TWI541195B - Use of acid washing to provide purified silicon crystals - Google Patents
Use of acid washing to provide purified silicon crystals Download PDFInfo
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本申請案主張於2007年7月23日提出申請之美國專利臨時申請案第60/951,374號及於2007年7月30日提出申請之美國專利臨時申請案第60/952,732號之優先權，該等專利申請案全文併入本案做為參考。 The present application claims the priority of U.S. Patent Application Serial No. 60/951,374, filed on Jul. 23, 2007, and the priority of U.S. Patent Application Serial No. 60/952,732, filed on Jul. 30, 2007. The full text of the patent application is incorporated into the present case for reference.
本發明提供一種用於純化矽的方法，及獲得純化矽的方法。 The present invention provides a method for purifying hydrazine, and a method for obtaining purified hydrazine.
已描述很多用於減少矽中的不純物量之不同方法及設備，包括如區域熔化、矽烷氣體蒸餾、氣體注入、酸性浸出、渣化及方向性固化。然而，依目前已知製程以高困難度及/或昂貴的製程步驟僅能除去硼、磷、鈦、鐵及一些其他元素至需要的純度。 A number of different methods and apparatus have been described for reducing the amount of impurities in the crucible, including, for example, zone melting, decane gas distillation, gas injection, acid leaching, slagging, and directional solidification. However, it is currently known that processes can only remove boron, phosphorus, titanium, iron and some other elements to the desired purity with high difficulty and/or expensive process steps.
目前，矽基本上以使用可揮發之極純矽化合物的還原及/或熱分解之製程純化，如以三氯矽烷。此製程非常昂貴且為一資本密集方式生產具有比在某些應用中如太陽 能電池所需之純度更高純度的矽。 Currently, ruthenium is essentially purified by a process using reduction and/or thermal decomposition of a volatile, very pure ruthenium compound, such as trichloromethane. This process is very expensive and produces in a capital intensive manner than in some applications such as the sun The purity of the battery can be higher purity.
本發明提供用以純化矽的方法，及用以獲得相對純化之矽的方法。本文提及的此些方法可以一相對具成本效益的方法有效地提供商業數量(如，至少約240kg)的純化矽。本文提及的此些方法可以一相對具成本效益的方法有效地提供至少約100公噸/年之純化矽。此外，描述於本文的方法可在約24至約94小時完成，基本上不超過約72小時。由本文描述之方法獲得相對之純化矽晶體可接著進一步純化，以提供太陽能級矽。 The present invention provides methods for purifying rhodium and methods for obtaining relatively purified rhodium. Such methods as referred to herein can effectively provide a commercial quantity (e.g., at least about 240 kg) of purified oxime in a relatively cost effective manner. Such methods as referred to herein can effectively provide at least about 100 metric tons per year of purified hydrazine in a relatively cost effective manner. Moreover, the methods described herein can be completed in about 24 to about 94 hours, and substantially no more than about 72 hours. The resulting purified ruthenium crystals obtained by the methods described herein can then be further purified to provide solar grade ruthenium.
本發明提供純化矽的方法，此方法包括：(a)由矽及一溶劑金屬形成第一熔融液體，該溶劑金屬為選自銅、錫、鋅、銻、銀、鉍、鋁、鎘、鎵、銦、鎂、鉛、其合金、及其組合；(b)將第一熔融液體與第一氣體接觸，以提供浮渣及第二熔融液體；(c)分離浮渣及第二熔融液體；(d)冷卻第二熔融液體以形成第一矽晶體及第一母液；(e)分離第一矽晶體及第一母液；(f)將第一矽晶體與可溶解溶劑金屬的酸、鹼、醇或化學品接觸，以提供清洗過的矽晶體及使用過的酸；及(g)分離清洗過的矽晶體及使用過的酸。 The invention provides a method for purifying cerium, the method comprising: (a) forming a first molten liquid from cerium and a solvent metal selected from the group consisting of copper, tin, zinc, antimony, silver, antimony, aluminum, cadmium, gallium. , indium, magnesium, lead, alloys thereof, and combinations thereof; (b) contacting the first molten liquid with the first gas to provide the scum and the second molten liquid; (c) separating the scum and the second molten liquid; (d) cooling the second molten liquid to form the first tantalum crystal and the first mother liquid; (e) separating the first tantalum crystal and the first mother liquid; (f) separating the first tantalum crystal with an acid or a base capable of dissolving the solvent metal The alcohol or chemical is contacted to provide cleaned ruthenium crystals and used acid; and (g) the cleaned ruthenium crystals and used acid are separated.
本發明也有關於用以純化矽的方法。此方法包括(a)從矽及鋁形成第一熔融液體；(b)將第一熔融液體與第一氣體接觸，以提供浮渣及第二熔融液體；(c)分離浮渣及第二熔融液體；(d)冷卻第二熔融液體以形成第一矽晶體及第 一母液；(e)分離第一矽晶體及第一母液；(f)熔融第一矽晶體與一溶劑金屬及重複步驟(a)-(e)；(g)將第一矽晶體與可溶解溶劑金屬的酸、鹼、醇或化學品接觸，以提供清洗過的矽晶體及使用過的酸；及(h)分離清洗過的矽晶體及使用過的酸，足以提供純化矽晶體；(i)熔化純化矽晶體，足以提供矽熔融物；(j)將矽熔融物與第二氣體接觸；及(k)方向性凝固矽熔融物。 The invention also relates to methods for purifying hydrazine. The method comprises (a) forming a first molten liquid from tantalum and aluminum; (b) contacting the first molten liquid with the first gas to provide dross and a second molten liquid; (c) separating the dross and the second melting a liquid; (d) cooling the second molten liquid to form the first tantalum crystal and a mother liquor; (e) separating the first ruthenium crystal and the first mother liquor; (f) melting the first ruthenium crystal and a solvent metal and repeating steps (a)-(e); (g) dissolving the first ruthenium crystal and being soluble Solvent metal acid, base, alcohol or chemical contact to provide cleaned ruthenium crystals and used acid; and (h) separation of washed ruthenium crystals and used acid, sufficient to provide purified ruthenium crystals; (i Melting and purifying the ruthenium crystal, sufficient to provide a ruthenium melt; (j) contacting the ruthenium melt with the second gas; and (k) directional solidification of the ruthenium melt.
102‧‧‧原料矽 102‧‧‧ Raw materials矽
103‧‧‧溶劑金屬 103‧‧‧Solvent metal
104‧‧‧第一熔融液體 104‧‧‧First molten liquid
106‧‧‧第一氣體 106‧‧‧First gas
108‧‧‧第二熔融液體 108‧‧‧Second molten liquid
110‧‧‧浮渣 110‧‧‧ scum
112‧‧‧冷卻 112‧‧‧cooling
114‧‧‧第一矽晶體 114‧‧‧First crystal
115‧‧‧濾器 115‧‧‧ filter
116‧‧‧第一母液 116‧‧‧First mother liquor
117‧‧‧再使用 117‧‧‧Re-use
119‧‧‧酸、鹼、醇或化學品 119‧‧‧Acids, bases, alcohols or chemicals
121‧‧‧矽晶體 121‧‧‧矽 crystal
123‧‧‧使用過的酸 123‧‧‧Used acid
125‧‧‧分離 125‧‧‧Separation
127‧‧‧純化矽晶體 127‧‧‧ Purified 矽 crystal
129‧‧‧熔融 129‧‧‧melting
131‧‧‧矽熔融物 131‧‧‧矽 melt
133‧‧‧第二氣體 133‧‧‧second gas
135‧‧‧矽熔融物 135‧‧‧矽 melt
137‧‧‧方向性固化 137‧‧‧ Directional curing
139‧‧‧多晶矽 139‧‧‧ Polysilicon
202‧‧‧氣泡 202‧‧‧ bubbles
204‧‧‧除氣器 204‧‧‧Deaerator
本發明實施例可參考下列描述及配合說明此實施例之附圖而有最佳的瞭解。在本文的圖式之編號為使在一圖式中的特定參考標號之配合圖的編號。在不同圖式中的相同參考標號為指相同的元件。在圖示中：第1圖繪示一純化矽的方法之方塊流程圖，其包括與一氣體接觸，用以獲得純化矽的方法，以及獲得純化矽晶體、純化粒狀矽、矽塊及/或純化矽錠之方法。 The embodiments of the present invention can be best understood by referring to the following description and the accompanying drawings. The figures in the figures are numbered to match the figures of a particular reference number in a drawing. The same reference numbers in the different drawings are the same. In the drawings: FIG. 1 is a block diagram showing a method for purifying hydrazine, which comprises contacting a gas to obtain a method for purifying hydrazine, and obtaining purified cerium crystals, purifying granules, strontium blocks and/or Or a method of purifying the ingot.
第2圖繪示一純化矽的方法之方塊流程圖，用以獲得純化矽的方法，以及獲得純化矽晶體、純化粒狀矽、矽塊及/或純化矽錠之方法。 Figure 2 is a block diagram showing a method for purifying hydrazine, a method for obtaining purified hydrazine, and a method for obtaining purified cerium crystals, purifying granulated cerium, cerium, and/or purifying cerium.
第3A-B圖繪示可用於實施本發明方法之例示設備系統。 3A-B illustrate an exemplary device system that can be used to implement the methods of the present invention.
第4圖繪示一純化矽的方法之方塊流程圖，其包括與第一及第二氣體接觸，用以獲得純化矽的方法，以及獲得純化矽晶體、純化粒狀矽、矽塊及/或純化矽錠之方法。 4 is a block flow diagram of a method for purifying hydrazine, comprising contacting a first gas and a second gas to obtain a purified hydrazine, and obtaining purified cerium crystals, purifying granules, strontium blocks, and/or A method of purifying a bismuth ingot.
將以詳細說明本發明之特定申請專利範圍及以結構及化學式說明的實施例。雖然本發明與數個申請專利範圍描述，應瞭解其非用以限制本發明至此些申請專利範圍。相反地，本發明傾向涵蓋所有的變化、潤飾及等效物，其等亦皆包括於本發明申請專利範圍所界定的範疇。 The specific scope of the invention and the embodiments described in the structural and chemical formula will be described in detail. While the invention has been described in connection with a number of claims, it should be understood that On the contrary, the invention is intended to cover all modifications, modifications, and equivalents, and the scope of the invention as defined by the scope of the invention.
在說明書中提及“一實施例(one embodiment)”、“一實施例(an embodiment)”、“an例示實施例(an example embodiment)”等詞為意指描述的實施例可包括特定的特徵、結構、或特性，但每個實施例可不必要包括此特定的特徵、結構、或特性。此外，此些詞並未用於指稱相同的實施例。再者，當依實施例描述特定的特徵、結構、或特性時，其提出係在熟於此項技術人士的專業知識內感受此些與其他實施例有關的特徵、結構、或特性是否明白描述。 The word "one embodiment", "an embodiment", "an example embodiment" is used in the specification to mean that the described embodiment may include specific features. , structure, or characteristic, but each embodiment may not necessarily include this particular feature, structure, or characteristic. Moreover, such words are not used to refer to the same embodiments. In addition, when a particular feature, structure, or characteristic is described in the embodiments, it is suggested that the features, structures, or characteristics relating to other embodiments are clearly described in the expert knowledge of those skilled in the art. .
本發明有關於純化矽的方法，及用以獲得純化矽的方法。當描述純化矽的方法及用以獲得純化矽的方法時，除非特別指明，下列詞具有下列定義。 The present invention relates to a method of purifying hydrazine, and a method for obtaining purified hydrazine. When describing the method of purifying hydrazine and the method for obtaining purified hydrazine, the following words have the following definitions unless otherwise specified.
