩堝系統以及專用固化設備。 The carrier gas and hydrogen can be introduced into the powder via a spray gun or the powder can be delivered via a gas frit. In Fig. 2, the drawing shows the configuration in which the air spray gun is used to treat the powder in situ. The air lance is composed of a gas impermeable material having chemical and mechanical stability at high temperatures. Depending on the type of application, for example, alumina (Al 2 O 3 ), other ceramics, and also quartz glass can be used. This gas is delivered to the powder via a spray gun. In order to protect the unit components from contamination and to reduce the risk of explosion due to powder vortex rise, a gas permeable cover may be used as needed. The cover is breathable due to the nature of the material, ceramic materials can be used for this purpose, and graphite can also be used. In addition, the cover may have small holes for exhaust. It should be considered that the selected cover has a sufficiently high temperature (at least 400 ° C) to avoid the transport of cerium oxide (SiO) without causing precipitation and reducing its gas permeability. Therefore, the "slurry" can be effectively pretreated and the crucible melting process thereafter. The molten ruthenium phase can then be directly cured or transferred to other ruthenium systems as well as dedicated curing equipment in liquid form.
1‧‧‧粉體原位處理構造 1‧‧‧ powder in situ treatment structure
2‧‧‧坩堝 2‧‧‧坩埚
3‧‧‧粉體 3‧‧‧ powder
4‧‧‧透氣覆蓋 4‧‧‧ breathable cover
5‧‧‧噴槍 5‧‧‧ spray gun
6‧‧‧氣體 6‧‧‧ gas
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| JPS6168313A (en) * | 1984-09-07 | 1986-04-08 | Osaka Titanium Seizo Kk | Recovery of high purity silicon from silicon chip |
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| CN102502650A (en) * | 2011-10-08 | 2012-06-20 | 江苏佳宇资源利用股份有限公司 | Method for preparing crystalline silicon components from crystalline silicon cutting waste mortar |
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| US20110147979A1 (en) * | 2008-07-09 | 2011-06-23 | Garbo S.R.L. | Method for purification and compaction of feedstock for photovoltaic applications |
| DE102008049303B4 (en) * | 2008-09-29 | 2012-05-24 | Qimonda Ag | Process for producing a silicon wafer and silicon wafers for solar cells |
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| JPS6168313A (en) * | 1984-09-07 | 1986-04-08 | Osaka Titanium Seizo Kk | Recovery of high purity silicon from silicon chip |
| CN102219220A (en) * | 2011-06-08 | 2011-10-19 | 大连理工大学 | Method for recovering Si and SiC from waste slurry by alloying method |
| CN102502650A (en) * | 2011-10-08 | 2012-06-20 | 江苏佳宇资源利用股份有限公司 | Method for preparing crystalline silicon components from crystalline silicon cutting waste mortar |
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