TW201323671A - Device for refining of silicon by directional solidification in an oxygen-containing atmosphere as well as a refining method of silicon - Google Patents
Device for refining of silicon by directional solidification in an oxygen-containing atmosphere as well as a refining method of silicon Download PDFInfo
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Abstract
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本發明關於製造太陽能級矽之領域。特別是，其關於藉由定向性固化將液態矽精煉並提供製造太陽能級矽之特別是液態矽的定向性固化程序之裝置及方法。該裝置包含具有加熱元件的爐，該等加熱元件容許含氧氣氛並置於底板上方，其中該底板上放著含有液態矽之坩堝/模子。該定向性固化包含於包含氧之氣氛中進行的步驟。因此，本發明提供一種定向性固化方法、儲存電腦軟體之電腦可讀性媒介及用於操作定向性固化裝置之程式元件。 The invention relates to the field of manufacturing solar grade crucibles. In particular, it relates to apparatus and methods for refining liquid helium by directional solidification and providing a directional curing procedure for the manufacture of solar grade germanium, particularly liquid helium. The apparatus comprises a furnace having heating elements that permit an oxygen-containing atmosphere and are placed above the bottom plate, wherein the bottom plate contains a crucible/mold containing liquid helium. The directional solidification is included in the step carried out in an atmosphere containing oxygen. Accordingly, the present invention provides a directional curing method, a computer readable medium for storing a computer software, and a program element for operating a directional curing device.
對於太陽能電池面板有越來越高之要求，部分起因於涉及全球暖化。結果，也越來越需要對於以有成本效益和保護生態環境方式(即有能量效益)製造太陽能面板所需之矽的製法。有數種製造矽之方法。這些是化學方法，其涉及以酸處理冶金級矽，接著HCl之氣相反應及氫在矽棒上之氣相分離。此化學方法，習稱為西門子方法，消耗大量能量所以昂貴。物理純化方法涉及精煉具有熔渣和氣體之半純性液態矽，接著固化。將此固體產物壓碎並溶濾Fe、Al、Ca及Ti。接著將此產物再熔化並進行定向性固化。此方法被Elkem公司所利用。 There is an increasing demand for solar panel panels, in part due to global warming. As a result, there is a growing need for a process for manufacturing solar panels that are cost effective and environmentally friendly (ie, energy efficient). There are several ways to make flaws. These are chemical processes involving the treatment of metallurgical grade ruthenium with acid followed by gas phase reaction of HCl and gas phase separation of hydrogen on the ruthenium rod. This chemical method, known as the Siemens method, consumes a lot of energy and is therefore expensive. The physical purification process involves refining a semi-pure liquid helium with slag and gas, followed by solidification. The solid product was crushed and leached with Fe, Al, Ca and Ti. This product is then remelted and subjected to directional solidification. This method is used by Elkem.
在第三種方法中，對純石英進行碳熱還原以獲得矽液，藉由以下步驟精煉該矽液：氣體精煉、溫度調節、沉降 、過濾、撇渣(skimming)及定向性固化。使用此方法之挑戰是製造夠純之矽產物。 In the third method, carbon-thermal reduction of pure quartz is carried out to obtain a mash, and the mash is refined by the following steps: gas refining, temperature regulation, sedimentation , filtration, skimming and directional solidification. The challenge with this method is to make a pure enough ruthenium product.
此定向性固化可例如依照WO 2009/153152進行，其描述包含穿過覆蓋結構頂部中之開口將冶金級矽轉移至在惰性氣體氣氛中的坩堝之步驟，藉由自該惰性氣體氣氛中的坩堝底部移除熱定向性固化之步驟，及由石英坩堝獲得矽錠(本方法的產物)之步驟。 This directional curing can be carried out, for example, in accordance with WO 2009/153152, which describes the step of transferring a metallurgical grade ruthenium into a ruthenium in an inert gas atmosphere through an opening in the top of the cover structure, by means of ruthenium from the inert gas atmosphere The step of removing the thermal directional solidification at the bottom and the step of obtaining the bismuth ingot (the product of the method) from the quartz crucible.
本發明之目的因此，在於提供一種精煉矽之方法，特別是藉由定向性固化，及將液態矽定向性固化為太陽能級矽之裝置，其中該裝置能用經濟方法。特別是不需要純惰性氣體氣氛或昂貴又具有環境污染性之冷凍劑或流體。再者，本發明藉由電腦程式部分自動驅動以製造矽錠之再現性純度。再者，此裝置需要儘可能少之操作空間。除了提供裝置加熱器之目的以外該等裝置加熱器之氣氛中容許至少某含量的O2。 It is therefore an object of the present invention to provide a method of refining crucibles, particularly by means of directional solidification, and the directed solidification of liquid helium into solar grade crucibles, wherein the apparatus can be economically operated. In particular, a pure inert gas atmosphere or an expensive and environmentally toxic refrigerant or fluid is not required. Furthermore, the present invention is automatically driven by a computer program portion to produce reproducible purity of the bismuth ingot. Furthermore, this device requires as little operating space as possible. At least a certain amount of O 2 is allowed in the atmosphere of the heaters of the devices other than the purpose of providing the device heaters.
發明人了解以石英碳熱還原為液態矽接著以液態精煉為基礎的方法是製造太陽能級矽有希望之替代方案，因為與今日此技藝現況相比其能達成低投資成本、低操作成本及低耗能。此精煉步驟包括矽液之定向性固化。更重要的是，發明人意外發現建立和保持純惰性氣氛或惰性氣體氣氛之難以處理的步驟本身在定向性固化方法中並非必要。因此發明人發現降低太陽能級矽製造時涉及之方法的複雜 度之方式。藉以，此方法變得更有效率且更便宜。 The inventors understand that a method based on the thermal reduction of quartz to liquid helium followed by liquid refining is a promising alternative to the manufacture of solar grades because of its low investment cost, low operating cost and low performance compared to today's state of the art. Energy consumption. This refining step involves the directional solidification of the mash. More importantly, the inventors have unexpectedly discovered that the difficult step of establishing and maintaining a purely inert atmosphere or an inert gas atmosphere is not inherently necessary in the directional solidification process. So the inventors found that the complexity of the methods involved in the manufacture of solar grade germanium is reduced. The way of the degree. As a result, this method becomes more efficient and cheaper.
因此，提供一種製造太陽能級矽之方法及用於精煉方法之裝置，其中將矽熔融物加於坩堝/模子，其後自上方加熱及自下方冷卻該坩堝/模子以產生由下往上之固化作用，其特徵在於該由下往上之固化作用係於含氧(O2)氣氛中進行。根據一個具體實施例在由下往上固化時為了更精確之溫度分佈及特別是關於由下往上之固化及重直固化為了更精確之溫度分佈可採取另外藉由加熱元件在底部下方加熱之方式。 Accordingly, there is provided a method of making a solar grade crucible and an apparatus for a refining method, wherein a crucible melt is applied to a crucible/mold, after which the crucible/mold is heated from above and cooled from below to produce a cure from bottom to top. The action is characterized in that the bottom-up curing action is carried out in an oxygen-containing (O 2 ) atmosphere. According to a specific embodiment, in order to achieve a more precise temperature distribution and, in particular, from bottom to top curing and straightening, for a more precise temperature distribution, it can be additionally heated by the heating element below the bottom. the way.
因此，提供提供用於製造太陽能級矽之精煉方法的裝置及製造太陽能級矽之精煉方法，其中將矽熔融物加於模子，其後自上方加熱及自下方冷卻該模子以產生由下往上之固化作用。該裝置及/或方法之特徵在於該由下往上之固化作用係於包含耐氧加熱元件的含氧氣氛中進行。根據一個具體實施例在由下往上固化時為了更精確之溫度分佈及特別是關於由下往上之固化及重直固化為了更精確之溫度分佈可採取另外藉由加熱元件在底部下方加熱之方式。 Accordingly, there is provided an apparatus for providing a refining method for manufacturing a solar grade crucible, and a refining method for manufacturing a solar grade crucible, wherein a crucible melt is applied to a mold, and then the mold is heated from above and cooled from below to produce a bottom to top The curing effect. The apparatus and/or method is characterized in that the bottom-up curing action is carried out in an oxygen-containing atmosphere comprising an oxygen-resistant heating element. According to a specific embodiment, in order to achieve a more precise temperature distribution and, in particular, from bottom to top curing and straightening, for a more precise temperature distribution, it can be additionally heated by the heating element below the bottom. the way.
在此揭示內容之上下文中，“含氧氣氛”表示包含至少1%氧(O2)之氣氛。熟練技術人員了解在定向性固化氣氛中之氧量可能隨著此程序的過程減少，因為可能會消耗一些氧。如文中討論的，這些利用氧之反應無論如何均不會顯著降低矽品質，因為可能消耗一些氧。在本揭示內 容之具體實施例中，該含氧氣氛在整個程序中可例如包含至少2%，如至少5%或至少10%，之氧，特別是至少1體積%，至少2體積%，至少5體積%，至少10體積%至約21體積%。在此程序開始時之氣氛可例如為空氣，其包含約21%氧。 In the context of this disclosure, "oxygen-containing atmosphere" means an atmosphere comprising at least 1% oxygen (O 2 ). The skilled artisan understands that the amount of oxygen in a directional solidification atmosphere may decrease with the process of this procedure as some oxygen may be consumed. As discussed herein, these reactions utilizing oxygen do not in any way significantly reduce the quality of the ruthenium, as some oxygen may be consumed. In a particular embodiment of the present disclosure, the oxygen-containing atmosphere may comprise, for example, at least 2%, such as at least 5% or at least 10%, oxygen, particularly at least 1% by volume, at least 2% by volume, at least throughout the procedure. 5 vol%, at least 10% by volume to about 21% by volume. The atmosphere at the beginning of this procedure can be, for example, air, which contains about 21% oxygen.
因此，本發明之一具體實施例是一種用於定向性固化程序之裝置，特別是製造太陽能級矽之矽熔融物的液態矽同義語，其中該裝置包含含有加熱元件之爐，該等加熱元件容許含氧(O2)氣氛，且該等加熱元件係置於底板上方，其中底板上任意放有坩鍋/模子。特別是該爐包含容許含氧(O2)氣氛之加熱元件，其中該等加熱元件係置於該爐之底板上方及任意放置之坩堝上方。在特定精煉步驟中將坩堝/模子放在該底板上。 Accordingly, one embodiment of the present invention is a device for a directional curing process, particularly a liquid 矽 synonym for the manufacture of a solar grade bismuth melt, wherein the device comprises a furnace containing heating elements, the heating elements An oxygen-containing (O 2 ) atmosphere is tolerated, and the heating elements are placed above the bottom plate, wherein any crucible/mold is placed on the bottom plate. In particular, the furnace comprises heating elements that permit an oxygen-containing (O 2 ) atmosphere, wherein the heating elements are placed above the floor of the furnace and above any desired crucible. The crucible/mold is placed on the bottom plate in a particular refining step.
在該等加熱元件預熱時沒在該底板上放置坩堝，其中在該坩堝之預熱步驟的期間，該坩堝放在該底板上。在之後的步驟中填充液態矽之坩堝放在該底板上並自該板下方冷卻，同時自上方加熱該坩堝。 The crucible is not placed on the bottom plate when the heating elements are preheated, wherein the crucible is placed on the bottom plate during the preheating step of the crucible. In the subsequent step, the liquid helium is filled on the bottom plate and cooled from below the plate while heating the crucible from above.