除非另外說明，下列字或詞當用於本文內時，為具有下列定義：在本發明描述的方法中，除非當特別明白提及時間或操作的順序，其步驟可在未偏離本發明技術思想下以任何順序實施。在申請專利範圍中提及先進行一步驟及接 著進行數個其他步驟之效用，此視為在任何的其他步驟前進行該第一步驟，但其他步驟可以任何適合的順序執行，除非在其他步驟中再提及一順序。例如，在提及“步驟A、步驟B、步驟C、步驟D、及步驟E”之申請專利元件應解釋為先進行步驟A，步驟E最後進行，及步驟B、C、及可在步驟A及E間以任何順序進行，且此順序仍屬於本發明主張之方法的解釋範圍內。 Unless otherwise stated, the following words or words, when used herein, have the following definitions: In the methods described herein, unless specifically stated to the time or the order of the operations, the steps may be without departing from the technical spirit of the invention. Implemented in any order. In the scope of patent application, it is mentioned that one step is followed and one step is taken. The effect of performing several other steps is considered to be performed prior to any other steps, but other steps may be performed in any suitable order unless a sequence is recited in other steps. For example, a patented component referring to "Step A, Step B, Step C, Step D, and Step E" should be interpreted as performing Step A first, Step E last, and Steps B, C, and in Step A. And E are performed in any order, and this order is still within the scope of the method claimed by the present invention.
此外，除非在專利範圍中明白指出提及特定的步驟為分開進行，則其可用時進行。例如，一製做X之申請專利範圍步驟及一製做Y之申請專利範圍的Y可同時在單一操作中進行，且結果製程將落於申請專利範圍方法所界定的範圍中。 Furthermore, unless it is expressly stated in the patent scope that reference to a particular step is performed separately, it can be performed as it is. For example, the process of applying for the patent scope of X and the Y of the patent application scope of Y can be performed in a single operation at the same time, and the result process will fall within the scope defined by the method of patent application.
在本文中，“多”意指二或更多，如2、3、4或5。 As used herein, "multi" means two or more, such as 2, 3, 4 or 5.
在本文中，“純化”意指主題之化學物質由外來或污染的物質中之物理性分離。 As used herein, "purified" means that the subject's chemical is physically separated from the foreign or contaminated material.
在本文中，“接觸”意指非常鄰近的接觸或達到接觸之作動。 As used herein, "contact" means a very close contact or a contact action.
在本文中，“結晶”包括一物質由溶液中形成晶體(結晶材料)的製程。此製程藉由冷卻餵入流或加入一降低預期產物之溶解度的沉澱物以形成晶體而由一液體流中分離一產物，該產物通常為非常純形式。純固體晶體接著藉由過濾或離心以由殘餘的液體中分離。 As used herein, "crystallization" includes a process in which a substance forms a crystal (crystalline material) from a solution. This process separates a product from a liquid stream by cooling the feed stream or by adding a precipitate which reduces the solubility of the desired product to form crystals, which are typically in very pure form. The pure solid crystals are then separated from the residual liquid by filtration or centrifugation.
在本文中，“晶體”包括在一固體中原子的規則、幾何排列。 As used herein, "crystal" includes the regular, geometric arrangement of atoms in a solid.
在本文中，“傾倒”或“傾倒作用”包括倒出一液體而留下沉積物或沈澱物，因此由沉積物或沈澱物分離液體。 As used herein, "dumping" or "dumping" includes pouring a liquid leaving a deposit or deposit, thus separating the liquid from the deposit or sediment.
在本文中，“過濾(filtering)”或“過濾(filteration)”意指一藉由將液體通過一多孔性片材如陶瓷或金屬膜以留下固體且允許液體通過以由液體分離固體的機械方法。此可藉由使用如一濾器之重力，或藉由壓力或真空(吸氣)而完成。過濾可有效由液體中分離沉積物或沈澱物。 As used herein, "filtering" or "filtering" means by passing a liquid through a porous sheet such as a ceramic or metal film to leave a solid and allowing the liquid to pass to separate the solid from the liquid. Mechanical method. This can be done by using gravity such as a filter, or by pressure or vacuum (suction). Filtration is effective in separating deposits or deposits from liquids.
在本文中，“分離”意指從另一物質移除一物質的製程(如，從混合物移除固體或液體)。製程可使用對熟知此技藝者任何已知技術，如，傾倒一混合物、從混合物撇渣至少一液體、離心混合物、由混合物過濾該固體，或其組合。 As used herein, "isolated" means the process of removing a substance from another substance (eg, removing solids or liquids from the mixture). The process can employ any of the known techniques known to those skilled in the art, such as pouring a mixture, slaging at least one liquid from the mixture, centrifuging the mixture, filtering the solid from the mixture, or a combination thereof.
在本文中，“過濾”意指藉由將液體通過一濾器，藉此將固體懸浮濾器上以由混合物除去固體的方法。 As used herein, "filtering" means a method of removing solids from a mixture by passing the liquid through a filter, thereby suspending the solids on the filter.
在本文中，“傾析”意指在未干擾沉積物下傾倒一液體的製程，或以最小干擾沉積物下傾倒液體的方法。 As used herein, "decanting" means a process of pouring a liquid without interfering with the deposit, or a method of pouring the liquid with minimal interference with the deposit.
在本文中，“離心”意指有關使用向心力之混合物分離的製程，如混合物的固體。離心作用在一容器上增加有效之重力，以更快速及完全的造成沈澱物聚集在容器的側邊或底部。此溶液(“上清液”)可迅速地由容器傾倒出而未干擾到沈澱物。離心的速率藉由施加至樣本的加速度而定，基本上以每分鐘轉速(RPM)量測。在離心作用中的顆粒沉降速度為顆粒尺寸及形狀、離心加速度、存在之固體體積分 量、顆粒及液體間的密度差異、與黏度間的功能。 As used herein, "centrifugation" means a process involving the separation of a mixture of centripetal forces, such as a solid of a mixture. Centrifugation adds an effective amount of gravity to a container to cause more rapid and complete accumulation of deposits on the sides or bottom of the container. This solution ("supernatant") can be quickly poured from the container without disturbing the precipitate. The rate of centrifugation is determined by the acceleration applied to the sample, measured substantially at revolutions per minute (RPM). The sedimentation velocity of the particles in the centrifugation is the particle size and shape, the centrifugal acceleration, and the solid volume fraction present. The difference in density between the particles, the liquid and the liquid, and the function between the viscosity.
在本文中，“撇渣”意指一由混合物中除去組合之至少一液體、固體的製程，其中至少一液體浮在混合物頂端。 As used herein, "slag" means a process for removing at least one liquid, solid from a mixture, wherein at least one liquid floats on top of the mixture.
在本文中，“攪動”意指將一混合物放入具擾流力作動的製程。適合的攪動方法包括，如攪拌、混合、及搖動。 As used herein, "stirring" means placing a mixture into a process that is turbulent. Suitable agitation methods include, for example, agitation, mixing, and shaking.
在本文中，“沈澱”意指將引起固體物質(如，晶體)由溶液分離的製程。沈澱可包括，如結晶。 As used herein, "precipitation" means a process that will cause a solid material (eg, crystals) to be separated from the solution. Precipitation can include, for example, crystallization.
在本文中，“母液”意指由在固體於液體中之溶液混合物除去固體(如，晶體)後所得的之固體或液體。因此，母液將不包括一可觀察到的固體量。 As used herein, "mother liquor" means a solid or liquid obtained by removing a solid (eg, crystal) from a solution mixture of a solid in a liquid. Therefore, the mother liquor will not include an observable amount of solids.
在本文中，“矽”意指具有符號Si及原子數14的化學元素。 As used herein, "矽" means a chemical element having the symbol Si and the atomic number 14.
當用於本文內，“原料矽”意指含有被純化之矽量的混合物或化合物。原料矽可以或可以不是冶金級。 As used herein, "raw material" means a mixture or compound containing the amount of purified material. The raw materials may or may not be metallurgical grade.
在本文中，“冶金級矽”意指相對純矽(如，至少約95.0wt.%)。 As used herein, "metallurgical grade ruthenium" means relatively pure ruthenium (eg, at least about 95.0 wt.%).
在本文中，“熔融物”意指一被熔融之物質，其中熔融為一加熱固體物質至其轉變為液體的温度(稱為熔點)之製程。 As used herein, "melt" means a substance that is molten, wherein the melting is a process of heating a solid material to a temperature at which it is converted to a liquid (referred to as a melting point).
在本文中，“溶劑金屬”意指至少一金屬或其合金，其當加熱時，可有效地熔解矽以生成一熔解液體。適合的例示溶劑金屬包括，如、銅、錫、鋅、銻、銀、鉍、鋁、 鎘、鎵、銦、鎂、鉛、其合金、及其組合。 As used herein, "solvent metal" means at least one metal or alloy thereof that, when heated, is effective to melt enthalpy to form a molten liquid. Suitable exemplary solvent metals include, for example, copper, tin, zinc, antimony, silver, antimony, aluminum, Cadmium, gallium, indium, magnesium, lead, alloys thereof, and combinations thereof.
當用於本文內，一“合金”意指二或更多的元素的均質混合物，至少其中之一為金屬，及其結果材料具有金屬性質。生成之金屬物質通常因其組份而具有不同性質(有時顯著地不同)。 As used herein, an "alloy" means a homogeneous mixture of two or more elements, at least one of which is a metal, and the resulting material has metallic properties. The resulting metallic species typically have different properties (sometimes significantly different) due to their composition.
在本文中，“液相線”意指一在相圖上的線，一特定物質在高於此線的温度時為液相安定的。最常見地，此線代表轉化溫度。液相線依物質可以是一直線，或其可以是曲線。液相線最常應用在二元系統如固體溶液，包括金屬合金。液相線可對照至固相線。固相線及液相線不必然對齊或重疊；若在液相線及固相線間存在差距，則在此差距間時，物質不論在液體或在固體為不安定的。 As used herein, "liquidus" means a line on a phase diagram in which a particular substance is settled in a liquid phase above the temperature of the line. Most commonly, this line represents the conversion temperature. The liquidus may be a straight line depending on the substance, or it may be a curve. Liquidus is most commonly used in binary systems such as solid solutions, including metal alloys. The liquidus can be compared to the solidus. The solidus and liquidus do not necessarily align or overlap; if there is a gap between the liquidus and the solidus, the substance is unstable between liquid and solid.
在本文中，“固相線”意指一在相圖上的線，一特定物質在低於此線的温度時為固相安定的。最常見地，此線代表轉移溫度。固相線依物質可以是一直線，或其可以是曲線。固相線通常應用在二元系統如固體溶液，包括金屬合金。固相線可對照至液相線。固相線及液相線不必然對齊或重疊。若在液相線及固相線間存在差距，則在此差距間時，物質不論在液體或在固體為不安定的；在此例中，例如橄欖石(鎂橄欖石-鐵橄欖石)系統。 As used herein, "solidus line" means a line on a phase diagram that is solid phase stable at temperatures below this line. Most commonly, this line represents the transfer temperature. The solid phase line may be a straight line depending on the substance, or it may be a curve. Solidus lines are commonly used in binary systems such as solid solutions, including metal alloys. The solidus line can be compared to the liquidus. The solid and liquid lines are not necessarily aligned or overlapped. If there is a gap between the liquidus and the solidus, the substance is unstable in the liquid or in the solid between the gaps; in this case, for example, the olivine (forsterite-fayalite) system .
在本文中，“釋出”或“釋出一氣體”意指液體或固體在一特定條件(典型地為高溫)下進行化學反應或分解以釋出氣體之製程。 As used herein, "releasing" or "releasing a gas" means the process by which a liquid or solid undergoes a chemical reaction or decomposition under a specific condition (typically high temperature) to liberate a gas.
在本文中，“浮渣”意指浮在熔解金屬浴之固體不 純物塊。此通常在低熔點金屬或合金如錫、鉛、鋅或鋁，或經由金屬氧化之熔融物上出現。其可被移除，如，藉由表面撇渣移除。對於某些金屬，可加入鹽回流以分離浮渣。浮渣可由熔渣區別，其為以固態的浮在合金上之(黏性)液體。 As used herein, "scum" means that the solid floating in the molten metal bath is not Pure block. This typically occurs on low melting point metals or alloys such as tin, lead, zinc or aluminum, or through metal oxidized melts. It can be removed, for example, by surface slag removal. For some metals, salt reflux can be added to separate the scum. The scum can be distinguished by slag, which is a (viscous) liquid that floats on the alloy in a solid state.
在本文中，“熔渣”意指熔煉礦砂的副產物以精煉金屬。其可視為金屬氧化物混合物；然而，其可包含元素形式之金屬硫化物及金屬原子。熔渣通常在金屬熔煉上用於廢棄物的移除。在性質上，為不純態、通常氧化且與其他金屬的矽酸鹽混合之金屬礦砂如鐵、銅、鉛、鋁、及其他金屬。在熔煉期間，當礦砂曝露於高溫，這些不純物由熔解金屬分離且可去除。收集的移除化合物為熔渣。 As used herein, "slag" means a by-product of smelting ore to refine a metal. It can be considered as a mixture of metal oxides; however, it can comprise metal sulfides and metal atoms in elemental form. Slag is commonly used in metal smelting for waste removal. In nature, metal ores such as iron, copper, lead, aluminum, and other metals that are impure, generally oxidized, and mixed with other metal silicates. During the smelting, when the ore is exposed to high temperatures, these impurities are separated by the molten metal and can be removed. The collected removal compound is slag.
在本文中，“鈍氣”意指任何氣體、或氣體組合，其在一般狀況下不易反應。不像貴重氣體，一鈍氣不必然是元素且通常是分子氣體。如同高貴氣體，在所有鈍氣中，因為價數，即最外層電子層，而不反應性的傾向為徹底的。例示之鈍氣包括，如氦(He)、氖(Ne)、氬(Ar)及氮(N2)。 As used herein, "blunt gas" means any gas, or combination of gases, that is not readily reactive under normal conditions. Unlike precious gases, a blunt gas is not necessarily an element and is usually a molecular gas. Like noble gases, in all blunt gases, because of the valence, the outermost electron layer, the tendency to be non-reactive is thorough. Exemplary blunt gases include, for example, helium (He), neon (Ne), argon (Ar), and nitrogen (N 2 ).
在本文中，“旋轉除氣器”意指一用於由熔解金屬除去不純物的設備，其包括一除氣器軸、一動葉輪塊及一偶合器。此軸較佳為中空以允許由其氣體通過。此動葉輪塊可連接至除氣器軸，該葉輪塊基本上由抗熱性材料形成且具有至少一金屬-傳送凹槽，其在當葉輪塊轉動時可排出熔解金屬。此塊較佳地包括至少一與除氣器軸中空部份相通的氣體入口及每一在金屬-傳送凹槽上形成的氣體釋放 開口。每一氣體釋放開口與至少一氣體入口相通。偶合器連接除氣器軸以驅動軸並由至少二偶合元件形成。其他在熔解金屬製造小氣泡的方法包括經由多孔性塞、吹管或管注入氣體。 As used herein, "rotary degasser" means a device for removing impurities from a molten metal that includes a degasser shaft, a moving impeller block, and a coupler. This shaft is preferably hollow to allow passage of gas therethrough. The impeller block can be coupled to a degasser shaft that is substantially formed of a heat resistant material and has at least one metal-transporting groove that can discharge the molten metal as the impeller block rotates. The block preferably includes at least one gas inlet in communication with the hollow portion of the degasser shaft and each gas release formed on the metal-transporting groove Opening. Each gas release opening is in communication with at least one gas inlet. A coupler is coupled to the degasser shaft to drive the shaft and is formed from at least two coupling elements. Other methods of making small bubbles in the molten metal include injecting a gas through a porous plug, blow tube or tube.
當用於本文內，“渦流”意指一具有密閉流線之旋轉、通常為洶湧的流(或任何螺旋作用)。介質或物質的形狀以一中心快速的旋轉以形成一渦流。其以一圓形成動的流動。 As used herein, "vortex" means a rotation, usually a turbulent flow (or any helix) with a closed streamline. The shape of the medium or substance is rapidly rotated at a center to form a vortex. It forms a moving flow with a circle.
在本文中，"方向性固化"意指熔解金屬的固化作用，其藉當冷凍時，施用一溫度梯度至金屬以使熔融餵入金屬可在進行固化作用中連續地以部份取得。當金屬固化時，適當使用方法使液體及固體金屬邊界的界面向加入的餵入金屬源移動並遠離固化作用開始的區域。方向性固化可用來作為純化製程。因為大多數不純物在固化作用期間在液體中比在固體相中可溶，不純物將因固化作用"推"向前端，引起完成的大部份鑄造具有一比原料較低濃度之不純物，同時最後固化之金屬將富含不純物。此金屬的最終部份可刮除或回收。方向性固化在金屬中除去特定不純度的合適性係依在討論中的金屬不純度的分配係數而定，如以Scheil方程式描。方向性固化通常在生產太陽能電池之多晶矽使用的一純化步驟。方向性固化製程的範例為柴氏法(Czochralski(Cz))、浮區式(Fz)、熱交換方法(HEM)、布氏法、區域提純、電磁鑄造(EMC)、水平布氏法等。 As used herein, "directional solidification" means the solidification of a molten metal by applying a temperature gradient to the metal when frozen so that the molten feed metal can be continuously obtained in part during curing. When the metal cures, the appropriate method of use moves the interface of the liquid and solid metal boundaries toward the added feed metal source and away from the area where the curing begins. Directional curing can be used as a purification process. Since most of the impurities are soluble in the liquid during solidification than in the solid phase, the impurities will "push" toward the front end due to the curing action, causing most of the finished casting to have a lower concentration of impurities than the raw material, and finally solidify. The metal will be rich in impurities. The final part of this metal can be scraped or recycled. The suitability of directional solidification to remove specific impurities in the metal depends on the partition coefficient of the metal impurity in question, as depicted by the Scheil equation. Directional curing is typically a purification step used in the production of polycrystalline silicon for solar cells. Examples of directional solidification processes are Czochralski (Cz), floating zone (Fz), heat exchange (HEM), Brinell, regional purification, electromagnetic casting (EMC), horizontal Brinell, and the like.
在本文中，“太陽能電池”意指經過光電效應直接 轉換太陽能為電能的裝置。裝置可主要來自於半導體，典型地為矽 In this paper, “solar battery” means direct photoelectric effect A device that converts solar energy into electrical energy. The device can be mainly from a semiconductor, typically 矽
在本文中，“矽太陽能晶圓”意指高純化矽(論是單或多-晶體)薄片，其形成太陽能電池的基材或基礎。 As used herein, "tantal solar wafer" means a highly purified ruthenium (on a single or multi-crystal) sheet that forms the substrate or foundation of a solar cell.
當用於本文內，“旋轉熔爐意指可以電加熱、氣體或油加熱、或雙燃料啟動的熔爐系統。其由旋轉(基本上為圓柱形)加熱區域組成，該區域可為密閉以控制氛圍。在旋轉熔爐中產物及渣化劑與氛圍的翻滾作用而導致高程度之溫度均一度及氣體-固體接觸。此造成較均一的產品、降低的製程時間及提高的生產速率。所有材料及旋轉熔爐內的氣體的緊密接觸確保任何化學或物理反應完成。 As used herein, "rotating furnace means a furnace system that can be electrically heated, gas or oil heated, or dual fuel activated. It consists of a rotating (substantially cylindrical) heating zone that can be sealed to control the atmosphere The tumbling action of the product and the slag agent in the rotary furnace results in a high degree of temperature uniformity and gas-solid contact. This results in a more uniform product, reduced process time and increased production rate. All materials and rotation The close contact of the gases within the furnace ensures that any chemical or physical reaction is completed.
在本文中，“渣化”意指加入特定的氧化物及或鹽類或其他非可溶材料至熔解金屬如矽的作動，目的在於由熔化物除去一元素不純物。一用於金屬純化的技術。 As used herein, "slag" means the act of adding a particular oxide and/or salt or other non-soluble material to a molten metal such as ruthenium in order to remove an elemental impurity from the melt. A technique for metal purification.
在本文中，“氣體注入”意指注入氣體(如氧、水蒸氣、氫等)至熔解金屬(如矽)浴之作動，其以一可確保氣體與熔融物浴最大接觸之方法達成。此接觸的目的是使不純物在熔化物與氣體反應以形成化合物，此化合物可由熔融物形成之相對無不純物之金屬浴中分離。 As used herein, "gas injection" means the action of injecting a gas (e.g., oxygen, water vapor, hydrogen, etc.) into a bath of a molten metal (e.g., helium), which is accomplished in a manner that ensures maximum contact of the gas with the bath of the melt. The purpose of this contact is to cause the impurities to react with the gas in the melt to form a compound which can be separated from the metal bath formed by the melt relative to the impurity-free.
在本文中，“真空處理”意指將熔解金屬浴如矽置於壓力低於大氣壓力之密閉容器中，其目的為除去蒸氣壓大於熔解金屬之蒸氣壓的不純物。 As used herein, "vacuum treatment" means placing a molten metal bath, such as helium, in a closed vessel at a pressure below atmospheric pressure for the purpose of removing impurities having a vapor pressure greater than the vapor pressure of the molten metal.
“太陽能板”一詞意指一太陽能電池模組，其為一太陽能電池總成以產生電力。在所有例子中，太陽能板基 本上為平的且可以高度及寬度不同取得。陣列為一太陽能電池(PV)模組總成；依設計目標，此太陽能板可串聯或並聯。太陽能板典型地使用於住家、商業、機關、及光電工業應用。 The term "solar panel" means a solar cell module that is a solar cell assembly to generate electricity. In all cases, solar panel base This is flat and can be obtained in different heights and widths. The array is a solar cell (PV) module assembly; the solar panels can be connected in series or in parallel depending on the design goal. Solar panels are typically used in home, commercial, institutional, and optoelectronic industrial applications.
在本文中，“mm”代表毫米，“ppm”代表每百萬份，“℃”意指攝氏度數，“wt%”代表重量百分比，“hr”代表小時，“kg”意指公斤，及“ppm wt.%”每百萬份之重量百分比。 As used herein, "mm" stands for millimeters, "ppm" stands for every million parts, "°C" means degrees Celsius, "wt%" stands for weight percentage, "hr" stands for hours, "kg" means kilograms, and " Ppm wt.%" by weight per million.
參照第1圖，其提供純化矽的方法，及用以獲得純化矽的方法。參照第2圖，其提供純化矽的方法，及用以獲得純化矽的方法。 Referring to Figure 1, there is provided a method of purifying hydrazine, and a method for obtaining purified hydrazine. Referring to Figure 2, there is provided a method of purifying hydrazine, and a method for obtaining purified hydrazine.
簡言之，從原料矽(102)及溶劑金屬(103)形成第一熔融液體(104)。第一熔融液體(104)與第一氣體(106)接觸，以提供第二熔融液體(108)及浮渣(110)。可移除浮渣(110)。冷卻第二熔融液體(108)以提供第一矽晶體(114)及第一母液(116)。第一母液(116)可從第一矽晶體(114)分離出。第一矽晶體(114)可為如下所述再使用(117)，或與可溶解、浸提或適合於與溶劑金屬反應的酸、鹼、醇或化學品接觸(119)以提供清洗過的矽晶體(121)及使用過的酸(123)。可分離(125)清洗過的矽晶體(121)及使用過的酸(123)以提供純化矽晶體(127)。 Briefly, a first molten liquid (104) is formed from the raw material enthalpy (102) and the solvent metal (103). The first molten liquid (104) is contacted with the first gas (106) to provide a second molten liquid (108) and scum (110). The dross (110) can be removed. The second molten liquid (108) is cooled to provide a first tantalum crystal (114) and a first mother liquor (116). The first mother liquor (116) can be separated from the first tantalum crystal (114). The first ruthenium crystal (114) can be reused (117) as described below, or contacted with an acid, base, alcohol or chemical that is soluble, leached or suitable for reaction with the solvent metal (119) to provide cleaning.矽 crystal (121) and used acid (123). The cleaned rhodium crystals (121) and the used acid (123) can be separated to provide purified rhodium crystals (127).
如上所述，從原料矽(102)及溶劑金屬(103)形成第一熔融液體(104)。較佳地，第一熔融液體(104)應該完全地熔解，沒有可觀察到的漿狀物存在。可替代地，第一熔融液體(104)可包括可觀察到的漿狀物存在。 As described above, the first molten liquid (104) is formed from the raw material crucible (102) and the solvent metal (103). Preferably, the first molten liquid (104) should be completely melted without the presence of an observable slurry. Alternatively, the first molten liquid (104) may comprise an observable slurry present.