本發明之另一個具體實施例是一種用於定向性固化程序之裝置，其中該裝置包含含有加熱元件之爐，該等加熱元件容許含氧(O2)氣氛並置於該爐之底板上方及，其中該底板並未固定於該爐結構。此外在該底板下方或下面還有為了冷卻通道而裝設之空氣入口。在該底板下方裝設用於冷卻通道之空氣出口。 Another embodiment of the present invention is a device for a directional curing process, wherein the device comprises a furnace containing heating elements that allow an oxygen-containing (O 2 ) atmosphere and are placed above the bottom plate of the furnace and Wherein the bottom plate is not fixed to the furnace structure. Furthermore, below or below the floor, there is an air inlet for the cooling channel. An air outlet for the cooling passage is installed below the bottom plate.
此外，根據一個具體實施例用於液態矽之定向性固化 程序之裝置另外包含含有MoSi2加熱元件之爐，特別是該等加熱元件設置在該爐之頂蓋內側。特別是用於加熱之加熱元件可達到至少1700℃，如至少1800℃之溫度，並容許氧處於這樣之溫度。較佳是由於此可達到之溫度，即不必在側邊設置加熱置。根據一個具體實施例該裝置包含供給至少166 kW/m2鑄造面積之加熱元件，特別是至少195 kW/m2，較佳60至160 kW/m2，特佳66至195 kW/m2。 Furthermore, the apparatus for the directional solidification procedure of liquid helium according to one embodiment additionally comprises a furnace comprising a MoSi 2 heating element, in particular the heating elements are arranged inside the roof of the furnace. In particular, the heating element for heating can reach a temperature of at least 1700 ° C, such as at least 1800 ° C, and allows oxygen to be at such a temperature. Preferably, due to this achievable temperature, it is not necessary to provide a heating on the side. According to a particular embodiment the device comprises a heating element supplying at least 166 kW/m 2 of casting area, in particular at least 195 kW/m 2 , preferably 60 to 160 kW/m 2 , particularly preferably 66 to 195 kW/m 2 .
本發明之更佳具體實施例包含一種裝置，其另外包含底板及裝設於任意放置之坩堝的側邊或任意放置之模子周圍的支撐結構，其中該底板及支撐結構沒固定於該爐，特別是該爐殼體。本發明之更佳具體實施例包含一種裝置，其中於該坩堝/模子之底部處的矽與該冷卻媒介之間的層之熱傳導率係至少0.75 W/°K，特別是至少0.85 W/°K。也可以，該坩堝/模子之側壁及支撐結構之熱傳導率加總所有層係低於0.75 W/°K，特別是低於0.80 W/°K。根據一個具體實施例穿過該模子底部至冷卻媒介之熱傳導率係至少0.75 W/°K，如至少0.85 W/°K且穿過該模子之側壁結構的熱傳導率係低於0.80 W/°K，如低於0.75 W/°K。 A more preferred embodiment of the present invention comprises a device further comprising a bottom plate and a support structure mounted around the side of any placed crucible or any placed mold, wherein the bottom plate and the support structure are not fixed to the furnace, particularly It is the furnace shell. A more preferred embodiment of the invention comprises a device wherein the layer between the crucible at the bottom of the crucible/die and the cooling medium has a thermal conductivity of at least 0.75 W/°K, in particular at least 0.85 W/°K . It is also possible that the thermal conductivity of the sidewalls of the crucible/mold and the support structure add up to less than 0.75 W/°K, especially less than 0.80 W/°K. According to one embodiment, the thermal conductivity through the bottom of the mold to the cooling medium is at least 0.75 W/°K, such as at least 0.85 W/°K and the thermal conductivity of the sidewall structure passing through the mold is less than 0.80 W/°K. , such as less than 0.75 W / °K.
特別是本發明之一具體實施例是包含底板及/或由碳化矽、氧化矽、石英或另一種具有必需之熱傳導率的純耐熱材料所構成之坩堝/模子的裝置。根據本發明之一具體實施例揭示一種裝置，其中該底板及/或坩堝/模子之尺寸涵蓋等於0.70 m2至4.0 m2的G5錠塊之鑄造面積。 In particular, one embodiment of the invention is a device comprising a substrate and/or a crucible/mold composed of tantalum carbide, yttria, quartz or another pure heat resistant material having the requisite thermal conductivity. In accordance with an embodiment of the present invention, a device is disclosed in which the size of the bottom plate and/or the jaw/mold covers a cast area of a G5 ingot equal to 0.70 m 2 to 4.0 m 2 .
另一個較佳具體實施例包含一種裝置，其另外包含含 有該底板之活動台，特別是該底板朝上放在該活動台上或在該活動台頂部上，並在該底板下方或下面的是冷卻通道之空氣入口及在該底板下方或下面的是空氣出口。特別是該活動台有輪子，較佳為至少4至12個輪子。其中用於冷卻之冷卻系統(包含空氣入口、冷卻通道及空氣出口)能移除至少20 kW/m2模子鑄造面積。根據本發明之一具體實施例的方法，其中用於冷卻之冷卻媒介是空氣。使用空氣特別能保護生態環境且便宜。另外該冷卻媒介，特別是空氣，係供應至設置在該模子底部下面之底板下方。任意於該底板處裝設加熱機構以更精準控制底部冷卻之溫度。因此，空氣可在比固化更早的某個步驟中預熱。底部加熱可於之後的步驟關掉。 Another preferred embodiment includes a device that additionally includes a movable table containing the bottom plate, particularly the bottom plate being placed upside down on the movable table or on top of the movable table, and below or below the bottom plate The air inlet of the cooling passage and below or below the floor are air outlets. In particular, the mobile station has wheels, preferably at least 4 to 12 wheels. The cooling system for cooling (including air inlet, cooling passage and air outlet) is capable of removing at least 20 kW/m 2 of mold casting area. A method according to an embodiment of the invention wherein the cooling medium for cooling is air. The use of air is particularly effective in protecting the environment and being cheap. In addition, the cooling medium, in particular air, is supplied below the floor which is arranged below the bottom of the mould. Any heating mechanism is installed at the bottom plate to more precisely control the temperature of the bottom cooling. Therefore, air can be preheated in a certain step earlier than curing. The bottom heating can be turned off in the subsequent steps.
本發明之較佳裝置包含一種爐，其中該爐包含殼體，該等加熱元件，特別是MoSi2加熱元件，裝設於該殼體中，及其中該殼體包含頂蓋及側壁。特別是該等加熱元件裝設於該頂蓋內側，特別是於該頂蓋之蓋頂。更佳為該爐包含密封殼體(頂部密封、底部敞開)，其中該等加熱元件裝設於該頂蓋之蓋頂內側。再者，該殼體、頂蓋及/或側壁可各自獨立地包含氣體入口。較佳之氣體入口係設置於該頂蓋，特別是具有氣體入口或氣體接管，處之殼體中。該殼體、側壁及/或頂蓋可能沒有其他開口，特別是沒有能透過彼將液態矽填入坩堝中之開口。 A preferred apparatus of the present invention comprises a furnace, wherein the furnace comprises a housing, the heating elements, in particular MoSi 2 heating elements, being mounted in the housing, and wherein the housing comprises a top cover and a side wall. In particular, the heating elements are mounted on the inside of the cover, in particular on the top of the cover. More preferably, the furnace comprises a sealed housing (top seal, open bottom), wherein the heating elements are mounted on the inside of the top of the top cover. Furthermore, the housing, the top cover and/or the side walls may each independently comprise a gas inlet. A preferred gas inlet is provided in the top cover, particularly in a housing having a gas inlet or gas connection. The housing, side walls and/or top cover may have no other openings, in particular, there is no opening through which the liquid helium can be filled into the crucible.
根據本發明之另一個具體實施例該裝置之爐的殼體包含一種密封刀，特別是在該等側壁下端的一種密封刀，特 別是在該等側壁下端處密封刀設置於該等側壁之下方及/或周圍，特別是該等密封刀基本上自該等側壁之下部水平延伸。該等密封刀之功能在於確實保存該爐內的熱。本發明之另一個具體實施例是一種用於定向性固化之裝置，其中該爐包含殼體，該等加熱元件裝設於該殼體中，及其中該殼體包含頂蓋及側壁，其中在該等側壁之下部有密封刀設置於該等側壁處及/或其周圍，特別是該等密封刀基本上自該等側壁之下部水平延伸。 According to another embodiment of the invention, the housing of the furnace of the apparatus comprises a sealing knife, in particular a sealing knife at the lower end of the side walls, The sealing knives are disposed below and/or around the side walls at the lower ends of the side walls, and in particular the sealing knives extend substantially horizontally from the lower portions of the side walls. The function of the sealing knives is to ensure that the heat in the furnace is preserved. Another embodiment of the present invention is a device for directional curing, wherein the furnace includes a housing, the heating elements are mounted in the housing, and wherein the housing includes a top cover and a side wall, wherein A sealing knife is disposed at the lower side of the side walls and/or around the side walls, and in particular, the sealing blades extend substantially horizontally from the lower portions of the side walls.
特別是該裝置包含至少一或多個密封刀，該密封刀能配合接近具有底部之爐的第二底部處之粒狀材料，並隔離該爐中之內部氣氛與周遭環境氣氛。這個利用密封刀之特殊封閉作用使定向性固化爐內側能得到非常準確之溫度控制。此準確度是使太陽能級矽錠之純度再現所必需。 In particular, the apparatus includes at least one or more sealing knives that can accommodate the granular material at the second bottom of the furnace having the bottom and isolate the internal atmosphere and ambient ambient atmosphere in the furnace. This special sealing action with a sealing knife allows very accurate temperature control of the inside of the directional curing oven. This accuracy is necessary to reproduce the purity of the solar grade bismuth ingot.
為了該裝置較好之冷卻準確度，該裝置包含放在該底板下面外周圍或下方之空氣入口，及其中冷卻通道自空氣入口延伸至基本上該底板在該鑄造區大約中間或該坩堝/模子大約中間任意放置之處，特別是放在各側上，特別是放在四側各者上，空氣入口設置於該底板下方或下面，可能有1至20個空氣入口連至冷卻通道。特別是一種自該鑄造區外周圍至該鑄造區中間之圓形冷卻。 For better cooling accuracy of the device, the device includes an air inlet disposed around or below the underside of the floor, and wherein the cooling passage extends from the air inlet to substantially the floor in the middle of the casting zone or the jaw/mold Arbitrarily placed in the middle, especially on each side, especially on each of the four sides, the air inlet is placed below or below the floor, and there may be 1 to 20 air inlets connected to the cooling channel. In particular, a circular cooling from the periphery of the casting zone to the middle of the casting zone.
根據本發明之一較佳具體實施例冷卻自該底板外周圍開始穿過底板至該底板中間進行。因此，該鑄造區中間冷卻得比外周圍更慢，因為空氣自外周圍採取熱能使該底板中間之溫度比空氣入口處暖。冷空氣在另一個較佳操作步 驟或模式中穿過該底板中間中之通道進來並穿過周圍抽出，特別是空氣能穿過“空氣入口”抽出。冷卻扇沒吹風抽出。該扇可轉成接著吹送該底板周圍部分中之最冷空氣。 According to a preferred embodiment of the invention, cooling is carried out from the outer periphery of the bottom plate through the bottom plate to the middle of the bottom plate. Therefore, the casting zone is cooled more slowly in the middle than in the outer periphery because the heat taken from the outer periphery of the air enables the temperature in the middle of the bottom plate to be warmer than the air inlet. Cold air in another preferred step In the mode or mode, the passage through the middle of the bottom plate comes in and is drawn through the surroundings, in particular the air can be drawn through the "air inlet". The cooling fan is not blown out. The fan can be converted to the coldest air that is then blown into the surrounding portion of the floor.
較佳為該等加熱元件之溫度可單獨變化或該等加熱元件可單獨開關，其中較佳為該等加熱元件之溫度可以變化。因此，固定溫度分佈可自液態矽頂部提供以進行定向性固化。外周圍之溫度可與其後之錠表面的中間不同。 Preferably, the temperature of the heating elements can be varied individually or the heating elements can be individually switched, wherein preferably the temperature of the heating elements can vary. Thus, a fixed temperature profile can be provided from the top of the liquid helium for directional solidification. The temperature of the outer periphery may be different from the middle of the surface of the ingot after it.
此外，有關該爐較佳為該爐側壁具有獨立之絕緣板(第3圖，218)。目標是達到該錠內側之極限熱控制以透過其他金屬之分佈係數自該液態矽熔融物分離出其他金屬。 Further, it is preferred that the furnace has a separate insulating plate on the side wall of the furnace (Fig. 3, 218). The goal is to achieve ultimate thermal control of the inside of the ingot to separate other metals from the liquid helium melt through the distribution coefficient of other metals.
根據本發明之第二方面提供一種裝置，其包含具有加熱元件之爐，其中該爐可垂直移動及，其中該底板可水平移動，特別是能供坩堝/模子置於爐中，依一個操作模式將該爐置於該活動台上之位置A及將該坩堝/模子置於位置B。依以下操作模式將具有該等加熱元件之爐向上移動，及任意依另一個操作模式使該活動台在該爐之下向側面移動，及依另一個操作模式使該爐在位置B之坩堝/模子正上方向下移動。特別是該等密封刀封閉該爐並分離內部氣氛與外部氣氛。在定向性固化時可能消耗掉氧含量。 According to a second aspect of the present invention, there is provided a device comprising a furnace having a heating element, wherein the furnace is vertically movable, wherein the bottom plate is horizontally movable, in particular, the crucible/die can be placed in the furnace, in an operating mode The furnace is placed in position A on the movable table and the crucible/mold is placed in position B. The furnace having the heating elements is moved upward according to the following operation mode, and the movable table is moved laterally under the furnace according to another operation mode, and the furnace is placed at position B according to another operation mode. The mold moves directly up and down. In particular, the sealing knives enclose the furnace and separate the internal atmosphere from the external atmosphere. Oxygen content may be consumed during directional solidification.
此方法中所用之模子可例如為坩堝。在定向性固化中使用之模子/坩堝一般具有小於1 m2之鑄造區。然而，在根據本揭示內容之大規模製造時，該模子/坩堝之鑄造區可例如為1至4 m2。在此，當自上方觀看時該鑄造區表 示該模子之截面積。 The mold used in this method can be, for example, ruthenium. The mold/twist used in the directional solidification typically has a casting zone of less than 1 m 2 . However, in the large-scale manufacturing according to the present disclosure, the casting zone of the mold/twist may be, for example, 1 to 4 m 2 . Here, the casting zone indicates the cross-sectional area of the mold when viewed from above.
根據本發明之第二方面揭示用於液態矽之定向性固化方法的裝置之操作方法，特別是上述裝置之操作方法，其中該方法包含在該定向性固化時不一定連續之操作步驟，如a)坩堝/模子移動步驟，特別是在有輪子之活動台上的水平移動步驟；及任意地；b)爐移動步驟；其中爐移動步驟特別是依垂直方式；及任意地；c)定向性固化步驟，其中定向性固化步驟包含以下操作步驟：(i)任意加熱坩堝/模子，特別是坩堝/模子之預熱；(ii)給坩堝/模子填充液態矽，特別是在空氣存在下；(iii)自上方加熱該填充液態矽之坩堝/模子，及任意地；(iv)自下方冷卻該坩堝/模子以產生由下往上之固化作用。一般在步驟(iv)時藉由該底板下方之空氣冷卻完成冷卻。但是根據一個替代方案冷卻可包含讓其本身自己冷卻下來及/或藉由減少該等加熱元件之熱能而冷卻。在工業程序中要將矽錠之純度及定向性固化方法耗掉之時間最適化能藉由具有個別加熱元件之最佳化恆定時間/溫度分佈及最佳化時間/空氣流量分佈的電腦程式完成精準空氣冷卻。 According to a second aspect of the present invention, there is disclosed a method of operating a device for a directional solidification method of liquid helium, and more particularly to a method of operating the above apparatus, wherein the method comprises a step which is not necessarily continuous during the directional solidification, such as a a 坩埚/mould movement step, in particular a horizontal movement step on a movable table with wheels; and optionally; b) a furnace moving step; wherein the furnace moving step is particularly in a vertical manner; and optionally; c) directional solidification a step wherein the directional solidification step comprises the steps of: (i) heating the crucible/die, especially the preheating of the crucible/mold; (ii) filling the crucible/die with liquid helium, especially in the presence of air; Heating the enthalpy/die of the liquid enthalpy from above, and optionally; (iv) cooling the enthalpy/die from below to produce a cure from bottom to top. Cooling is typically accomplished by air cooling under the bottom plate during step (iv). However, cooling according to an alternative may involve cooling itself down and/or cooling by reducing the thermal energy of the heating elements. In industrial processes, the purity of the bismuth ingot and the time taken by the directional solidification method can be optimized by a computer program with optimized constant time/temperature distribution and optimized time/air flow distribution for individual heating elements. Precision air cooling.
在本發明之較佳具體實施例中該方法另外包含在該定向性固化時不一定連續之操作步驟：a)坩堝/模子移動步驟，b)爐水平移動步驟，其中 特別是該爐也藉由活動台之側向移動步驟於位置A與B之間相對移動，c)定向性固化步驟，其包含以下操作步驟：(i)加熱坩堝/模子；(ii)在空氣存在下給坩堝/模子填充液態矽；(iii)自上方加熱該填充液態矽之坩堝/模子，及任意地；(iv)自下方冷卻該坩堝/模子以產生由下往上之固化作用，及特別是，其中(i)及/或(iii)自MoSi2加熱元件上方加熱該坩堝/模子，- 其中步驟c)，(i)包含在添加該矽熔融物之前將該坩堝/模子預熱至至少1000℃之步驟，其中該坩堝/模子係位於該活動台上之位置B且該爐係位於位置B，特別是使該爐在該坩堝/模子正上方向下移動；- 在後續步驟b)中使爐向上移動，特別是垂直向上，在後續步驟a)中使具有坩堝/模子之活動台向側面移動，特別是水平向側面，及在後續步驟b)中使爐在活動台之位置A上向下移動，任意地在步驟c)(ii)中給該坩堝/模子填充液態矽，特別是在空氣存在下；- 在後續步驟b)中使爐向上移動，及a)使活動台向側面移動以將坩堝/模子設立在爐之下，其後在步驟b)中使爐在位置B之坩堝/模子正上方向下移動；- 在後續步驟c)中進行定向性固化，藉由(iii)自上方加熱該填充液態矽之坩堝/模子，及(iv)藉由冷卻該坩堝/模子，特別是藉由空氣自下方，以產生由下往上之固化作用。所用之空氣可先預熱以供於該定 向性固化的某些步驟中冷卻，特別是於開始時，於其後步驟時均可使用一般冷空氣。預熱空氣意指在任何案例中空氣均比該矽熔融物冷而能冷卻該熔融物。 In a preferred embodiment of the invention the method additionally comprises a step of operation which is not necessarily continuous during the directional solidification: a) a 坩埚/die movement step, b) a furnace horizontal movement step, wherein in particular the furnace is also The lateral movement of the movable table is relatively moved between positions A and B, c) a directional curing step comprising the following steps: (i) heating the crucible/mold; (ii) filling the crucible/die in the presence of air Liquid helium; (iii) heating the liquid helium/die from above, and optionally; (iv) cooling the crucible/die from below to produce a bottom-up curing effect, and in particular, (i) And/or (iii) heating the crucible/mold from above the MoSi 2 heating element, wherein step c), (i) comprises the step of preheating the crucible/mold to at least 1000 ° C prior to adding the crucible melt, wherein The crucible/mould is located at position B on the movable table and the furnace is located at position B, in particular to move the furnace downwards directly above the crucible/mold; - in the subsequent step b), the furnace is moved upwards, in particular Is vertical up, in the subsequent step a) to have 坩埚 / The movable table moves to the side, in particular horizontally to the side, and in the subsequent step b) moves the furnace downwards at the position A of the movable table, optionally filling the cassette in the step c) (ii) Liquid helium, especially in the presence of air; - moving the furnace upwards in a subsequent step b), and a) moving the movable table to the side to set the crucible/mold under the furnace, and thereafter in step b) The furnace moves downwardly above the position B/mold; - in the subsequent step c), by (iii) heating the liquid helium/die from above, and (iv) by cooling The crucible/mould, especially by air from below, produces a curing action from bottom to top. The air used may be preheated for cooling in certain steps of the directional solidification, particularly at the beginning, where normal cold air may be used in subsequent steps. Preheating the air means that in any case the air is cooler than the crucible melt to cool the melt.
根據本發明之一具體實施例坩堝/模子之任意加熱步驟，特別是坩堝/模子之預熱可藉由該定向性固化爐或也可以藉由具有加熱機構之可加熱澆桶或坩堝進行，或根據另一個替代方案預熱可於獨立爐如保溫爐中進行。 According to one embodiment of the invention, any heating step of the crucible/mold, in particular the preheating of the crucible/mould can be carried out by the directional solidification oven or also by a heated ladle or crucible having a heating mechanism, or According to another alternative, the preheating can be carried out in a separate furnace such as a holding furnace.
關於該(i)預熱步驟將一定量之固態矽，例如矽片或塊狀矽，較佳是具有一定純度之固態矽填入坩堝中以便在填充液態矽時保護該坩堝，其中該矽包含低於0.55 ppm(重量比)硼，較佳等於或低於0.3至0.55 ppm(重量比)硼，特別是0.1至0.3 ppm(重量比)硼，低於0.8 ppm(重量比)磷，較佳0.4 ppm(重量比)硼，特別是低於0.1至0.01 ppm(重量比)磷，低於2 ppm(重量比)鋁，特別是低於0.1至2 ppm(重量比)鋁，經去除這些層之後低於0.1 ppm(重量比)，如低於0.01 ppm(重量比)銅，低於0.05 ppm(重量比)鈉，低於0.1 ppm(重量比)，如低於0.05 ppm(重量比)鈣，低於0.05 ppm(重量比)鐵，低於0.05 ppm(重量比)鈦。在較佳具體實施例中，純度可為0.3 ppm(重量比)硼、0.4磷(ppm(重量比))且所有金屬元素(除了矽)之總量低於5 ppm(重量比)，特別是低於4 ppm(重量比)。具有固態矽之坩堝的預熱能於約1200℃之爐溫或約1000至約1410℃，特別是1100至1200℃，每分鐘增加10℃。為了達到這 些高溫該加熱元件可具有至少1550℃之溫度，特別是至高1700℃。經過預熱步驟之後將該爐向上移並將具有經預熱之坩堝的活動台向側面移至填充位置。在此步驟期間將此爐再向下移並置於該活動台上，以保存熱能。在空氣存在下自澆桶將液態矽填入底部包含固態矽之經預熱的坩堝。再將該爐往上移，該活動向側面移至該底板上具有填充液態矽之位置B且該爐向下移。由於爐水平移動步驟，其中該藉由活動台側向移動之步驟僅在兩位置A與B之間相對移動，該裝置需要非常小之空間。 With respect to the (i) preheating step, a certain amount of solid hydrazine, such as a crucible or a lumpy lumpy, preferably a solid mash having a certain purity, is filled into the crucible to protect the crucible when filled with liquid hydrazine, wherein the hydrazine contains Less than 0.55 ppm by weight of boron, preferably equal to or lower than 0.3 to 0.55 ppm by weight of boron, particularly 0.1 to 0.3 ppm by weight of boron, and less than 0.8 ppm by weight of phosphorus. 0.4 ppm by weight of boron, especially less than 0.1 to 0.01 ppm by weight of phosphorus, less than 2 ppm by weight of aluminum, especially less than 0.1 to 2 ppm by weight of aluminum, after removal of these layers Then less than 0.1 ppm (by weight), such as less than 0.01 ppm (by weight) copper, less than 0.05 ppm (by weight) sodium, less than 0.1 ppm (by weight), such as less than 0.05 ppm (by weight) calcium , less than 0.05 ppm by weight of iron, less than 0.05 ppm by weight of titanium. In a preferred embodiment, the purity may be 0.3 ppm by weight boron, 0.4 phosphorus (ppm (by weight)) and the total amount of all metal elements (except hydrazine) is less than 5 ppm (by weight), especially Less than 4 ppm (weight ratio). The preheating energy of the crucible having a solid crucible can be at a furnace temperature of about 1200 ° C or about 1000 to about 1410 ° C, especially 1100 to 1200 ° C, and an increase of 10 ° C per minute. In order to achieve this The high temperature heating element can have a temperature of at least 1550 ° C, especially up to 1700 ° C. After the preheating step, the furnace is moved up and the stage with the preheated helium is moved to the side to the filling position. During this step the furnace is moved down again and placed on the table to conserve heat. In the presence of air, the liquid helium is filled into the bottom of the tank containing the preheated helium of the solid helium. The furnace is then moved up and the activity is moved sideways to a position B on the floor which is filled with liquid helium and the furnace is moved downwards. Due to the horizontal movement of the furnace, wherein the step of lateral movement by the movable table is only relatively moved between the two positions A and B, the device requires a very small space.