在一範例中，在從浮渣(110)分離出第二熔融液體(108)後，第二熔融液體(108)可被移到第二容器，如第二熔爐。在另一範例中，分離第一矽晶體(114)後，第一母液(116)可被移到第二或第三容器，如熔爐。經由使用第二或後續容器，可達到一較高純度。當轉移熔融液體或母液時，一實質量之污染物會留在先前的容器上，因此作用如一分離或過濾步驟。 In one example, after separating the second molten liquid (108) from the dross (110), the second molten liquid (108) can be moved to a second vessel, such as a second furnace. In another example, after separating the first germanium crystal (114), the first mother liquor (116) can be moved to a second or third vessel, such as a furnace. A higher purity can be achieved by using a second or subsequent container. When the molten liquid or mother liquor is transferred, a substantial amount of contaminant will remain on the previous vessel, thus acting as a separation or filtration step.
可選擇地，在形成第一熔融液體(104)前，可預先處理原料矽(102)。預-處理可包括渣化、氣體注入、電漿火炬、真空處理或其某些組合。預-處理可發生在感應熔爐、電阻熔爐或旋轉熔爐，或其組合。此外或可替代地，鈦(Ti)、釩(V)、鉻(Cr)、鋯(Zr)、鈣(Ca)、鉿(Hf)、鎂(Mg)、鍶(Sr)或其某些組合可加進原料矽(102)。例如，加入作用之進行可在與一氣體接觸前、與一氣體接觸後、或若未用使用氣體導入步驟則加至第一熔融液體(104)。預-處理可降低原料矽(102)中的硼及磷程度。可替代地，原料矽(102)可與二氧化矽及鋁一起加至熔爐，以提供一矽及鋁混合物。可形成氧化鋁浮渣。 Alternatively, the raw material crucible (102) may be pretreated prior to forming the first molten liquid (104). Pre-treatment can include slag formation, gas injection, plasma torch, vacuum processing, or some combination thereof. Pre-treatment can occur in induction furnaces, electric resistance furnaces or rotary furnaces, or a combination thereof. Additionally or alternatively, titanium (Ti), vanadium (V), chromium (Cr), zirconium (Zr), calcium (Ca), hafnium (Hf), magnesium (Mg), antimony (Sr), or some combination thereof Raw material 矽 (102) can be added. For example, the effect of the addition may be applied to the first molten liquid (104) prior to contact with a gas, after contact with a gas, or if no gas introduction step is employed. The pre-treatment can reduce the degree of boron and phosphorus in the raw material mash (102). Alternatively, the raw material crucible (102) may be added to the furnace together with ceria and aluminum to provide a mixture of antimony and aluminum. Alumina scum can be formed.
若再使用(117)，第一矽晶體(114)可與溶劑金屬(103)加熱或熔融並再次引至第一熔融液體(104)。例如，晶體(114)可以比例為約20%矽晶體及約80%鋁、約50%矽晶體及約50%鋁、或約60%矽及約40%鋁之熔解金屬熔融。也可使用鋁合金。 If (117) is used again, the first tantalum crystal (114) can be heated or melted with the solvent metal (103) and introduced again to the first molten liquid (104). For example, the crystals (114) may be melted in a proportion of about 20% germanium crystals and about 80% aluminum, about 50% germanium crystals, and about 50% aluminum, or about 60% germanium and about 40% aluminum melt metal. Aluminum alloys can also be used.
可使用任何適合的原料矽(102)。例如，冶金級 矽或鋁熔爐級之矽(如、553、441、2202、1502、1101等)可作為原料矽(102)。此外，使用的原料矽(102)可包括可觀察到量的不純物(如，高於約10.0ppm wt.%，高於約50.0ppmwt.%，或高於約100ppmwt.%)，如磷及硼。例如，原料矽(102)可以是約95wt.%至約99.9wt.%純度。更特別地，原料矽(102)可包括約5ppm wt%至約15ppm wt%硼及約30ppm wt%至約60ppm wt%磷。在一特定實施例中，使用的原料矽(102)可以是在先前純化之第一矽晶體(114)。 Any suitable starting material (102) can be used. For example, metallurgical grade 矽 or aluminum furnace grades (eg, 553, 441, 2202, 1502, 1101, etc.) can be used as the raw material 102 (102). Additionally, the starting material ruthenium (102) may comprise an observable amount of impurities (eg, greater than about 10.0 ppm wt.%, greater than about 50.0 ppm wt.%, or greater than about 100 ppm wt.%), such as phosphorus and boron. . For example, the feedstock rhodium (102) can be from about 95 wt.% to about 99.9 wt.% purity. More particularly, the starting material cerium (102) may comprise from about 5 ppm wt% to about 15 ppm wt% boron and from about 30 ppm wt% to about 60 ppm wt% phosphorus. In a particular embodiment, the starting material ruthenium (102) may be the first ruthenium crystal (114) previously purified.
溶劑金屬(103)可包括任何合適的金屬、金屬組合、或其合金，其當加熱時可有效地熔解矽，以生成一熔解液體。適合的例示溶劑金屬(103)包括，如，銅、錫、鋅、銻、銀、鉍、鋁、鎘、鎵、銦、鎂、鉛，其合金，及其組合。一特定溶劑金屬(103)為鋁，或其合金。 The solvent metal (103) may comprise any suitable metal, combination of metals, or alloys thereof that, when heated, effectively melt the ruthenium to form a molten liquid. Suitable exemplary solvent metals (103) include, for example, copper, tin, zinc, antimony, silver, antimony, aluminum, cadmium, gallium, indium, magnesium, lead, alloys thereof, and combinations thereof. A particular solvent metal (103) is aluminum, or an alloy thereof.
原料矽(102)及溶劑金屬(103)可以任何適合的量或比例存在，但前提為第一熔融液體(104)可有效形成。例如，可使用約20wt.%至約60wt.%原料矽(102)，及可使用約40wt.%至約80wt.%做為溶劑金屬(103)之鋁或其合金。更特別地，原料矽(102)可以是約40%鋁及約60%第一熔融液體(104)。 The raw material hydrazine (102) and the solvent metal (103) may be present in any suitable amount or ratio, provided that the first molten liquid (104) is effectively formed. For example, from about 20 wt.% to about 60 wt.% of the raw material ruthenium (102) may be used, and from about 40 wt.% to about 80 wt.% of aluminum as the solvent metal (103) or an alloy thereof may be used. More particularly, the feedstock crucible (102) can be about 40% aluminum and about 60% first melt liquid (104).
如上所述，第一熔融液體(104)與第一氣體(106)接觸，以提供第二熔融液體(108)及浮渣(110)。未受限於任何特定理論，其相信第一氣體(106)改變氣泡(202)及第一熔融液體(104)表面的潤濕角。此造成不預期的包容物或沈澱物附著於的氣泡表面，故其可拉至熔融物表面或留在浮渣 (110)中。而且，氣體(106)可由第一熔融液體(104)反應形成鹽類(如，MgCl2、CaCl2、SrCl2及NaCl)，其可移動至表面以與浮渣(110)一起移除。特別地，包含物及沈澱物藉由附著至第一氣體(106)氣泡(202)可被拉至第二熔融液體(108)的表面，以與浮渣(110)一起移除。就此而言，比大氣泡具有相對較大的表面積對體積比例的相對小氣泡(202)特別地適合於本發明。例如，小氣泡(202)可以是大小約1mm至約5mm。 As described above, the first molten liquid (104) is in contact with the first gas (106) to provide a second molten liquid (108) and scum (110). Without being bound by any particular theory, it is believed that the first gas (106) changes the wetting angle of the bubble (202) and the surface of the first molten liquid (104). This causes undesired inclusions or deposits to adhere to the surface of the bubble so that it can be pulled to the surface of the melt or left in the scum (110). Further, the gas (106) may be formed (104) to form a first liquid molten salt (e.g., MgCl 2, CaCl 2, SrCl 2 and NaCI), which can be moved to the surface together with removing dross (110). In particular, the inclusions and precipitates can be pulled to the surface of the second molten liquid (108) by attachment to the first gas (106) bubble (202) for removal with the scum (110). In this regard, relatively small bubbles (202) having a relatively large surface area to volume ratio over large bubbles are particularly suitable for the present invention. For example, the small bubbles (202) can be from about 1 mm to about 5 mm in size.
使用的第一氣體(106)可被直接導入包含第一熔融液體(104)的容器。在此情勢中，至少氯(Cl2)、氧(O2)、氮(N2)、氦(He)、氬(Ar)、氫(H2)、六氟化硫(SF6)、光氣(COCl2)、四氯化碳(CCl4)、水蒸氣(H2O)、氧(O2)、二氧化碳(CO2)、一氧化碳(CO)、四氯化矽(SiCl4)及四氟化矽(SiF4)之一可被直接導入包含第一熔融液體(104)的容器。第一氣體可導入或接觸至少一次。例如，氯可在氧之後被導入。可替代地，使用的第一氣體(106)可導入至含有第一熔融液體(104)為前驅物之容器，以可有效地釋出第一氣體(106)。前驅物本身可以是固體或液體或鹽熔劑。例如，第一氣體可藉由將第一熔融液體與一液體、固體、或其組合以有效地釋出第一氣體而形成。典型地，液體或固體前驅物將在第一熔融液體(104)的相對高溫情況下進行化學反應或分解以釋放第一氣體(106)。 The first gas (106) used can be directed into the vessel containing the first molten liquid (104). In this case, at least chlorine (Cl 2 ), oxygen (O 2 ), nitrogen (N 2 ), helium (He), argon (Ar), hydrogen (H 2 ), sulfur hexafluoride (SF 6 ), light Gas (COCl 2 ), carbon tetrachloride (CCl 4 ), water vapor (H 2 O), oxygen (O 2 ), carbon dioxide (CO 2 ), carbon monoxide (CO), antimony tetrachloride (SiCl 4 ) and One of the cesium fluoride (SiF4) can be directly introduced into the vessel containing the first molten liquid (104). The first gas can be introduced or contacted at least once. For example, chlorine can be introduced after oxygen. Alternatively, the first gas (106) used can be introduced into a vessel containing the first molten liquid (104) as a precursor to effectively release the first gas (106). The precursor itself can be a solid or liquid or salt flux. For example, the first gas can be formed by effectively releasing the first gas by combining the first molten liquid with a liquid, a solid, or a combination thereof. Typically, the liquid or solid precursor will undergo a chemical reaction or decomposition at a relatively high temperature of the first molten liquid (104) to release the first gas (106).
在一特定實施例中，第一氣體(106)包括100wt.%氯(Cl2)。在另一特定實施例中，第一氣體(106)包括氯(Cl2) 及氮(N2)。例如，在另一特定實施例中，第一氣體(106)包括氯(Cl2)及氮(N2)，其比例為高至約1：4，高至約1：6或高至約1：10。例如，第一氣體(106)可包括約30%氯及約70%氮，約15%氯及約85%氮或約5%氯及約95%氮。 In a particular embodiment, the first gas (106) comprises a 100wt.% Chlorine (Cl 2). In another particular embodiment, the first gas (106) comprises chlorine (Cl 2 ) and nitrogen (N 2 ). For example, in another particular embodiment, the first gas (106) comprises chlorine (Cl 2 ) and nitrogen (N 2 ) in a ratio of up to about 1:4, up to about 1:6 or up to about 1 :10. For example, the first gas (106) can comprise about 30% chlorine and about 70% nitrogen, about 15% chlorine and about 85% nitrogen or about 5% chlorine and about 95% nitrogen.
在一實施例中，第一熔融液體(104)可接觸使用旋轉除氣器(204)以接觸第一氣體(106)。旋轉除氣器(204)可有效將第一氣體(106)導入至第一熔融液體(104)中。此外，旋轉除氣器(204)可有效地攪動(如，攪拌)第一熔融液體(104)以產生相對小氣泡，同時導入第一氣體(106)至第一熔融液體(104)中。例如，氣泡可以是約1mm至約5mm。 In an embodiment, the first molten liquid (104) may be contacted with a rotary degasser (204) to contact the first gas (106). The rotary degasser (204) is effective to introduce the first gas (106) into the first molten liquid (104). Additionally, the rotary degasser (204) can effectively agitate (e.g., agitate) the first molten liquid (104) to produce relatively small bubbles while introducing the first gas (106) into the first molten liquid (104). For example, the bubbles can be from about 1 mm to about 5 mm.
浮渣(110)可接著由第二熔融液體(108)中移除，例如使用一撇渣器。典型地，浮渣(110)可以是與母液混合之白、灰或黑粉末、半-固體浮渣及氧化物，位於第二熔融液體(108)表面。第二熔融液體(108)可過濾包容物(如，二硼化鈦包容物)或沈澱物，如藉由利用一陶瓷泡沫體濾器、過濾床、在過濾床中的過濾餅或玻璃纖維布。此過濾亦可移除任何加至原料矽(102)之預-處理製程部份之元素。在一可選擇之實施例中，旋轉除氣器(204)可建立第二熔融液體渦流(108)，其可有效地混合第二熔融液體(108)中的浮渣(110)。在此實施例中，渦流可接觸氧以提供額外的浮渣(110)。 The dross (110) can then be removed from the second molten liquid (108), for example using a skimmer. Typically, the dross (110) may be a white, ash or black powder, semi-solid dross and oxide mixed with the mother liquor, on the surface of the second molten liquid (108). The second molten liquid (108) can filter the inclusions (e.g., titanium diboride inclusions) or precipitates, such as by using a ceramic foam filter, a filter bed, a filter cake in a filter bed, or a fiberglass cloth. This filtration also removes any elements added to the pre-treatment process portion of the stock crucible (102). In an alternative embodiment, the rotary degasser (204) establishes a second molten liquid vortex (108) that effectively mixes the scum (110) in the second molten liquid (108). In this embodiment, the vortex may contact oxygen to provide additional scum (110).
在一實施例中，在接觸第一氣體(106)前，可冷卻第一熔融液體(104)。特別地，在接觸第一氣體(106)前，可冷卻第一熔融液體(104)，至剛好高於液相線溫度(如，在高於液相線溫度之約50℃內)或冷卻至介於液相線及固相 線溫度的溫度。預期溫度將依混合物中的矽及溶劑金屬比例而定。 In an embodiment, the first molten liquid (104) may be cooled prior to contacting the first gas (106). In particular, prior to contacting the first gas (106), the first molten liquid (104) may be cooled to just above the liquidus temperature (eg, within about 50 ° C above the liquidus temperature) or cooled to Between liquidus and solid phase The temperature of the line temperature. The expected temperature will depend on the ratio of bismuth and solvent metal in the mixture.
在一實施例中，可加熱第二熔融液體(108)在將第一熔融液體(104)接觸第一氣體(106)後，及在浮渣(110)及第二熔融液體(108)分離前。特別地，在第一熔融液體(104)與第一氣體(106)接觸後，及在浮渣(110)及第二熔融液體(108)分離前可加熱第二熔融液體(108)至高於液相線溫度。更特別地，在第一熔融液體(104)與第一氣體(106)接觸後，及在浮渣(110)及第二熔融液體(108)分離前，加熱第二熔融液體(108)高於液相線溫度之約20℃內。 In one embodiment, the second molten liquid (108) may be heated after contacting the first molten liquid (104) with the first gas (106) and before the scum (110) and the second molten liquid (108) are separated. . Specifically, after the first molten liquid (104) is in contact with the first gas (106), and before the dross (110) and the second molten liquid (108) are separated, the second molten liquid (108) may be heated to be higher than the liquid. Phase line temperature. More specifically, after the first molten liquid (104) is in contact with the first gas (106), and before the scum (110) and the second molten liquid (108) are separated, heating the second molten liquid (108) is higher than The liquidus temperature is within about 20 °C.
如上所述，冷卻(112)第二熔融液體(108)以提供第一矽晶體(114)及第一母液(116)。在一實施例中，當攪動第二熔融液體(108)時，可冷卻(112)第二熔融液體(108)。未關聯至任何特定的理論，其相信在冷卻(112)期間，攪動可提供具有相對高約純度之相對小矽晶體(114)，其難以過濾。一小量的混合可提供約1mm(厚度)、約3mm(寬度)及約3mm(長度)的矽晶體(114)。 As described above, the second molten liquid (108) is cooled (112) to provide a first tantalum crystal (114) and a first mother liquor (116). In an embodiment, the second molten liquid (108) may be cooled (112) while agitating the second molten liquid (108). Not being associated with any particular theory, it is believed that during cooling (112), agitation can provide relatively small germanium crystals (114) having relatively high purity, which is difficult to filter. A small amount of mixing provides a germanium crystal (114) of about 1 mm (thickness), about 3 mm (width), and about 3 mm (length).
此外，若在第一母液(116)中獲得第一矽晶體(114)，可冷卻(112)第二熔融液體(108)至任何適合及適當溫度提。特別地，第二熔融液體(108)可冷卻(112)接近但高於固相線溫度(如，在高於固相線溫度之約100℃內，在高於固相線溫度之約125℃內，或在高於固相線溫度之約150℃內)。更特別地，第二熔融液體(108)可被冷卻(112)至高於固相線溫度及低於液相線溫度。預期的溫度依矽對溶劑金屬 的比例及加至之混合物的預-處理元素型式與量而定。 Additionally, if the first tantalum crystal (114) is obtained in the first mother liquor (116), the second molten liquid (108) may be cooled (112) to any suitable and suitable temperature. In particular, the second molten liquid (108) may be cooled (112) close to but above the solidus temperature (eg, within about 100 ° C above the solidus temperature, about 125 ° C above the solidus temperature) Within, or within about 150 ° C above the solidus temperature). More specifically, the second molten liquid (108) can be cooled (112) to above the solidus temperature and below the liquidus temperature. Expected temperature depends on solvent metal The ratio and the pre-treatment element type and amount of the mixture added are determined.
若在第一母液(116)中第一矽晶體(114)以一可接受純度獲得，則第二熔融液體(108)可在任何適合的速率冷卻(112)。若在第一母液(116)中獲得第一矽晶體(114)，則第二熔融液體(108)可在任何適合且適當長的時間冷卻(112)。例如，第二熔融液體(108)可在至少約1小時、至少約8小時或至少約24小時的時間冷卻(112)。 If the first tantalum crystal (114) is obtained in an acceptable purity in the first mother liquor (116), the second molten liquid (108) can be cooled (112) at any suitable rate. If the first tantalum crystal (114) is obtained in the first mother liquor (116), the second molten liquid (108) can be cooled (112) at any suitable and suitable length of time. For example, the second molten liquid (108) can be cooled (112) for a period of at least about 1 hour, at least about 8 hours, or at least about 24 hours.
在一實施例中，可分離第一矽晶體(114)及第一母液(116)。此分離可以任何適合及適當方法進行。例如，此分離可以由第一矽晶體(114)中傾倒第一母液(116)而實施。可替代地，分離可使用離心實施。如第2(b)圖中可見，可使用一濾器(115)以施用壓力至第一矽晶體(114)，藉此助於分離。 In one embodiment, the first germanium crystal (114) and the first mother liquor (116) can be separated. This separation can be carried out in any suitable and suitable manner. For example, this separation can be performed by pouring the first mother liquor (116) from the first tantalum crystal (114). Alternatively, the separation can be carried out using centrifugation. As can be seen in Figure 2(b), a filter (115) can be used to apply pressure to the first helium crystal (114), thereby aiding in separation.
在一特定實施例中，在後續純化中，可使用或再使用(117)獲得的第一矽晶體(114)為第二熔融液體(108)。此再使用或回收(117)可進行多次(如，2、3、4或5)以提供具有需要純度程度的第二熔融液體(108)。在此一實施例中，在形成後續第二熔融液體(108)前，鋁(Al)可加入至第一矽晶體(114)。 In a particular embodiment, in subsequent purification, the first ruthenium crystal (114) obtained (117) can be used or reused as the second molten liquid (108). This reuse or recovery (117) can be carried out multiple times (e.g., 2, 3, 4, or 5) to provide a second molten liquid (108) having a desired degree of purity. In this embodiment, aluminum (Al) may be added to the first tantalum crystal (114) prior to forming the subsequent second molten liquid (108).
第一矽晶體(114)可使用任何適合及有效技術由第一母液(116)分離。第一矽晶體(114)與酸、鹼、醇或可溶解溶劑金屬的化學品接觸，以提供清洗過的矽晶體(121)及使用過的酸(123)。可分離清洗過的矽晶體(121)及使用過的酸(123)，以提供純化矽晶體。使用過的酸(123)意指不僅為 任何存在之使用過的酸，但亦為用於溶解、浸提或易於與溶劑金屬反應之使用過的鹼、醇或其他化合物。使用過的酸意指在與第一矽晶體(114)接觸後存在之至少一此材料。 The first tantalum crystal (114) can be separated from the first mother liquor (116) using any suitable and efficient technique. The first ruthenium crystal (114) is contacted with an acid, a base, an alcohol, or a chemical that dissolves the solvent metal to provide cleaned ruthenium crystals (121) and used acid (123). The cleaned ruthenium crystal (121) and the used acid (123) can be separated to provide purified ruthenium crystals. Used acid (123) means not only Any used acid present, but also a used base, alcohol or other compound for dissolution, leaching or ease of reaction with solvent metals. Used acid means at least one such material present after contact with the first tantalum crystal (114).
酸可包括氯化氫(HCl)、硝酸(HNO3)、硫酸(H2SO4)、氫氟酸(HF)、乙酸、水或其組合。酸可包括約8莫耳酸；及水。例如，8莫耳酸可包括約95%(v)氯化氫(HCl)及約5%(v)硝酸(HNO3)、硫酸(H2SO4)、氫氟酸(HF)、或其組合。使用的鹼，如強鹼，可包括氫氧化鈉(NaOH)及氫氧化鉀(KOH)。清洗過的矽晶體可包括約800ppm(wt.)至約2,000ppm(wt)鋁(Al)，如以感應耦合電漿光學放射光譜儀(Inductively Coupled Plasma Optical Emission Spectrometer(ICPOES))測量。 The acid may include hydrogen chloride (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), hydrofluoric acid (HF), acetic acid, water, or a combination thereof. The acid can include about 8 moles of acid; and water. For example, 8 moles of acid can include about 95% (v) hydrogen chloride (HCl) and about 5% (v) nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), hydrofluoric acid (HF), or a combination thereof. The base used, such as a strong base, may include sodium hydroxide (NaOH) and potassium hydroxide (KOH). The cleaned germanium crystal may comprise from about 800 ppm (wt.) to about 2,000 ppm (wt) aluminum (Al) as measured by an Inductively Coupled Plasma Optical Emission Spectrometer (ICPOES).
參照第2圖，其提供純化矽的方法，及用以獲得純化矽的方法。簡言之，從原料矽(102)及溶劑金屬(103)形成第一熔融液體(104)。冷卻第一熔融液體(104)以提供第一矽晶體(114)及第一母液116)。第一矽晶體(114)可為如下所述再使用過的(117)，或與可有效溶解或浸提鋁的酸、鹼、醇或化學品(119)接觸，以提供清洗過的矽晶體(121)及使用過的酸(123)。可分離(125)清洗過的矽晶體(121)及使用過的酸(123)以提供純化矽晶體(127)。 Referring to Figure 2, there is provided a method of purifying hydrazine, and a method for obtaining purified hydrazine. Briefly, a first molten liquid (104) is formed from the raw material enthalpy (102) and the solvent metal (103). The first molten liquid (104) is cooled to provide a first tantalum crystal (114) and a first mother liquor 116). The first ruthenium crystal (114) may be re-used (117) as described below, or contacted with an acid, base, alcohol or chemical (119) that is effective for dissolving or leaching aluminum to provide cleaned ruthenium crystals. (121) and used acid (123). The cleaned rhodium crystals (121) and the used acid (123) can be separated to provide purified rhodium crystals (127).
如上所述，冷卻(112)第一熔融液體(104)以提供第一矽晶體(114)及第一母液(116)。在一實施例中，當攪動時可冷卻(112)第一熔融液體(104)。不受任何理論限制任何特別的理論，其相信在冷卻(112)期間，攪動可提供相對高 純度之相對小的矽晶體(114)，其難以過濾。一小量之混合提供約1mm(厚度)、約3mm(寬度)及約3mm(長度)的矽晶體(114)。假如晶體沒有混合，其大小可高至約1mm(厚度)、約15mm(寬度)及約15mm(長度)或高至約2mm(厚度)、約60mm(寬度)及約60mm(長度)。 As described above, the first molten liquid (104) is cooled (112) to provide a first tantalum crystal (114) and a first mother liquor (116). In an embodiment, the first molten liquid (104) may be cooled (112) when agitated. Without being bound by any theory, it is believed that agitation can provide relatively high during cooling (112). A relatively small purity of germanium crystals (114), which is difficult to filter. A small amount of mixing provides a ruthenium crystal (114) of about 1 mm (thickness), about 3 mm (width), and about 3 mm (length). If the crystals are not mixed, they can be up to about 1 mm (thickness), about 15 mm (width), and about 15 mm (length) or up to about 2 mm (thickness), about 60 mm (width), and about 60 mm (length).