因為該爐包含密封刀，所以該定向性固化方法之內部氣氛與外部氣氛確實分開。由於測量結果及氬之氣體接管，在該定向性固化步驟時可藉由提供氬控制由空氣及一些氬開始之內部氣氛。固化時可能消耗氧。於該定向性固化步驟結束時加熱器不再需要其他氧，因為該等加熱器之加熱溫度降低或被關掉。在定向性固化時加熱元件之溫度可降至1000至1400℃，在一些步驟中較佳降至1000℃。經過一定時間之後加熱器溫度再分幾步驟降低。在整個定向性固化步驟期間在該底板下方之空氣冷卻仍在持續中。沖洗氬也可預熱以使液態矽之冷卻作用可視需要減緩。於該固化步驟結束時關掉加熱器，氬可關掉，而空氣冷卻仍然運行。等到進一步冷卻之後，該爐往上移且該活動台往側面移且爐向下移以保存熱能。現在坩堝已經準備釋出富含雜質之錠外層的切削步驟之太陽能級矽錠。 Since the furnace contains a sealing knife, the internal atmosphere of the directional solidification method is indeed separated from the external atmosphere. Due to the measurement results and the argon gas connection, the internal atmosphere initiated by air and some argon can be controlled by providing argon during the directional solidification step. Oxygen may be consumed during curing. At the end of the directional curing step, the heater no longer requires additional oxygen because the heating temperature of the heaters is reduced or turned off. The temperature of the heating element during directional solidification can be reduced to 1000 to 1400 ° C, preferably to 1000 ° C in some steps. After a certain period of time, the heater temperature is further reduced in several steps. Air cooling below the floor during the entire directional curing step is still ongoing. The flushing argon may also be preheated to allow the cooling of the liquid helium to be slowed down as desired. The heater is turned off at the end of the curing step, argon can be turned off, and air cooling is still running. After further cooling, the furnace moves up and the table moves to the side and the furnace moves down to conserve heat. Now the solar grade bismuth ingots are ready to release the cutting step of the outer layer of the impurity-rich ingot.
發明人發現矽熔融物加於該坩堝/模子可於空氣氣氛 中進行，其中該液態矽熔融物係藉由自澆桶或於感應爐中直接將該液態矽熔融物澆注至模子而加於該模子，上述澆注係於空氣氣氛中進行。因此，該爐中之加熱元件可置於該爐頂部以自矽上方加熱矽，導致正在固化之矽錠中的溫度分佈更精準之控制並導致較佳錠純度。在另一個較佳具體實施例中步驟c)(i)及/或(iii)之加熱效應係至少170 kW/m2鑄造面積，如至少195 kW/m2鑄造面積。此外，此方法另外包含移除自固化作用獲得之固態矽錠的頂層之步驟並包含移除自固化作用獲得之固態矽錠的側層和底層之另一個步驟，其中被移除之側層及底層可於一個運行提供矽熔融物給定向性固化的獨立程序中集中並再循環。此定向性再循環較不宜，因為雜質會累積。根據一個選擇方案，於底板處，特別是在該底板202裡面、底下或上方，裝設加熱機構232。此加熱機構232可提供至高1500℃，特別是至高1258℃之溫度。 The inventors have found that the addition of the ruthenium melt to the ruthenium/mold can be carried out in an air atmosphere, wherein the liquid ruthenium melt is applied to the mold by pouring the liquid ruthenium melt directly into the mold from a ladle or in an induction furnace. In the mold, the above casting is carried out in an air atmosphere. Thus, the heating elements in the furnace can be placed on top of the furnace to heat the crucible from above the crucible, resulting in a more precise control of the temperature distribution in the crucible being solidified and resulting in better ingot purity. In another preferred embodiment the heating effect of step c) (i) and / or (iii) is at least 170 kW / m 2 of casting area, such as at least 195 kW / m 2 of casting area. In addition, the method additionally comprises the steps of removing the top layer of the solid bismuth ingot obtained by self-cure and including the step of removing the side layer and the bottom layer of the solid bismuth ingot obtained by self-cure, wherein the removed side layer and The bottom layer can be concentrated and recycled in a separate process running to provide a bismuth melt for directional solidification. This directional recycling is less desirable because impurities can accumulate. According to an alternative, a heating mechanism 232 is provided at the bottom plate, in particular inside, below or above the bottom plate 202. This heating mechanism 232 can provide temperatures up to 1500 ° C, especially up to 1258 ° C.
較佳於含氧氣氛，如空氣，中進行將液態矽加於該坩堝/模子。這樣之添加可在進行定向性固化之爐外側發生。通常，當該坩堝以液態矽填充時該坩堝係置於該活動台之底板上的位置B且該爐係置於位置A。因此，在填充或固化時一般沒提供保護性惰性氣體。此方法添加之液態矽可例如自石英之碳熱還原或自升級之冶金級矽獲得。熟練者知道均可於此獨創性裝置之坩堝中填充任何一定純度的液態矽。另外，該液態矽可能在其進行定向性固化之前已經以液態精煉或過濾過。為了使該液態矽可以儘可能精準 且緩慢冷卻下來，在該液態矽填入之前預熱該坩堝/模子(第8圖)。 Preferably, liquid helium is applied to the crucible/mold in an oxygen-containing atmosphere such as air. Such addition can occur outside of the furnace where the directional solidification is performed. Typically, when the crucible is filled with liquid helium, the crucible is placed in position B on the floor of the movable table and the furnace is placed in position A. Therefore, a protective inert gas is generally not provided at the time of filling or curing. The liquid helium added by this method can be obtained, for example, from the carbothermal reduction of quartz or from an upgraded metallurgical grade. The skilled person knows that the liquid helium of any purity can be filled in the crucible of this original device. Additionally, the liquid helium may have been refined or filtered in liquid form prior to its directional solidification. In order to make the liquid helium as accurate as possible And slowly cooled down, preheating the crucible/mold before filling the liquid helium (Fig. 8).
例如，該液態矽可能已經濾掉碳化物並藉由氣體萃取精煉，例如以氯氣，任意與惰性氣體，如氬，合併。此萃取作用移除鋁(Al)、鈣(Ca)及其他能在支配條件之下與氯氣形成鹽類或熔渣的元素。 For example, the liquid helium may have been filtered out of the carbide and refined by gas extraction, for example with chlorine, optionally combined with an inert gas such as argon. This extraction removes aluminum (Al), calcium (Ca) and other elements that can form salts or slag with chlorine under controlled conditions.
在定向性固化時，自正在固化之矽分離出鐵(Fe)、Al及其他具有低分佈係數的金屬，因為其於熔融物中具有較高溶解度。因此，該定向性固化是精煉步驟。特別是在本發明之方法的具體實施例中加熱時用之加熱元件能達到至少1700℃之元件溫度，如至少1800℃，並容許氧處於此溫度。根據本發明之方法該定向性固化步驟需要加熱元件以及冷卻媒介，例如空氣，之精準溫度控制。為了避免該錠之外周圍處較早固化，一般冷卻空氣可透過空氣入口提供至冷卻通道並透過空氣出口離開。但是在一些案例中透過空氣出口提供冷空氣至冷卻通道可能更方便並讓熱空氣於空氣入口離開，以便能自底部中間至外周圍產生冷卻作用。以下表1及2顯示由碳熱還原但是沒接著氯氣之氣體萃取所獲得之矽液的定向性固化結果。 In the directional solidification, iron (Fe), Al, and other metals having a low distribution coefficient are separated from the crucible being solidified because of its high solubility in the melt. Therefore, the directional solidification is a refining step. In particular, in a particular embodiment of the method of the invention, the heating element used for heating can achieve a component temperature of at least 1700 ° C, such as at least 1800 ° C, and allows oxygen to be at this temperature. The directional curing step in accordance with the method of the present invention requires precise temperature control of the heating element as well as a cooling medium, such as air. In order to avoid earlier curing of the periphery of the ingot, generally cooling air can be supplied to the cooling passage through the air inlet and exit through the air outlet. However, in some cases it may be more convenient to provide cold air through the air outlet to the cooling passage and allow hot air to exit the air inlet so that cooling can occur from the middle of the bottom to the outer circumference. Tables 1 and 2 below show the results of the directional solidification of the mash obtained by carbothermal reduction but without gas extraction with chlorine.
在定向性固化之前，該液態矽可例如藉由自澆桶或感應爐直接澆注至該坩堝/模子中而加於該坩鍋或模子。在此具體實施例中此澆注較佳係於空氣氣氛中進行。該定向性固化期間之冷卻可例如具有至少20 kW/m2鑄造面積之效應。此鑄造面積正常與該坩堝/模子內側之底部面積相同。 Prior to directional solidification, the liquid helium may be applied to the crucible or mold, for example, by pouring directly into the crucible/mold from a ladle or induction furnace. This casting is preferably carried out in an air atmosphere in this embodiment. The cooling during the directional solidification may for example have an effect of a casting area of at least 20 kW/m 2 . This cast area is normally the same as the bottom area of the inside of the crucible/die.
冷卻所用之冷卻媒介較佳為空氣。該冷卻媒介可被供應至設置於該坩堝/模子底部之下的板子下方。此板可為用於定向性固化之裝置的一部分。也可以，該底板可為非固定物體，該坩堝在底板上轉移至用於定向性固化之裝置 上。該底板及該坩堝/模子可例如由碳化矽、氧化矽、石英或另一種具有必需之熱傳導率的純耐熱材料構成。該底板及坩堝/模子之尺寸可經變化以涵蓋等於至多4.0 m2的G5錠(0.70 m2)之鑄造面積。冷卻時，熱穿過該坩堝/模子之底部且，如果適用的話，穿過設置於該坩堝/模子之下的板或另一個結構傳導至該冷卻媒介。 The cooling medium used for cooling is preferably air. The cooling medium can be supplied below the board disposed below the bottom of the die. This plate can be part of a device for directional curing. Alternatively, the bottom plate can be a non-stationary object that is transferred to the device for directional solidification on the bottom plate. The bottom plate and the crucible/mold may be composed, for example, of tantalum carbide, tantalum oxide, quartz or another pure heat resistant material having the necessary thermal conductivity. The size of the bottom plate and the jaw/mold can be varied to cover a cast area equal to a G5 ingot (0.70 m 2 ) of up to 4.0 m 2 . Upon cooling, heat passes through the bottom of the crucible/mold and, if applicable, is conducted to the cooling medium through a plate or another structure disposed beneath the crucible/mold.