此外，若第一矽晶體(114)在第一母液(116)中獲得，則可冷卻(112)第一熔融液體(104)至任何適合且適當的溫度。更特別地，可冷卻(112)第一熔融液體(104)至高於固相線溫度及低於液相線溫度。 Additionally, if the first germanium crystal (114) is obtained in the first mother liquor (116), the first molten liquid (104) may be cooled (112) to any suitable and suitable temperature. More specifically, the first molten liquid (104) may be cooled (112) to above the solidus temperature and below the liquidus temperature.
若第一矽晶體(114)在第一母液(116)中獲得，則第一熔融液體(104)可在任何適合且任何適當之速率被冷卻(112)。若第一矽晶體(114)在第一母液(116)中獲得，則第一熔融液體(104)可在任何適合且任何適當長之時間被冷卻(112)。例如，可在至少約1小時、至少約8小時或至少約24小時之時間冷卻(112)第一熔融液體(104)。 If the first germanium crystal (114) is obtained in the first mother liquor (116), the first molten liquid (104) can be cooled (112) at any suitable and any suitable rate. If the first germanium crystal (114) is obtained in the first mother liquor (116), the first molten liquid (104) can be cooled (112) at any suitable and any suitable length of time. For example, the first molten liquid (104) can be cooled (112) for at least about 1 hour, at least about 8 hours, or at least about 24 hours.
在一實施例中，可分離第一矽晶體(114)及第一母液(116)。分離可以任何適合的及適當的方式進行。例如，藉由從第一矽晶體(114)倒出第一母液(116)進行分離。可替代地，分離可使用離心實施。如第2(b)圖所示，可使用一濾器(115)以施加壓力至第一矽晶體(114)，而促進分離。 In one embodiment, the first germanium crystal (114) and the first mother liquor (116) can be separated. Separation can be carried out in any suitable and suitable manner. For example, the separation is performed by pouring the first mother liquor (116) from the first tantalum crystal (114). Alternatively, the separation can be carried out using centrifugation. As shown in Figure 2(b), a filter (115) can be used to apply pressure to the first helium crystal (114) to promote separation.
在一特定實施例中，在後續純化中，可使用或再使用(117)獲得的第一矽晶體(114)為第一熔融液體(104)之部份。此再使用或回收(117)可實施多次(如，2、3、4或5)以提供具有需要純度程度的第一熔融液體(104)。在此實施 例中，在形成後續第一熔融液體(104)前，鋁(Al)可加入至第一矽晶體(114)。 In a particular embodiment, the first ruthenium crystal (114) obtained or used (117) may be part of the first molten liquid (104) in subsequent purification. This reuse or recovery (117) can be carried out multiple times (e.g., 2, 3, 4, or 5) to provide a first molten liquid (104) having a desired degree of purity. Implemented here In the example, aluminum (Al) may be added to the first tantalum crystal (114) before forming the subsequent first molten liquid (104).
第一矽晶體(114)可使用任何適合及有效技術由第一母液(116)分離。將第一矽晶體(114)接觸酸，以提供清洗過的矽晶體(121)及使用過的酸(123)。可分離清洗過的矽晶體(121)及使用過的酸(123)，以提供純化矽晶體。 The first tantalum crystal (114) can be separated from the first mother liquor (116) using any suitable and efficient technique. The first ruthenium crystal (114) is contacted with an acid to provide cleaned ruthenium crystals (121) and used acid (123). The cleaned ruthenium crystal (121) and the used acid (123) can be separated to provide purified ruthenium crystals.
當獲得純化矽晶體，不論使用前述之何者方法，晶體可熔化於熔爐中以提供熔融矽。此熔融矽可接著與氣體接觸，如實質之純O2(如，99.5%O2)及接著可選擇地過濾。矽可被方向性固化以提供矽錠。錠的頂部可選擇的移除，如藉由切除、打斷或傾倒掉部份熔融錠的頂部。矽可被後處理，如經由氣體注入(如，使用水、氫、氬或氧)、渣化、電漿火炬或真空處理。後-處理可發生於感應熔爐、電阻熔爐、旋轉熔爐或其組合以降低硼、鋁及磷程度。氣體注入可藉由例如在一熔爐中利用旋轉除氣器、吹管或多孔性插塞而產生。可選擇地，矽可被方向性固化以提供多晶系錠或單晶系梨晶。方向性固化可重複多次。 When purified germanium crystals are obtained, the crystals can be melted in a furnace to provide molten germanium, regardless of which of the foregoing methods is used. Then the molten silicon may be contacted with a gas, such as pure essence of O 2 (eg, 99.5% O 2) and optionally followed by filtration. The crucible can be directionally cured to provide a crucible ingot. The top of the ingot can be selectively removed, such as by cutting, breaking or pouring off the top of a portion of the molten ingot. The crucible can be post-treated, such as via gas injection (eg, using water, hydrogen, argon or oxygen), slagging, plasma torch or vacuum treatment. Post-treatment can occur in induction furnaces, electric resistance furnaces, rotary furnaces, or combinations thereof to reduce the extent of boron, aluminum, and phosphorus. Gas injection can be produced, for example, by using a rotary degasser, a blow tube or a porous plug in a furnace. Alternatively, the ruthenium may be directionally cured to provide a polycrystalline ingot or a single crystal type of pear crystal. Directional curing can be repeated multiple times.
參照第4圖，顯示用以純化矽之方法的一範例，包括從原料矽(102)及溶劑金屬(103)，如鋁，形成第一熔融液體(104)；將第一熔融液體(104)與第一氣體(106)接觸，以提供浮渣(110)及第二熔融液體(108)；分離浮渣及第二熔融液體(108)；冷卻(112)第二熔融液體以形成第一矽晶體(114)及第一母液(116)及接著分離第一矽晶體及第一母液。第一矽晶體(114)藉由與溶劑金屬(103)熔融以形成另一第一熔 融液體(104)或與溶劑金屬(103)熔融並與一氣體以形成第二熔融液體(108)而再使用(117)。此方法亦可選擇地包括熔融第一矽晶體與溶劑金屬及重複上述步驟。 Referring to Figure 4, there is shown an example of a method for purifying a crucible comprising forming a first molten liquid (104) from a raw material crucible (102) and a solvent metal (103) such as aluminum; and a first molten liquid (104) Contacting the first gas (106) to provide the dross (110) and the second molten liquid (108); separating the dross and the second molten liquid (108); cooling (112) the second molten liquid to form the first crucible The crystal (114) and the first mother liquor (116) and then the first ruthenium crystal and the first mother liquor are separated. The first germanium crystal (114) is melted by the solvent metal (103) to form another first melt The molten liquid (104) or molten with the solvent metal (103) and with a gas to form a second molten liquid (108) is reused (117). The method may also optionally include melting the first tantalum crystal and the solvent metal and repeating the above steps.
第一矽晶體(114)可與酸、鹼、醇或可溶解鋁或溶劑金屬(119)的化學品接觸，以提供清洗過的矽晶體(121)及使用過的酸(123)。清洗過的矽晶體(121)可從使用過的酸(123)分離(125)，足以提供純化矽晶體(127)。可接著熔解(129)純化矽晶體(127)以形成矽熔融物(131)。第二氣體(133)，如氧，可接觸矽熔融物(131)。接觸第二氣體的矽熔融物(135)，可接著方向性固化(137)以形成多晶矽(139)。 The first ruthenium crystal (114) can be contacted with an acid, a base, an alcohol, or a chemical that dissolves the aluminum or solvent metal (119) to provide cleaned ruthenium crystals (121) and used acid (123). The cleaned ruthenium crystal (121) can be separated (125) from the used acid (123), sufficient to provide purified ruthenium crystals (127). The ruthenium crystals (127) can then be melted (129) to form a ruthenium melt (131). A second gas (133), such as oxygen, can contact the bismuth melt (131). The tantalum melt (135) contacting the second gas may then be directionally cured (137) to form polycrystalline germanium (139).
在一實施例中，第一矽晶體(114)在接觸酸之前，粉碎至約1mm或至約較小的塊。 In one embodiment, the first tantalum crystal (114) is comminuted to about 1 mm or to about a smaller block prior to contacting the acid.
在酸性浸出後由一例示GDMS測試的分析結果提供於下表，單位為ppm(wt)。 The results of the analysis by an example of the GDMS test after acid leaching are provided in the following table in ppm (wt).
在酸性浸出後由一例示GDMS測試的分析結果，單位為ppm(wt)， Analysis results of an example of GDMS test after acid leaching in ppm (wt),
及重複步驟：(a)從矽及選自於銅、錫、鋅、銻、銀、鉍、鋁、鎘、鎵、銦、鎂、鉛、其合金、及其組合之群組的溶劑金屬形成第一熔融液體；(b)將第一熔融液體與第一氣體接觸，以提供浮渣及第二熔融液體；(c)分離浮渣及第二熔融液體；(d)冷卻第二熔融液體以形成第一矽晶體及第一母液；及(e)分離第一矽晶體及第一母液。 And repeating steps: (a) forming from a solvent metal selected from the group consisting of copper, tin, zinc, antimony, silver, antimony, aluminum, cadmium, gallium, indium, magnesium, lead, alloys thereof, and combinations thereof a first molten liquid; (b) contacting the first molten liquid with the first gas to provide the dross and the second molten liquid; (c) separating the dross and the second molten liquid; (d) cooling the second molten liquid to Forming a first germanium crystal and a first mother liquor; and (e) separating the first germanium crystal and the first mother liquor.
描述於本文的方法在一相對有成本效益的方法及相對短時間(如，在約24-94小時內)可有效地提供商業數量的(如，至少約240kg)純化矽晶體。本文描述的方法在一相對有成本效益的方法及相對短時間(如，在約24-94小時內)有效地提供至少約100公噸/年的純化矽。獲得的相對純化矽可接著進行進一步處理以提供太陽能板、太陽能電池、晶圓或積體電路。 The methods described herein are effective to provide commercial quantities (e.g., at least about 240 kg) of purified ruthenium crystals in a relatively cost effective manner and for relatively short periods of time (e.g., within about 24-94 hours). The methods described herein effectively provide at least about 100 metric tons per year of purified hydrazine in a relatively cost effective process and for a relatively short period of time (e.g., within about 24-94 hours). The relative purification enthalpy obtained can then be further processed to provide solar panels, solar cells, wafers or integrated circuits.
獲得之相對純矽可由週期表的所有元素中純化， 包括鋰(Li)、硼(B)、鈉(Na)、鈦(Ti)、鐵(Fe)、鎂(Mg)、釩(V)、鋅(Zn)、磷(P)、硫(S)、鉀(K)、鈣(Ca)、鍶(Sr)、氯(Cl)、鉻(Cr)、錳(Mn)、鋁(Al)、砷(As)、銻(Sb)、鎵(Ga)、銦(In)、鎳(Ni)及銅(Cu)之至少一者。本發明實施例可提供包含下列任一者之相對純矽，其中每一者為少於約15ppm：鋰(Li)、硼(B)、鈉(Na)、鈦(Ti)、鐵(Fe)、鎂(Mg)、釩(V)、鋅(Zn)、磷(P)、硫(S)、鉀(K)、鈣(Ca)、鍶(Sr)、氯(Cl)、鉻(Cr)、錳(Mn)、鋁(Al)、砷(As)、銻(Sb)、鎵(Ga)、銦(In)、鎳(Ni)及銅(Cu)。更特別地，獲得之相對純矽可包含下列任一者之相對純矽，其中每一者為少於約15ppm：鐵(Fe)及鋁(Al)。此外，獲得之相對純矽可包含下列任一者之相對純矽，其中每一者為少於約1ppm：鋰(Li)、硼(B)、鈉(Na)、鈦(Ti)、鎂(Mg)、釩(V)、鋅(Zn)、磷(P)、硫(S)、鉀(K)、鈣(Ca)、鍶(Sr)、氯(Cl)、鉻(Cr)、錳(Mn)、砷(As)、銻(Sb)、鎵(Ga)、銦(In)、鎳(Ni)、銅(Cu)、鐵(Fe)及鋁(Al)。 The relative purity obtained is purified from all elements of the periodic table. Including lithium (Li), boron (B), sodium (Na), titanium (Ti), iron (Fe), magnesium (Mg), vanadium (V), zinc (Zn), phosphorus (P), sulfur (S) , potassium (K), calcium (Ca), strontium (Sr), chlorine (Cl), chromium (Cr), manganese (Mn), aluminum (Al), arsenic (As), antimony (Sb), gallium (Ga) At least one of indium (In), nickel (Ni), and copper (Cu). Embodiments of the invention may provide relatively pure ruthenium comprising any of the following, each of which is less than about 15 ppm: lithium (Li), boron (B), sodium (Na), titanium (Ti), iron (Fe) , magnesium (Mg), vanadium (V), zinc (Zn), phosphorus (P), sulfur (S), potassium (K), calcium (Ca), antimony (Sr), chlorine (Cl), chromium (Cr) Manganese (Mn), aluminum (Al), arsenic (As), antimony (Sb), gallium (Ga), indium (In), nickel (Ni), and copper (Cu). More particularly, the relatively pure enthalpy obtained may comprise relatively pure enthalpy of any of the following, each of which is less than about 15 ppm: iron (Fe) and aluminum (Al). Furthermore, the relatively pure enthalpy obtained may comprise relatively pure enthalpy of any of the following, each of which is less than about 1 ppm: lithium (Li), boron (B), sodium (Na), titanium (Ti), magnesium ( Mg), vanadium (V), zinc (Zn), phosphorus (P), sulfur (S), potassium (K), calcium (Ca), strontium (Sr), chlorine (Cl), chromium (Cr), manganese ( Mn), arsenic (As), antimony (Sb), gallium (Ga), indium (In), nickel (Ni), copper (Cu), iron (Fe), and aluminum (Al).
任何上述步驟可在高純度耐火材料中進行。耐火材料可包含低程度的硼及磷。耐火材料可以是熔矽石或65-85%矽土，例如。任何上述所用的容器(如，坩鍋)可以例如石英、熔矽石、石墨、Si3N4或SiC製造或內襯。容器可具有一低P及B程度的高純度模塗漿(塗層)。 Any of the above steps can be carried out in a high purity refractory. The refractory material can contain a low degree of boron and phosphorus. The refractory material may be fused vermiculite or 65-85% alumina, for example. Any of the above-described containers (e.g., crucibles) may be made or lined with, for example, quartz, fused vermiculite, graphite, Si 3 N 4 or SiC. The container may have a high purity mold spread (coating) of low P and B degrees.
熔解950lb的40%冶金矽及60%初生鋁混合物及在熔爐中加熱至975℃。使用鋁-鈣母合金將0.25lb的Ca加進熔化物。浮渣由熔化物表面撇去。降低溫度至950℃且 85% N2及15% Cl2氣體以一旋轉除氣器在3小時內注入熔融混合物中，接著注入100% N2氣體15分鐘。每30分鐘，由熔化物表面撇去浮渣。加熱混合物至1000℃。熔融混合物被倒入新熔爐及溫度在8小時期間降低至750℃。熔融母液接著倒出熔爐，且殘留的矽晶體/薄片耙出熔爐。矽薄片/晶體與鋁以50-50wt%之比例在一熔爐中熔融。重複氣體注入、浮渣去除及晶體成長的程序。此薄片接著置於8wt% HCl+水的溶液中且在72小時此薄片溶去鋁。薄片接著由酸過濾並乾燥。乾燥之薄片接著在熔爐中熔融。一旦熔融，經由一吹管在3小時期間注入99.5% O2至熔融的矽中。浮渣或熔渣由熔爐撇去且熔融的矽倒入熔爐中，其由底部向上方向性固化該矽。切除矽錠頂部並在美國新罕不什爾州美利默克市(Merrimack，NH)GT Solar公司製造的GT-DSS240熔爐中熔融殘餘的矽以得方向性固化的矽。生成之多晶矽具有硼量為0.79-1.1ppmw及介於0.27-1.1ppmw間之P與低於1ppmw之其他金屬，其係以GDMS測量。 950 lbs of 40% metallurgical crucible and 60% primary aluminum mixture were melted and heated to 975 ° C in a furnace. 0.25 lb of Ca was added to the melt using an aluminum-calcium master alloy. The scum is removed from the surface of the melt. The temperature was lowered to 950 ° C and 85% N 2 and 15% Cl 2 gas was injected into the molten mixture in a rotary degasser for 3 hours, followed by injection of 100% N 2 gas for 15 minutes. Every 30 minutes, the dross is removed from the surface of the melt. The mixture was heated to 1000 °C. The molten mixture was poured into a new furnace and the temperature was lowered to 750 ° C during 8 hours. The molten mother liquor is then poured out of the furnace and the remaining ruthenium crystals/sheets are thrown out of the furnace. The crucible/crystal and aluminum are melted in a furnace at a ratio of 50-50% by weight. Repeat the procedure of gas injection, scum removal and crystal growth. This sheet was then placed in a solution of 8 wt% HCl + water and the sheet was stripped of aluminum at 72 hours. The flakes are then filtered through an acid and dried. The dried flakes are then melted in a furnace. Once molten, 99.5% O 2 was injected into the molten crucible over a period of 3 hours via a blow tube. The scum or slag is removed from the furnace and the molten crucible is poured into the furnace, which solidifies the crucible upward from the bottom. The top of the crucible was cut and the residual crucible was melted in a GT-DSS 240 furnace manufactured by GT Solar, Merrimack, NH, USA to obtain a directional solidified crucible. The resulting polycrystalline germanium has a boron content of 0.79-1.1 ppmw and a P between 0.27-1.1 ppmw and other metals below 1 ppmw, as measured by GDMS.
熔解950 lb的40%冶金矽及60%初生鋁混合物及在熔爐中加熱至975℃。使用鋁-鈣母合金將1 lb的Ca加進熔化物。浮渣由熔化物表面撇去。降低溫度至950℃且85% N2及15% Cl2氣體氣體以一旋轉除氣器在3小時內注入熔融混合物中，接著注入100% N2氣體15分鐘。加熱混合物至975℃及浮渣由熔化物表面撇去。將熔融混合物倒入新熔爐及溫度在8小時期間降低至750℃。熔融母液接著倒出熔爐，且 殘留的矽晶體/薄片耙出熔爐。鋁母液可賣至晶圓代工業以製成鋁鑄塊。矽薄片與鋁以50-50wt%之比例在一熔爐中熔融。重複氣體注入、浮渣去除及晶體成長的程序。此薄片接著置於8wt% HCl+水的溶液中且在48小時此薄片溶去鋁。薄片接著由酸過濾並乾燥。乾燥之薄片接著在DSS240 GT熔爐中熔融。切除矽錠頂部並在美國新罕不什爾州美利默克市(Merrimack，NH)GT Solar公司製造的GT-DSS240熔爐中熔融殘餘的矽以得方向性固化的矽。生成之多晶矽具有硼量為0.41-1.1ppmw及介於0.27-1.1ppmw間之P與低於1ppmw之其他金屬，其係以GDMS測量。 Melt 950 lb of 40% metallurgical crucible and 60% primary aluminum mixture and heat to 975 ° C in a furnace. One lb of Ca was added to the melt using an aluminum-calcium master alloy. The scum is removed from the surface of the melt. The temperature was lowered to 950 ° C and 85% N 2 and 15% Cl 2 gas were injected into the molten mixture in a rotary degasser for 3 hours, followed by injection of 100% N 2 gas for 15 minutes. The mixture was heated to 975 ° C and the scum was skimmed off the surface of the melt. The molten mixture was poured into a new furnace and the temperature was lowered to 750 ° C during 8 hours. The molten mother liquor is then poured out of the furnace and the remaining ruthenium crystals/sheets are thrown out of the furnace. Aluminum mother liquor can be sold to the foundry industry to make aluminum ingots. The crucible sheet and aluminum are melted in a furnace at a ratio of 50 to 50% by weight. Repeat the procedure of gas injection, scum removal and crystal growth. This sheet was then placed in a solution of 8 wt% HCl + water and the sheet was stripped of aluminum at 48 hours. The flakes are then filtered through an acid and dried. The dried flakes were then melted in a DSS 240 GT furnace. The top of the crucible was cut and the residual crucible was melted in a GT-DSS 240 furnace manufactured by GT Solar, Merrimack, NH, USA to obtain a directional solidified crucible. The resulting polycrystalline germanium has a boron content of from 0.41 to 1.1 ppmw and a P between 0.27-1.1 ppmw and other metals below 1 ppmw, as measured by GDMS.
熔解950 lb的40%冶金矽及60%初生鋁混合物及在熔爐中加熱至975℃。浮渣由熔化物表面撇去。熔融混合物被倒入新熔爐及溫度在2小時期間降低至750℃。熔融母液接著倒出熔爐，且殘留的矽晶體/薄片耙出熔爐。此已生長的薄片接著置於8wt% HCl+水的溶液中且在48小時此薄片溶去鋁。薄片接著由酸過濾並乾燥。乾燥之薄片接著在熔爐中熔融。一旦熔融，經由一吹管在3小時期間注入99.5% O2至熔融的矽中。浮渣或熔渣由熔爐撇去且熔融的矽倒入熔爐中，其由底部向上方向性固化該矽。切除矽錠頂部且剩餘的矽在GT-DSS240熔爐中熔融以得方向性固化的矽。 Melt 950 lb of 40% metallurgical crucible and 60% primary aluminum mixture and heat to 975 ° C in a furnace. The scum is removed from the surface of the melt. The molten mixture was poured into a new furnace and the temperature was lowered to 750 ° C during 2 hours. The molten mother liquor is then poured out of the furnace and the remaining ruthenium crystals/sheets are thrown out of the furnace. This grown sheet was then placed in a solution of 8 wt% HCl + water and the sheet was stripped of aluminum at 48 hours. The flakes are then filtered through an acid and dried. The dried flakes are then melted in a furnace. Once molten, 99.5% O 2 was injected into the molten crucible over a period of 3 hours via a blow tube. The scum or slag is removed from the furnace and the molten crucible is poured into the furnace, which solidifies the crucible upward from the bottom. The top of the crucible was cut off and the remaining crucible was melted in a GT-DSS 240 furnace to obtain a directional solidified crucible.
熔解950 lb的40%冶金矽及60%初生鋁混合物及 在熔爐中加熱至975℃。浮渣由熔化物表面撇去。降低溫度至950℃且85% N2及15% Cl2氣體以一旋轉除氣器在3小時內注入熔融混合物中，接著注入100% N2氣體15分鐘。加熱混合物至975℃及浮渣由熔化物表面撇去浮渣。熔融混合物被倒入新熔爐及溫度在8小時期間降低至750℃。熔融母液接著倒出熔爐，且殘留的矽晶體/薄片耙出熔爐。此已生長之薄片接著置於8wt% HCl+水的溶液中且在72小時此薄片溶去鋁。薄片接著由酸過濾並乾燥。乾燥之薄片接著在熔爐中熔融。一旦熔融，經由一吹管在3小時期間注入99.5% O2至熔融的矽中。浮渣或熔渣由熔爐撇去且熔融的矽倒入熔爐中，其由底部向上方向性固化該矽。切除矽錠頂部並及在GT-DSS240熔爐中熔融殘餘的矽以得方向性固化的矽。生成之多晶矽具有硼量為1.2-1.8ppmw及介於0.5-2.0ppmw間之P與低於1ppmw之其他金屬，其係以GDMS測量。 Melt 950 lb of 40% metallurgical crucible and 60% primary aluminum mixture and heat to 975 ° C in a furnace. The scum is removed from the surface of the melt. The temperature was lowered to 950 ° C and 85% N 2 and 15% Cl 2 gas was injected into the molten mixture in a rotary degasser for 3 hours, followed by injection of 100% N 2 gas for 15 minutes. The mixture was heated to 975 ° C and the scum was degreased from the surface of the melt. The molten mixture was poured into a new furnace and the temperature was lowered to 750 ° C during 8 hours. The molten mother liquor is then poured out of the furnace and the remaining ruthenium crystals/sheets are thrown out of the furnace. This grown sheet was then placed in a solution of 8 wt% HCl + water and the sheet was stripped of aluminum at 72 hours. The flakes are then filtered through an acid and dried. The dried flakes are then melted in a furnace. Once molten, 99.5% O 2 was injected into the molten crucible over a period of 3 hours via a blow tube. The scum or slag is removed from the furnace and the molten crucible is poured into the furnace, which solidifies the crucible upward from the bottom. The top of the crucible was cut and the remaining crucible was melted in a GT-DSS 240 furnace to obtain a directional solidified crucible. The resulting polycrystalline germanium has a boron content of 1.2-1.8 ppmw and a P between 0.5-2.0 ppmw and less than 1 ppmw of other metals, as measured by GDMS.