已發現如果於該坩堝/模子之底部處的矽與該冷卻媒介之間的層之熱傳導率係至少0.75 W/°K，如至少0.85 W/°K即可獲得有效之冷卻。在此，其表示所有相關層之聯合熱傳導率。該坩堝/模子及該坩堝/模子與該冷卻媒介之間的任何其他結構之尺寸和材料可據此選擇。 It has been found that effective cooling can be achieved if the thermal conductivity of the layer between the crucible at the bottom of the crucible/die and the cooling medium is at least 0.75 W/°K, such as at least 0.85 W/°K. Here, it represents the combined thermal conductivity of all relevant layers. The size and material of the crucible/mold and any other structure between the crucible/mold and the cooling medium can be selected accordingly.
為了獲得固化正面之平坦至稍凸的外形，包括支撐結構之坩堝/模子的側壁較佳具有低熱傳導率。如果側壁結構之熱傳導率加總所有層係低於0.75 W/°K，如至少低於0.80 W/°K。此外，有關該爐較佳是該爐之側壁具有獨立的絕緣板(第3圖，218)。目標是達到該錠內側之極限熱控制以透過其他金屬之分佈係數自該液態矽熔融物分離出其他金屬。 In order to obtain a flat to slightly convex shape of the cured front surface, the side walls of the crucible/mold including the support structure preferably have a low thermal conductivity. If the thermal conductivity of the sidewall structure is increased, all layers are below 0.75 W/°K, such as at least below 0.80 W/°K. Further, it is preferred that the furnace has a separate insulating plate on its side wall (Fig. 3, 218). The goal is to achieve ultimate thermal control of the inside of the ingot to separate other metals from the liquid helium melt through the distribution coefficient of other metals.
在由上而下之定向性固化程序至少部分期間自上方加熱該矽液(第3和11圖)。依此方式，該由上而下之定向性固化程序可更正確地控制。較佳地，在整個由上而下之定向性固化程序期間均自上方加熱該矽液。加熱程度也可隨著該定向性固化程序之過程變換。例如，當越來越多矽部分固化時可減少加熱程度。例如，該爐中之加熱器溫 度可設定於接近該固化程序結束時之矽的固化溫度。 The mash is heated from above during at least a portion of the directional curing process from top to bottom (Figs. 3 and 11). In this way, the top-down directional curing process can be more accurately controlled. Preferably, the mash is heated from above during the entire top-down directional solidification procedure. The degree of heating can also vary with the course of the directional curing process. For example, the degree of heating can be reduced as more and more of the crucible is partially cured. For example, the heater temperature in the furnace The degree can be set to a curing temperature close to the end of the curing process.
因此，此程序開始時可供應比此程序結束時更多熱。在一個具體實施例中，在定向性固化程序時之加熱效應為60至160 kW/m2鑄造面積。在更特定之具體實施例中，該加熱效應為66至195 kW/m2。 Therefore, this program can be supplied more hotter than the end of this program. In a specific embodiment, the heating effect during the directional solidification procedure is 60 to 160 kW/m 2 of casting area. In a more specific embodiment, the heating effect is 66 to 195 kW/m 2 .
一種用於定向性固化程序之裝置因此可裝設加熱機構。較佳地，這樣之裝置能供給至少166 kW/m2鑄造面積，如至少195 kW/m2鑄造面積。這樣之裝置於高溫也容許含氧氣氛。在一個具體實施例中，加熱所用之加熱元件能達到至少1700℃，如至少1800℃之溫度。這樣之加熱元件可例如為MoSi2；加熱元件(例如KANTHAL Super)。該MoSi2加熱元件實際上需要含氧氣氛以達到這樣之高溫。因此，在先前技藝之技術中，如WO 2009/153152之揭示內容，其中該定向性固化係於惰性氣氛中進行，其若無法達到超過1700℃之元件溫度可能會有困難。 A device for a directional curing procedure can therefore be provided with a heating mechanism. Preferably, such a device is capable of supplying a casting area of at least 166 kW/m 2 , such as a casting area of at least 195 kW/m 2 . Such a device also allows an oxygen-containing atmosphere at high temperatures. In a specific embodiment, the heating element used for heating can reach a temperature of at least 1700 ° C, such as at least 1800 ° C. Such a heating element may for example be MoSi 2 ; a heating element (for example KANTHAL Super). The MoSi 2 heating element actually requires an oxygen-containing atmosphere to achieve such a high temperature. Thus, in the prior art, as disclosed in WO 2009/153152, wherein the directional solidification is carried out in an inert atmosphere, it may be difficult if the temperature of the component exceeding 1700 ° C cannot be reached.
因此與本揭示內容之定向性固化程序相比較不可能控制先前技藝之控制定向性固化程序。該坩堝/模子較佳可在矽液添加之前先預熱。預熱可於與後續定向性固化相同之裝置中進行。在此具體實施例中，該坩堝可於該裝置中預熱並接著以液態矽填於該裝置外側，及其後，於此裝置中進行液態矽在該坩堝/模子中之定向性固化。因此，只要一個裝置即可用於兩種不同作業。 It is therefore not possible to control the prior art control directional curing procedure as compared to the directional curing procedure of the present disclosure. Preferably, the file/mold is preheated prior to the addition of the mash. Preheating can be carried out in the same apparatus as the subsequent directional solidification. In this embodiment, the crucible can be preheated in the apparatus and then filled in the liquid outside of the apparatus, and thereafter, the orientation of the liquid helium in the crucible/mold is cured in the apparatus. Therefore, as long as one device can be used for two different jobs.
也可以，於兩種不同裝置中進行預熱及定向性固化。此具體實施例在大規模製造時可能有所益處。在工業裝置 中，預熱裝置可置於一或多個用於定向性固化之裝置的下游位置。因為該定向性固化通常比預熱花更多時間，所以其可能有益於聯合多個用於定向性固化之裝置與單一預熱裝置。在添加該液態矽之前，將該坩堝/模子例如加熱至至少1000℃，最佳1250℃。也就是說，當由下往上之定向性固化期間添加液態矽時該坩堝/模子可具有至少1000℃之溫度，污染物將累積於液相中且最後，當固化完成時，累積於所得之矽錠的頂層中。因此，在矽作為製造太陽能電池之原料之前移除頂層。另外，該錠之側層及底層也可被移除，因為其可能含有來自該坩堝/模子及塗層之雜質。 It is also possible to carry out preheating and directional solidification in two different devices. This particular embodiment may be of benefit in large scale manufacturing. In industrial installations The preheating device can be placed in a downstream position of one or more devices for directional solidification. Because this directional cure typically takes more time than preheating, it may be beneficial to combine multiple devices for directional solidification with a single preheat device. The crucible/mold is heated, for example, to at least 1000 ° C, preferably 1250 ° C, prior to the addition of the liquid helium. That is, the enthalpy/mold may have a temperature of at least 1000 ° C when liquid hydrazine is added during the directional solidification from bottom to top, contaminants will accumulate in the liquid phase and finally, when the curing is completed, it is accumulated in the obtained In the top layer of the ingot. Therefore, the top layer is removed before the crucible is used as a raw material for manufacturing the solar cell. Additionally, the side and bottom layers of the ingot may also be removed as it may contain impurities from the crucible/mold and coating.
該頂層及任意其他層可由太陽能電池製造商移除。然而，該等層較佳藉由進行定向性固化程序之參與者移除。該等層可例如藉由切削或研磨自該錠分離。在移除之前被移除之頂層的厚度可例如為該錠高度之10至15%。同樣地，在移除之前被移除之頂層的體積可例如為該錠體積之10至15%。 The top layer and any other layers can be removed by the solar cell manufacturer. However, the layers are preferably removed by the participant performing the directional curing process. The layers can be separated from the ingot by, for example, cutting or grinding. The thickness of the top layer that is removed prior to removal may be, for example, 10 to 15% of the height of the ingot. Likewise, the volume of the top layer that was removed prior to removal may be, for example, 10 to 15% of the volume of the ingot.
被移除之側層的厚度可例如為10至30 mm，如約20 mm。同樣地，如果鑄造面積增加，被移除之側層的體積可換算成該錠體積之%。關於G5錠(840mm×840mm)在移除之前20 mm之側面切削部表示該錠體積的9.3%，而自具有2.0 m2之鑄造面積的錠切掉之側面切削部表示該錠體積的5.9%。在移除之前被移除之底層的厚度可例如為該錠高度之5至7%。同樣地，在移除之前被移除之底 層的體積可例如為該錠體積之5至7%。 The thickness of the side layer to be removed may be, for example, 10 to 30 mm, such as about 20 mm. Likewise, if the cast area is increased, the volume of the removed side layer can be converted to % of the ingot volume. Regarding the G5 ingot (840 mm × 840 mm), the side cutting portion of 20 mm before removal indicates 9.3% of the volume of the ingot, and the side cutting portion cut from the ingot having a casting area of 2.0 m 2 indicates 5.9% of the volume of the ingot. . The thickness of the underlayer that is removed prior to removal may be, for example, from 5 to 7% of the height of the ingot. Likewise, the volume of the underlayer that was removed prior to removal may be, for example, 5 to 7% of the volume of the ingot.
等移除該等層之後，該錠可為例如包含少於0.55 ppm(重量比)，如0.3至0.55 ppm(重量比)硼。如上表所示，在定向性固化時並未有效地分離硼。藉由以上說明之氯氣萃取也無法有效地移除硼。因此，關於碳熱還原反應可選擇具有低硼量之起始材料。 After removing the layers, the ingot may, for example, comprise less than 0.55 ppm by weight, such as from 0.3 to 0.55 ppm by weight of boron. As shown in the above table, boron was not effectively separated during directional solidification. Boron cannot be effectively removed by the chlorine extraction described above. Therefore, a starting material having a low boron amount can be selected for the carbothermal reduction reaction.
另外，等移除那些層之後該錠可包含少於0.8 ppm(重量比)，特別是少於0.5 ppm(重量比)磷。如上表所示，在定向性固化時並未有效地分離磷。藉由以上說明之氯氣萃取也無法有效地移除磷。因此，關於碳熱還原反應可選擇具有低磷量之起始材料。 Additionally, the ingot may comprise less than 0.8 ppm by weight, particularly less than 0.5 ppm by weight, of phosphorus, after removing those layers. As shown in the above table, phosphorus was not effectively separated during directional solidification. Phosphorus is also not effectively removed by the chlorine extraction described above. Therefore, a starting material having a low phosphorus amount can be selected for the carbothermal reduction reaction.
另外，等移除那些層之後該錠可包含少於2 ppm(重量比)，特別是少於1.5 ppm(重量比)，較佳少於1.0 ppm(重量比)鋁。如上表所示，在定向性固化時並未有效地分離鋁。另外，等移除那些層之後該錠可包含少於0.1 ppm(重量比)，如少於0.01 ppm(重量比)銅。如上表所示，在定向性固化時有效地分離銅。另外，等移除那些層之後該錠可包含少於0.05 ppm(重量比)鈉。如上表所示，在定向性固化時有效地分離鈉。另外，等移除那些層之後該錠可包含少於0.1 ppm(重量比)，如少於0.05 ppm(重量比)鈣。在氯氣萃取時有效地分離鈣。另外，等移除那些層之後該錠可包含少於0.05 ppm(重量比)鐵。在定向性固化時有效地分離鐵。另外，等移除那些層之後該錠可包含少於0.05 ppm(重量比)鈦。在定向性 固化時有效地分離鈦。較佳之錠含有總計少於5 ppm(重量比)，較佳少於1 ppm(重量比)的所有金屬雜質(矽除外)。 Additionally, the ingot may comprise less than 2 ppm by weight, particularly less than 1.5 ppm by weight, and preferably less than 1.0 ppm by weight of aluminum, after removal of those layers. As shown in the above table, aluminum was not effectively separated during directional solidification. Additionally, the ingot may comprise less than 0.1 ppm (by weight), such as less than 0.01 ppm by weight copper, after removal of those layers. As shown in the above table, copper is effectively separated during directional solidification. Additionally, the ingot may contain less than 0.05 ppm by weight sodium after the layers are removed. As shown in the above table, sodium is effectively separated during directional solidification. Additionally, the ingot may comprise less than 0.1 ppm by weight, such as less than 0.05 ppm by weight, of calcium after the layers are removed. Effectively separates calcium during chlorine extraction. Additionally, the ingot may contain less than 0.05 ppm by weight iron after the layers are removed. Iron is effectively separated during directional solidification. Additionally, the ingot may comprise less than 0.05 ppm by weight titanium after the layers are removed. Directivity The titanium is effectively separated during curing. Preferred ingots contain all metal impurities (except hydrazine) totaling less than 5 ppm by weight, preferably less than 1 ppm by weight.
上述量也可表示等移除頂層和任何其他層之前或之後該錠中間的量。被移除之頂層和被移除之側層可任意經清潔之後再循環至矽製造程序。例如，其可再循環至製造矽熔融物之碳熱還原程序，其後再精煉該矽熔融物。較佳為獨立再循環以免雜質累積。 The above amounts may also indicate the amount intermediate the ingot before or after removal of the top layer and any other layers. The removed top layer and the removed side layer can be recycled to the crucible manufacturing process after any cleaning. For example, it can be recycled to the carbothermal reduction process for making the crucible melt, after which the crucible melt is refined. It is preferred to recycle independently to avoid accumulation of impurities.
本發明之第三個方面為一種電腦可讀性媒介，電腦軟體係儲存於該電腦可讀性媒介上，且當藉由微處理器執行該軟體時，該電腦可讀性媒介適於進行上揭定向性固化方法。特別是本發明之第三個方面為儲存電腦軟體之電腦可讀性媒介上，且當藉由微處理器執行該軟體時，該電腦可讀性媒介適於進行用於操作供該定向性固化程序(如c)iii)自上方加熱該填充液態矽之坩堝/模子及任意地(iv)自下方冷卻該坩堝/模子以產生由下往上之固化作用)用之裝置的方法，其中該冷卻作用係藉由空氣溫度及/或空氣流動控制。為了使矽錠之純度及工業程序中之定向性固化程序耗掉之時間最適化能藉由具有個別加熱元件之最佳化恆定時間/溫度分佈及最佳化時間/空氣流量分佈的電腦程式完成精準空氣冷卻。此外該冷卻媒介之溫度，特別是冷卻媒介之空氣溫度，能藉由電腦軟體最佳化。其中該冷卻媒介之溫度可藉由裝設於底板的其他加熱機構最佳化。 A third aspect of the present invention is a computer readable medium stored on a computer readable medium, and wherein the computer readable medium is adapted to be executed when the software is executed by a microprocessor Reveal the directional curing method. In particular, a third aspect of the invention is a computer readable medium for storing computer software, and when the software is executed by a microprocessor, the computer readable medium is adapted for operation for the directional cure Procedure (e.g., c) iii) heating the liquid helium/die from above and optionally (iv) cooling the crucible/die from below to produce a bottom-up curing device, wherein the cooling The effect is controlled by air temperature and/or air flow. In order to optimize the purity of the antimony ingot and the time spent in the directional curing process in the industrial process, it can be accomplished by a computer program with optimized constant time/temperature distribution and optimized time/air flow distribution for individual heating elements. Precision air cooling. Furthermore, the temperature of the cooling medium, in particular the air temperature of the cooling medium, can be optimized by the computer software. The temperature of the cooling medium can be optimized by other heating mechanisms mounted on the bottom plate.
因此，本發明之一方面為一種電腦可讀性媒介，電腦軟體係儲存於該電腦可讀性媒介上，且當藉由微處理器執行該軟體時，該電腦可讀性媒介適於進行用於操作供該定向性固化程序用之裝置的方法，如自上方加熱該填充液態矽之坩堝/模子及任意地自下方冷卻該坩堝/模子以產生由下往上之固化作用並獲得太陽能級矽。 Accordingly, one aspect of the present invention is a computer readable medium on which a computer software system is stored, and when the software is executed by a microprocessor, the computer readable medium is suitable for use For operating the apparatus for the directional curing process, such as heating the enthalpy/die of the liquid enthalpy from above and optionally cooling the enthalpy/die from below to produce a bottom-up curing effect and obtaining a solar grade 矽.
本發明之較佳第三方面為一種電腦可讀性媒介，電腦軟體係儲存於該電腦可讀性媒介上，且當藉由微處理器執行該軟體時，該電腦可讀性媒介適於進行用於操作供液態矽定向性固化程序用之裝置的方法，特別是上述方法及/或上述裝置之操作方法，其中該方法在此定向性固化時包含一些不一定連續之操作步驟，如：任意地a)坩堝/模子移動步驟，特別是在有輪子之活動台上水平移動的步驟；及任意地b)爐水平移動步驟；其中該爐移動步驟特別是垂直的；且特別是使該軟體適於進行c)定向性固化步驟，其中該等定向性固化步驟包含以下操作步驟：(i)任意加熱坩堝/模子；(ii)特別是在空氣存在下給坩堝/模子填充液態矽；(iii)自上方加熱該填充液態矽之坩堝/模子，及任意地；(iv)自下方冷卻該坩堝/模子以產生由下往上之固化作用。 A preferred third aspect of the present invention is a computer readable medium on which a computer software system is stored, and when the software is executed by a microprocessor, the computer readable medium is adapted to perform A method for operating a device for a liquid crucible directional curing process, in particular a method as described above and/or a method of operating the above device, wherein the method comprises, during the directional solidification, some operational steps that are not necessarily continuous, such as: a) a 坩埚/mold moving step, in particular a step of horizontal movement on a movable table with wheels; and optionally b) a horizontal movement step of the furnace; wherein the furnace moving step is particularly vertical; and in particular making the soft body suitable The c) directional curing step, wherein the directional curing step comprises the following steps: (i) arbitrarily heating the crucible/mold; (ii) filling the crucible/die with liquid helium, especially in the presence of air; (iii) The liquid helium filled mold/die is heated from above, and optionally; (iv) the crucible/mold is cooled from below to produce a bottom-up curing action.
本發明之第四方面為一種用於操作定向性固化裝置且藉由微處理器執行之程式元件，其中該程式元件適於進行上述方法，如c)iii)自上方加熱該填充液態矽之坩堝/模子及任意地(iv)自下方冷卻該坩堝/模子以產生由下往 上之固化作用，其中該冷卻作用係藉由空氣溫度及/或空氣流動控制。 A fourth aspect of the invention is a program component for operating a directional curing device and being executed by a microprocessor, wherein the programming component is adapted to perform the above method, such as c) iii) heating the liquid enthalpy from above / mold and optionally (iv) cooling the crucible / mold from below to produce A curing action in which the cooling action is controlled by air temperature and/or air flow.
本發明之較佳第四方面為一種用於操作定向性固化裝置且藉由微處理器執行之程式元件，其中該程式元件適於進行用於操作供液態矽定向性固化程序用之裝置的上述方法，特別是上述方法及/或上述裝置之操作方法，其中該方法在此定向性固化時包含一些不一定是連續操作步驟之操作步驟，如：任意地a)坩堝/模子移動步驟，特別是在有輪子之活動台上水平移動的步驟；及任意地b)爐水平移動步驟；其中該爐移動步驟特別是垂直的；且特別是使該軟體適於進行c)定向性固化步驟，其中該等定向性固化步驟包含以下操作步驟：(i)任意加熱坩堝/模子，特別是坩堝/模子之預熱；任意地(ii)給坩堝/模子填充液態矽，特別是在空氣存在下；(iii)自上方加熱該填充液態矽之坩堝/模子，(iv)自下方冷卻該坩堝/模子以產生由下往上之固化作用。 A preferred fourth aspect of the present invention is a program element for operating a directional curing apparatus and being executed by a microprocessor, wherein the program element is adapted to perform the above-described means for operating a liquid 矽 directional curing program a method, particularly the above method and/or method of operating the above apparatus, wherein the method comprises, during the directional solidification, some operational steps which are not necessarily continuous operation steps, such as: arbitrarily a) 坩埚/mould movement step, in particular a step of horizontally moving on a movable table with wheels; and optionally b) a horizontal movement step of the furnace; wherein the furnace moving step is particularly vertical; and in particular, the software is adapted to perform c) a directional curing step, wherein The isotropic curing step comprises the following steps: (i) any heating of the crucible/mold, in particular the preheating of the crucible/mold; optionally (ii) filling the crucible/die with liquid helium, especially in the presence of air; The crucible/mold filled with liquid helium is heated from above, and (iv) the crucible/mold is cooled from below to produce a curing action from bottom to top.
以下參照第1圖描述用於製造太陽能級矽之示範系統。將來自礦山之天然石英101加於石英加工設備102，其中天然石英進行壓碎、篩選、研磨、光學分級、磁分離、重力分離浮選及酸性處理之一或多個步驟。光學分級包含天然石英中之雜質的光學偵測。例如，雜質可以黑點方式見到。另外，光學分級可包含藉由壓縮空氣移除有這種已 經偵測到之點的材料片。也就是說，這樣的片可能被吹離運送皮帶，如輸送帶等。酸性處理可能包含溶解及移除雜質。在浮選時分離出具有與石英不同之物化表面性質的材料片。磁分離包含含磁性材料之材料片的移除。 An exemplary system for manufacturing a solar grade crucible is described below with reference to FIG. Natural quartz 101 from the mine is applied to a quartz processing apparatus 102 in which natural quartz is subjected to one or more steps of crushing, screening, grinding, optical grading, magnetic separation, gravity separation flotation, and acid treatment. Optical grading involves optical detection of impurities in natural quartz. For example, impurities can be seen as black spots. In addition, optical grading can include the removal of this by compressed air. A piece of material that has been detected. That is to say, such a sheet may be blown off from a transport belt such as a conveyor belt or the like. Acidic treatment may involve dissolution and removal of impurities. A piece of material having a different materialized surface property than quartz is separated during flotation. Magnetic separation involves the removal of a sheet of material containing a magnetic material.
將來自該石英加工設備102之一些石英103加於碳化矽製造設備105，也添加高純度碳黑104。此碳黑可能例如衍生自天然氣。 Some quartz 103 from the quartz processing equipment 102 is applied to the tantalum carbide manufacturing apparatus 105, and high-purity carbon black 104 is also added. This carbon black may for example be derived from natural gas.
來自該石英加工設備102之相同類型的經加工之石英106與該系統下游位置的再循環之矽金屬107和來自該碳化矽製造設備105之碳化矽108一同加於用於稱重和混合之設備109。經適當混合之材料接著藉由裝填設備110加於還原爐/反應容器111。加於該還原爐111之材料中的石英對碳化矽之重量比係為約1.1：1。在該還原爐111上方設置排煙罩112以收集還原程序時形成之氣體。收集到之氣體經由導管116送至用於煙道氣過濾和灰塵處理之裝置117。該裝置117包含煙囪118，經純化之氣體穿過該煙囪118排出。將第一電極113，較佳由石墨構成，設置成自上方延伸至還原爐111中。將第二電極114，較佳也由石墨構成，設置於還原爐底部。將第一113及第二114電極連至電源115，如用於產生加熱碳熱還原程序之電弧的DC或AC電源。 The same type of processed quartz 106 from the quartz processing apparatus 102 is added to the apparatus for weighing and mixing together with the recycled base metal 107 at the downstream of the system and the niobium carbide 108 from the niobium carbide manufacturing apparatus 105. 109. The appropriately mixed material is then applied to the reduction furnace/reaction vessel 111 by means of a filling apparatus 110. The weight ratio of quartz to tantalum carbide added to the material of the reduction furnace 111 is about 1.1:1. A fume hood 112 is disposed above the reduction furnace 111 to collect gas formed during the reduction process. The collected gas is sent via conduit 116 to a device 117 for flue gas filtration and dust treatment. The device 117 includes a chimney 118 through which purified gas is discharged. The first electrode 113, preferably made of graphite, is disposed to extend from above into the reduction furnace 111. The second electrode 114, preferably made of graphite, is placed on the bottom of the reduction furnace. The first 113 and second 114 electrodes are connected to a power source 115, such as a DC or AC power source for generating an arc that heats the carbothermal reduction process.
透過該還原爐114之洩放區將還原爐114中形成的矽熔融物洩放至已經藉由澆桶預熱裝置135預熱過之澆桶119中。在洩放時，惰性氣體(如氬)可穿過該澆桶起泡 以攪拌其中之矽熔融物。材料可連續加於該還原爐111。 The crucible melt formed in the reduction furnace 114 is vented to the ladle 119 which has been preheated by the ladle preheating unit 135 through the discharge zone of the reduction furnace 114. An inert gas such as argon can be bubbled through the pour during venting To stir the melt in it. Material can be continuously applied to the reduction furnace 111.
填滿之澆桶119移至用於氯精煉之設備，期間氯氣任意與惰性氣體(如氬)穿過該澆桶119中之液態矽起泡以與雜質(如鋁或鈣)反應形成氯鹽(例如AlCl3和CaCl2)。氣體接著在氣體清潔系統121中純化。用於氯精煉之設備較佳包含該液態矽之加熱(如感應加熱)機構120，這確保此程序期間矽保持液態。 The filled ladle 119 is moved to a facility for chlorine refining, during which chlorine gas is bubbled with an inert gas such as argon through the liquid helium in the ladle 119 to react with impurities such as aluminum or calcium to form a chloride salt. (eg AlCl 3 and CaCl 2 ). The gas is then purified in a gas cleaning system 121. The apparatus for chlorine refining preferably includes a heating (e.g., induction heating) mechanism 120 for the liquid helium, which ensures that helium remains liquid during this procedure.
精煉過之矽熔融物接著，任意在過濾之後，加於處於填充位置123之定向性固化裝置上的較佳預熱過之坩堝122。在加於該預熱過之坩堝122之前經精煉之矽也可儲存於感應爐或保溫爐一段時間。將矽熔融物加於該坩堝而不使用任何保護氣體。該裝置包含具有加熱元件125之爐124(該坩堝可例如已經在該爐124中預熱過)。當該坩堝122填滿時，定向性固化裝置係調定於其加工位置126，其中該坩堝122係置於該爐124中。在加工期間，進行加工但是不使用任何保護氣體(如氬)，該坩堝122係藉由加熱元件125自上方加熱並自下方冷卻以產生受控制之由下往上的固化，造成污染物/雜質累積於形成之固態矽錠的頂層。該坩堝122接著在坩堝移除步驟127中自該錠移除。 The refined melt is then applied, optionally after filtration, to a preferred preheated crucible 122 on the directional solidification apparatus at fill location 123. The refined crucible may also be stored in the induction furnace or holding furnace for a period of time before being applied to the preheated crucible 122. The niobium melt is added to the crucible without using any shielding gas. The apparatus includes a furnace 124 having a heating element 125 (which may have been preheated, for example, in the furnace 124). When the crucible 122 is filled, the directional curing device is set at its processing position 126, wherein the crucible 122 is placed in the furnace 124. During processing, but without the use of any shielding gas (such as argon), the crucible 122 is heated from above by the heating element 125 and cooled from below to produce a controlled bottom-up curing, causing contaminants/impurities Accumulated on the top layer of the formed solid bismuth ingot. The crucible 122 is then removed from the ingot in a crucible removal step 127.
這通常涉及打破該坩堝122以釋出該錠。該錠接著在錠切削步驟128中切削以移除其側面和底部之最外層以及含污染物之頂層。該錠可接著在其運送給客戶之前進行蝕刻和清洗129、裝填130和儲存131之步驟，客戶可將該 錠再結晶化並接著切削成晶圓以供製造太陽能電池面板。 This typically involves breaking the crucible 122 to release the ingot. The ingot is then cut in an ingot cutting step 128 to remove the outermost layer of its sides and bottom and the top layer containing contaminants. The ingot can then be etched and cleaned 129, filled 130 and stored 131 before it is shipped to the customer, which the customer can The ingot is recrystallized and then cut into wafers for fabrication of solar panel panels.
將所有或部分在錠切削步驟128中移除之側層和底層再循環至該程序，較佳是用於稱重和混合之設備109，經過研磨步驟之後，噴砂及/或壓碎132。清洗來自該錠切削步驟128之頂層以防止累積系統100中之雜質。該研磨、噴砂及/或壓碎步驟132也產生一些廢棄物。 The side and bottom layers removed in whole or in part in the ingot cutting step 128 are recycled to the process, preferably the apparatus 109 for weighing and mixing, after the grinding step, sandblasting and/or crushing 132. The top layer from the ingot cutting step 128 is purged to prevent accumulation of impurities in the system 100. The grinding, sand blasting and/or crushing step 132 also produces some waste.
以下參照第2圖描述用於進行根據本揭示內容之定向性固化的爐之示範具體實施例。 Exemplary embodiments of a furnace for performing directional solidification in accordance with the present disclosure are described below with reference to FIG.
坩堝或模子201係置於該爐中之底板202上。支撐結構203裝設於該坩堝側面或該模子201周圍。該底板202和支撐結構203沒固定於該爐結構。因此，該坩堝/模子201可在該底板202上運入及運出該爐200。例如，該坩堝/模子201可在置於該底板202上的另一個爐中預熱並接著在被移入該底板202上之爐200中之前填充置於該爐200外側之底板202上的液態矽。將加熱元件204設置於該爐200中之坩堝201上方，使該坩堝201中之液態矽可自上方加熱。密封刀219之功能在於確實保存該爐內側之熱能。226描繪鑄造面積中間及224描繪具有一定熱傳導率之第二底部部件。 A cassette or mold 201 is placed on the bottom plate 202 in the furnace. The support structure 203 is mounted on the side of the crucible or around the mold 201. The bottom plate 202 and the support structure 203 are not fixed to the furnace structure. Therefore, the crucible/die 201 can be carried in and out of the furnace 200 on the bottom plate 202. For example, the crucible/die 201 can be preheated in another furnace placed on the bottom plate 202 and then filled with liquid helium placed on the bottom plate 202 outside the furnace 200 prior to being moved into the furnace 200 on the bottom plate 202. . The heating element 204 is disposed above the crucible 201 in the furnace 200 such that the liquid crucible in the crucible 201 can be heated from above. The function of the sealing knife 219 is to secure the thermal energy inside the furnace. 226 depicts the middle of the cast area and 224 depicts a second bottom member having a certain thermal conductivity.
在該底板202下方提供冷卻作用。穿過空氣入口205供應作為冷卻媒介之空氣至裝設在該底板之下的冷卻通道206。熱空氣穿過空氣出口207排出。 Cooling action is provided below the bottom plate 202. Air as a cooling medium is supplied through the air inlet 205 to a cooling passage 206 installed below the floor. Hot air is discharged through the air outlet 207.
第3和4圖顯示頂蓋220上具有氣體連接件215且側壁221具有密封刀219之爐的殼體213。該密封刀219將 陷入粒狀材料222(如砂)中。熱係保存於內部氣氛223中。外部氣氛係由225描繪。此外其他絕緣材料，特別是設置於該爐側壁內側之絕緣板218也能保存該爐內側的熱能。在該頂層220內側設置加熱器216和217(216加熱元件(角落)，217加熱元件(側面))。該底板202是活動板(沒顯示)和該冷卻系統(205,207)之一部分。在爐支架214處設置，特別是供垂直移動用之機構。在該活動台下方設置經冷卻之輸送管227，以及在該底板下方之耐熱混凝土228，底座229可為矽砂。 Figures 3 and 4 show the housing 213 of the furnace having a gas connection 215 on the top cover 220 and a side wall 221 having a sealing knife 219. The sealing knife 219 will Into the granular material 222 (such as sand). The heat is stored in the internal atmosphere 223. The external atmosphere is depicted by 225. In addition, other insulating materials, particularly the insulating plate 218 disposed inside the side wall of the furnace, can also retain the thermal energy inside the furnace. Heaters 216 and 217 (216 heating elements (corners), 217 heating elements (side)) are disposed inside the top layer 220. The bottom plate 202 is part of a movable plate (not shown) and the cooling system (205, 207). It is provided at the furnace support 214, in particular for vertical movement. A cooled transfer pipe 227 is disposed under the movable table, and a heat resistant concrete 228 below the bottom plate, and the base 229 may be sand.
此外第4圖顯示具有位置A和B之活動台208。該活動台有輪子209。隔熱屏210設於位置A以免裝置受熱影響。空氣入口基底控制塊212與撓性空氣連接件一起設置於該活動台208處。將空氣入口顯示成205。具有側壁213之爐124/200具有供給氬用之氣體連接件215。活動台之側向移動係藉由汽缸台運動231進行(第7圖)。 In addition, FIG. 4 shows the activity stage 208 having positions A and B. The activity stage has wheels 209. The heat shield 210 is placed at position A to protect the device from heat. An air inlet substrate control block 212 is disposed with the flexible air connection at the mobile station 208. The air inlet is shown as 205. Furnace 124/200 having side walls 213 has a gas connection 215 for supplying argon. The lateral movement of the movable table is performed by the cylinder block motion 231 (Fig. 7).
第5圖顯示於角落216之加熱元件及於側面217之加熱元件。第6圖是具有空氣入口205及空氣出口206之冷卻通道的詳細圖式。 Figure 5 shows the heating element at corner 216 and the heating element on side 217. Figure 6 is a detailed view of a cooling passage having an air inlet 205 and an air outlet 206.
第7至11圖中顯示典型液態矽之定向性固化的方法。在第7圖中固定於加熱器230(例如爐)上之隔熱屏位於位置A。打開該爐並以固態矽填充空坩堝(位置B)。其顯示撓性空氣連接件211及氣缸台運動231。在第8圖中該爐於位置A向上移。坩堝能在該爐下方移動，且接下來該爐能於第9圖所示之位置A向下移。該坩堝之 預熱開始，特別是於約1200℃。在下一個步驟中該爐再往上移，該活動台向側面移以便能依第10圖所示以液態矽填充預熱過之坩堝。在正常空氣存在下進行填充。以液態矽填充時爐再向下移以保存熱能。接下來該爐能再於位置A向上移，活動台在該爐之下向側面移，爐於位置B向下移以開始液態矽之定向性固化以在進一步處理(如錠之頂部、側面及底部等等)之後獲得太陽能級矽錠。根據第12圖所示的一個選擇方案於該底板，特別是在該底板202裡面、之下或上方裝設加熱元件232。該等加熱元件可提供至高1500℃之溫度，特別是至高1258℃。 A method of directional solidification of a typical liquid helium is shown in Figures 7 through 11. The heat shield fixed to the heater 230 (e.g., furnace) in Fig. 7 is located at position A. Open the furnace and fill the space with solid helium (position B). It shows the flexible air connection 211 and the cylinder block motion 231. In Figure 8, the furnace is moved up at position A. The crucible can be moved under the furnace, and then the furnace can be moved downward at the position A shown in Fig. 9. The 坩埚 Preheating begins, especially at about 1200 °C. In the next step, the furnace is moved up again, and the movable table is moved to the side so that the preheated crucible can be filled with liquid helium as shown in Fig. 10. Filling is performed in the presence of normal air. When filled with liquid helium, the furnace is moved down to conserve heat. Next the furnace can be moved up again at position A, the movable table is moved laterally under the furnace, and the furnace is moved downward at position B to initiate the directional solidification of the liquid crucible for further processing (eg top, side and A solar grade bismuth ingot is obtained after the bottom, etc.). A heating element 232 is mounted to the bottom plate, in particular below, below or above the bottom plate 202, according to an alternative shown in FIG. These heating elements can be supplied to temperatures as high as 1500 ° C, especially up to 1258 ° C.
A‧‧‧位置 A‧‧‧ position
B‧‧‧位置 B‧‧‧ position
100‧‧‧系統 100‧‧‧ system
101‧‧‧天然石英 101‧‧‧Natural quartz
102‧‧‧石英加工設備 102‧‧‧Quartz processing equipment
103‧‧‧石英 103‧‧‧Quartz
104‧‧‧碳黑 104‧‧‧Carbon black
105‧‧‧碳化矽製造設備 105‧‧‧Carbide manufacturing equipment
106‧‧‧經加工之石英 106‧‧‧Processed quartz
107‧‧‧再循環之矽金屬 107‧‧‧Recycled base metal
108‧‧‧碳化矽 108‧‧‧Carbide
109‧‧‧用於稱重和混合之設備 109‧‧‧Equipment for weighing and mixing
110‧‧‧裝填設備 110‧‧‧Loading equipment
111‧‧‧還原爐 111‧‧‧Reduction furnace
112‧‧‧排煙罩 112‧‧‧Exhaust hood
113‧‧‧第一電極 113‧‧‧First electrode
114‧‧‧第二電極 114‧‧‧second electrode
115‧‧‧電源 115‧‧‧Power supply
116‧‧‧導管 116‧‧‧ catheter
117‧‧‧用於煙道氣過濾和灰塵處理之裝置 117‧‧‧Devices for flue gas filtration and dust treatment
118‧‧‧煙囪 118‧‧‧ chimney
119‧‧‧澆桶 119‧‧ ‧ pouring bucket
120‧‧‧加熱機構 120‧‧‧heating mechanism
121‧‧‧氣體清潔系統 121‧‧‧Gas cleaning system
122‧‧‧預熱過之坩堝 122‧‧‧ Preheated
123‧‧‧填充位置 123‧‧‧fill position
124‧‧‧具有加熱元件之爐 124‧‧‧furnace with heating elements
125‧‧‧加熱元件 125‧‧‧ heating element
126‧‧‧加工位置 126‧‧‧Processing location
127‧‧‧坩堝移除步驟 127‧‧‧坩埚 removal steps
128‧‧‧錠切削步驟 128‧‧‧Ingot cutting steps
129‧‧‧蝕刻和清洗 129‧‧‧etching and cleaning
130‧‧‧裝填 130‧‧‧Loading
131‧‧‧儲存 131‧‧‧Storage
132‧‧‧噴砂及/或壓碎 132‧‧‧Sandblasting and/or crushing
135‧‧‧澆桶預熱裝置 135‧‧‧Pour bucket preheating device
200‧‧‧爐 200‧‧‧ furnace
201‧‧‧坩堝 201‧‧‧坩埚
202‧‧‧底板 202‧‧‧floor
203‧‧‧支撐結構 203‧‧‧Support structure
204‧‧‧加熱元件 204‧‧‧ heating element
205‧‧‧空氣入口 205‧‧‧Air inlet
206‧‧‧冷卻通道 206‧‧‧Cooling channel
207‧‧‧空氣出口 207‧‧‧Air outlet
208‧‧‧活動台 208‧‧‧ activity table
209‧‧‧輪子 209‧‧‧ wheels
210‧‧‧隔熱屏 210‧‧‧Heat screen
211‧‧‧撓性空氣連接件 211‧‧‧Flexible air connectors
212‧‧‧空氣入口基底控制塊 212‧‧‧Air inlet base control block
213‧‧‧殼體 213‧‧‧Shell
214‧‧‧爐支架 214‧‧‧ furnace bracket
215‧‧‧氣體連接件 215‧‧‧ gas connections
216‧‧‧加熱元件 216‧‧‧ heating element
217‧‧‧加熱元件 217‧‧‧ heating elements
218‧‧‧絕緣板 218‧‧‧Insulation board
219‧‧‧密封刀 219‧‧‧Sealing knife
220‧‧‧頂蓋 220‧‧‧Top cover
221‧‧‧側壁 221‧‧‧ side wall
222‧‧‧粒狀材料 222‧‧‧Grain materials
223‧‧‧內部氣氛 223‧‧‧ internal atmosphere
224‧‧‧第二底部部件 224‧‧‧Second bottom part
225‧‧‧外部氣氛 225‧‧‧ outside atmosphere
226‧‧‧鑄造面積中間 226‧‧‧In the middle of the casting area
227‧‧‧經冷卻之輸送管 227‧‧‧cooled duct
228‧‧‧耐熱混凝土 228‧‧‧heat-resistant concrete
229‧‧‧底座 229‧‧‧Base
230‧‧‧加熱器 230‧‧‧heater
231‧‧‧汽缸台運動 231‧‧‧Cylinder table movement
第1圖顯示用於製造太陽能電池級矽之系統的具體實施例。 Figure 1 shows a specific embodiment of a system for manufacturing a solar cell grade crucible.
第2圖顯示根據本揭示內容之用於進行定向性固化的裝置之具體實施例。 Figure 2 shows a specific embodiment of an apparatus for performing directional curing in accordance with the present disclosure.
第3圖顯示該裝置之具體實施例的一部分，換言之該爐、底板、活動台之一部分及冷卻系統。 Figure 3 shows a portion of a particular embodiment of the apparatus, in other words a portion of the furnace, floor, mobile station, and cooling system.
第4圖顯示該裝置之具體實施例，具有該冷卻系統之活動台、隔熱屏及該爐。 Figure 4 shows a specific embodiment of the apparatus having a movable table, a heat shield and the furnace of the cooling system.
第5圖顯示加熱元件。 Figure 5 shows the heating element.
第6圖顯示熱槽，特別是冷卻通道及空氣入口。 Figure 6 shows the hot trough, especially the cooling channels and air inlets.
第7圖顯示包含該活動台、爐及氬供應源之裝置的具體實施例，預熱之前。 Figure 7 shows a specific embodiment of a device containing the mobile station, furnace and argon supply, prior to preheating.
第8圖顯示包含該活動台、爐及氬供應源之裝置的具體實施例，爐向上移，坩堝預熱之前。 Figure 8 shows a specific embodiment of a device containing the moving table, furnace and argon supply, with the furnace moving up and before the preheating.
第9圖顯示包含該活動台、爐及氬供應源之裝置的具體實施例，坩堝預熱之前。 Figure 9 shows a specific embodiment of a device containing the movable table, furnace and argon supply, prior to preheating.
第10圖顯示包含該活動台、爐及氬供應源之裝置的具體實施例，以液態矽填充坩堝。 Figure 10 shows a specific embodiment of a device containing the mobile station, furnace and argon supply source, filled with helium in a liquid helium.
第11圖顯示包含該活動台、爐及氬供應源之裝置的具體實施例，矽之定向性固化。 Figure 11 shows a specific embodiment of a device comprising the movable table, furnace and argon supply, directional solidification of the crucible.
第12圖顯示包含底部加熱機構之裝置的具體實施例。 Figure 12 shows a specific embodiment of a device comprising a bottom heating mechanism.
100‧‧‧系統 100‧‧‧ system
101‧‧‧天然石英 101‧‧‧Natural quartz
102‧‧‧石英加工設備 102‧‧‧Quartz processing equipment
103‧‧‧石英 103‧‧‧Quartz
104‧‧‧碳黑 104‧‧‧Carbon black
105‧‧‧碳化矽製造設備 105‧‧‧Carbide manufacturing equipment
106‧‧‧經加工之石英 106‧‧‧Processed quartz
107‧‧‧再循環之矽金屬 107‧‧‧Recycled base metal
108‧‧‧碳化矽 108‧‧‧Carbide
109‧‧‧用於稱重和混合之設備 109‧‧‧Equipment for weighing and mixing
110‧‧‧裝填設備 110‧‧‧Loading equipment
111‧‧‧還原爐 111‧‧‧Reduction furnace
112‧‧‧排煙罩 112‧‧‧Exhaust hood
113‧‧‧第一電極 113‧‧‧First electrode
114‧‧‧第二電極 114‧‧‧second electrode
115‧‧‧電源 115‧‧‧Power supply
116‧‧‧導管 116‧‧‧ catheter
117‧‧‧用於煙道氣過濾和灰塵處理之裝置 117‧‧‧Devices for flue gas filtration and dust treatment
118‧‧‧煙囪 118‧‧‧ chimney
119‧‧‧澆桶 119‧‧ ‧ pouring bucket
120‧‧‧加熱機構 120‧‧‧heating mechanism
121‧‧‧氣體清潔系統 121‧‧‧Gas cleaning system
122‧‧‧預熱過之坩堝 122‧‧‧ Preheated
123‧‧‧填充位置 123‧‧‧fill position
124‧‧‧具有加熱元件之爐 124‧‧‧furnace with heating elements
125‧‧‧加熱元件 125‧‧‧ heating element
126‧‧‧加工位置 126‧‧‧Processing location
127‧‧‧坩堝移除步驟 127‧‧‧坩埚 removal steps
128‧‧‧錠切削步驟 128‧‧‧Ingot cutting steps
129‧‧‧蝕刻和清洗 129‧‧‧etching and cleaning
130‧‧‧裝填 130‧‧‧Loading
131‧‧‧儲存 131‧‧‧Storage
132‧‧‧噴砂及/或壓碎 132‧‧‧Sandblasting and/or crushing
135‧‧‧澆桶預熱裝置 135‧‧‧Pour bucket preheating device
Claims (25)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11016872 | 2011-06-03 | ||
| PCT/EP2012/002308 WO2012163531A1 (en) | 2011-06-03 | 2012-05-31 | Device for refining of silicon by directional solidification in an oxygen-containing atmosphere as well as a refining method of silicon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201323671A true TW201323671A (en) | 2013-06-16 |
Family
ID=48872326
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101119766A TW201319338A (en) | 2011-06-03 | 2012-06-01 | Starting materials for production of solar grade silicon feedstock |
| TW101119767A TW201323671A (en) | 2011-06-03 | 2012-06-01 | Device for refining of silicon by directional solidification in an oxygen-containing atmosphere as well as a refining method of silicon |
| TW101119765A TW201319003A (en) | 2011-06-03 | 2012-06-01 | Components of plant, such as reduction furnace body and/or electrode, in particular for a reduction furnace |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101119766A TW201319338A (en) | 2011-06-03 | 2012-06-01 | Starting materials for production of solar grade silicon feedstock |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101119765A TW201319003A (en) | 2011-06-03 | 2012-06-01 | Components of plant, such as reduction furnace body and/or electrode, in particular for a reduction furnace |
Country Status (1)
| Country | Link |
|---|---|
| TW (3) | TW201319338A (en) |
-
2012
- 2012-06-01 TW TW101119766A patent/TW201319338A/en unknown
- 2012-06-01 TW TW101119767A patent/TW201323671A/en unknown
- 2012-06-01 TW TW101119765A patent/TW201319003A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| TW201319338A (en) | 2013-05-16 |
| TW201319003A (en) | 2013-05-16 |
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