熔解950 lb的30%冶金矽及70%初生鋁混合物及在熔爐中加熱至850℃。使用鈦鋁母合金合金將1 lb鈦及1 lb鋯加進熔化物。浮渣由熔化物表面撇去。降低溫度至800℃且95% N2及5% Cl2氣體以一旋轉除氣器在4小時內注入熔融混合物中，接著注入100% N2氣體15分鐘。浮渣由熔化物表面撇去。將熔融混合物經陶瓷泡沫體濾器倒進新熔爐且溫度在8小時期間降低至690℃。熔融母液接著倒出熔爐，且殘留的矽晶體/薄片耙出熔爐。此已生長之薄片接著置於8wt% HCl+水的溶液中且在48小時此薄片溶去鋁。薄片 接著由酸過濾並乾燥。乾燥之薄片接著在熔爐中熔融。一旦熔融，經由一吹管在3小時期間注入99.5% O2至熔融的矽中。浮渣或熔渣由熔爐撇去且熔融的矽經陶瓷泡沫體濾器倒入熔爐中，其由底部向上方向性固化該矽。矽錠斷裂成塊且移除最後凝結的矽。 Melt 950 lb of 30% metallurgical crucible and 70% primary aluminum mixture and heat to 850 ° C in a furnace. 1 lb of titanium and 1 lb of zirconium were added to the melt using a titanium aluminum master alloy. The scum is removed from the surface of the melt. The temperature was lowered to 800 ° C and 95% N 2 and 5% Cl 2 gas was injected into the molten mixture in a rotary degasser for 4 hours, followed by injection of 100% N 2 gas for 15 minutes. The scum is removed from the surface of the melt. The molten mixture was poured into a new furnace through a ceramic foam filter and the temperature was lowered to 690 °C during 8 hours. The molten mother liquor is then poured out of the furnace and the remaining ruthenium crystals/sheets are thrown out of the furnace. This grown sheet was then placed in a solution of 8 wt% HCl + water and the sheet was stripped of aluminum at 48 hours. The flakes are then filtered through an acid and dried. The dried flakes are then melted in a furnace. Once molten, 99.5% O 2 was injected into the molten crucible over a period of 3 hours via a blow tube. The dross or slag is removed from the furnace and the molten crucible is poured into the furnace via a ceramic foam filter which solidifies the crucible upwardly from the bottom. The ingot is broken into pieces and the last coagulated crucible is removed.
冶金級矽在熔爐中熔融且一Ar、H2O及H2氣體混合物在3小時經由一吹管注入熔融矽中。接著加入鋁以達一40%冶金矽及60%初生鋁之組合物並在熔爐中加熱至975℃。浮渣由熔化物表面撇去。降低溫度至950℃且85% N2及15% Cl2氣體以一旋轉除氣器在3小時內注入熔融混合物中，接著注入100% N2氣體15分鐘。加熱混合物至975℃及由熔化物表面撇去浮渣。將熔融混合物倒進新熔爐及溫度在8小時期間降低至750℃。熔融母液接著倒出熔爐，且殘留的矽晶體/薄片耙出熔爐。此已生長之薄片接著置於8wt% HCl+水的溶液中且在48小時此薄片溶去鋁。薄片接著由酸過濾並乾燥。乾燥之薄片接著在熔爐中熔融。一旦熔融，經由一吹管在3小時期間注入99.5% O2至熔融的矽中。在氣體注入期間將SiO2、Na2SiO3、及CaO組成的熔渣加至熔融矽的表面。熔渣經在熔融矽中的感應熔爐電流拉至表面下。一旦熔融，經由一吹管在3小時期間注入99.5% O2至熔融的矽中。切除矽錠頂部，且殘餘的矽熔融並倒回至方向性固化作用的熔爐中並再次由底部向上方向性固化矽。接著切除頂部。 The metallurgical grade crucible was melted in a furnace and a mixture of Ar, H 2 O and H 2 gases was injected into the molten crucible via a blow tube for 3 hours. Aluminum was then added to a composition of 40% metallurgical tantalum and 60% primary aluminum and heated to 975 ° C in a furnace. The scum is removed from the surface of the melt. The temperature was lowered to 950 ° C and 85% N 2 and 15% Cl 2 gas was injected into the molten mixture in a rotary degasser for 3 hours, followed by injection of 100% N 2 gas for 15 minutes. The mixture was heated to 975 ° C and the scum was removed from the surface of the melt. The molten mixture was poured into a new furnace and the temperature was lowered to 750 ° C during 8 hours. The molten mother liquor is then poured out of the furnace and the remaining ruthenium crystals/sheets are thrown out of the furnace. This grown sheet was then placed in a solution of 8 wt% HCl + water and the sheet was stripped of aluminum at 48 hours. The flakes are then filtered through an acid and dried. The dried flakes are then melted in a furnace. Once molten, 99.5% O 2 was injected into the molten crucible over a period of 3 hours via a blow tube. A slag composed of SiO 2 , Na 2 SiO 3 , and CaO is added to the surface of the molten crucible during gas injection. The slag is drawn under the surface by an induction furnace current in the melting crucible. Once molten, 99.5% O 2 was injected into the molten crucible over a period of 3 hours via a blow tube. The top of the crucible is cut off and the remaining crucible is melted and poured back into the furnace for directional solidification and the crucible is solidified again upward from the bottom. Then cut off the top.
熔解950 lb的40%冶金矽及60%初生鋁混合物及在熔爐中加熱至975℃。浮渣由熔化物表面撇去。降低溫度至950℃且85% N2及15% Cl2氣體以一旋轉除氣器在3小時內注入熔融混合物中，接著注入100% N2氣體15分鐘。加熱混合物至975℃及浮渣由熔化物表面撇去浮渣。熔融混合物被倒入新熔爐及溫度在8小時期間降低至750℃。熔融母液接著由熔爐倒出至第二熔爐。將殘留的矽晶體/薄片耙出第一熔爐。在第二熔爐中的母液冷卻至650℃並接著將第二母液倒出且薄片/晶體由第二熔爐耙出。此增加薄片的量，其可由一加熱達成。此長成的薄片置於8wt% HCl+水的溶液中且在48小時此薄片溶去鋁。薄片接著由酸過濾並乾燥。乾燥之薄片接著在熔爐中熔融。一旦熔融，經由一吹管在4小時期間注入空氣至熔融的矽中。浮渣或熔渣由熔爐撇去且熔融的矽倒入熔爐中，其由底部向上方向性固化該矽。切除矽錠頂部並及在GT Solar DSS240熔爐中熔融殘餘的矽以得方向性固化的矽。 Melt 950 lb of 40% metallurgical crucible and 60% primary aluminum mixture and heat to 975 ° C in a furnace. The scum is removed from the surface of the melt. The temperature was lowered to 950 ° C and 85% N 2 and 15% Cl 2 gas was injected into the molten mixture in a rotary degasser for 3 hours, followed by injection of 100% N 2 gas for 15 minutes. The mixture was heated to 975 ° C and the scum was degreased from the surface of the melt. The molten mixture was poured into a new furnace and the temperature was lowered to 750 ° C during 8 hours. The molten mother liquor is then poured from the furnace to the second furnace. The remaining ruthenium crystals/sheets are taken out of the first furnace. The mother liquor in the second furnace was cooled to 650 ° C and then the second mother liquor was poured out and the flakes/crystals were scooped out of the second furnace. This increases the amount of flakes which can be achieved by a heat. This grown sheet was placed in a solution of 8 wt% HCl + water and the sheet was stripped of aluminum at 48 hours. The flakes are then filtered through an acid and dried. The dried flakes are then melted in a furnace. Once molten, air was injected into the molten crucible during a 4 hour period via a blow tube. The scum or slag is removed from the furnace and the molten crucible is poured into the furnace, which solidifies the crucible upward from the bottom. The top of the crucible was cut and the remaining crucible was melted in a GT Solar DSS 240 furnace to obtain a directional solidified crucible.
1.一種純化矽之方法，該方法包括：(a)由原料矽及選自於銅、錫、鋅、銻、銀、鉍、鋁、鎘、鎵、銦、鎂、鉛、其合金、及其組合之群組的溶劑金屬形成第一熔融液體；(b)將第一熔融液體與一第一氣體接觸，以提供浮渣及一第二熔融液體； (c)分離浮渣及第二熔融液體；(d)冷卻第二熔融液體以形成第一矽晶體及第一母液；(e)分離第一矽晶體及第一母液；(f)將第一矽晶體與可溶解溶劑金屬的酸、鹼、醇或化學品接觸，以提供清洗過的矽晶體及使用過的酸；及(g)分離清洗過的矽晶體及使用過的酸。 A method for purifying a crucible, the method comprising: (a) from a raw material and selected from the group consisting of copper, tin, zinc, antimony, silver, antimony, aluminum, cadmium, gallium, indium, magnesium, lead, alloys thereof, and a solvent group of the combined group forming a first molten liquid; (b) contacting the first molten liquid with a first gas to provide dross and a second molten liquid; (c) separating the scum and the second molten liquid; (d) cooling the second molten liquid to form the first ruthenium crystal and the first mother liquid; (e) separating the first ruthenium crystal and the first mother liquid; (f) first The ruthenium crystal is contacted with an acid, a base, an alcohol or a chemical which dissolves the solvent metal to provide cleaned ruthenium crystals and used acid; and (g) separates the cleaned ruthenium crystals and used acid.
2.如實施例1之方法，其更包含在形成第一熔融液體前，藉由渣化、氣體注入、電漿火炬、真空處理、或其組合預處理原料矽。 2. The method of embodiment 1, further comprising pretreating the raw material crucible by slag, gas injection, plasma torch, vacuum treatment, or a combination thereof prior to forming the first molten liquid.
3.如實施例1之方法，其更包含在形成第一熔融液體前，添加鈦(Ti)、釩(V)、鉻(Cr)、鋯(Zr)、鈣(Ca)、鉿(Hf)、鎂(Mg)、鍶(Sr)或其等之組合至原料矽中。 3. The method of embodiment 1, further comprising adding titanium (Ti), vanadium (V), chromium (Cr), zirconium (Zr), calcium (Ca), hafnium (Hf) prior to forming the first molten liquid. A combination of magnesium (Mg), strontium (Sr) or the like is added to the raw material mash.
4.如實施例1之方法，其中與第一氣體接觸以提供小氣泡。 4. The method of embodiment 1, wherein contacting the first gas to provide small bubbles.
5.如實施例1之方法，其更包含過濾第二熔融液體。 5. The method of embodiment 1, further comprising filtering the second molten liquid.
6.如實施例1之方法，其中在步驟(a)中，第一熔融液體藉由加熱至高於液相線溫度之温度而形成。 6. The method of embodiment 1, wherein in step (a), the first molten liquid is formed by heating to a temperature above the liquidus temperature.
7.如實施例1之方法，其中在步驟(a)中，使用具有磷量低於60ppmw及硼量低於15ppmw之冶金級矽。 7. The method of embodiment 1, wherein in step (a), a metallurgical grade ruthenium having a phosphorus content of less than 60 ppmw and a boron content of less than 15 ppmw is used.
8.如實施例1之方法，其中在步驟(a)中，矽使用量為約20wt.%至約60wt.%。 8. The method of embodiment 1, wherein in step (a), the amount of rhodium used is from about 20 wt.% to about 60 wt.%.
9.如實施例1之方法，其中在步驟(a)中，使用約40wt.%至約80wt.%鋁或其合金為溶劑金屬。 9. The method of embodiment 1, wherein in step (a), from about 40 wt.% to about 80 wt.% aluminum or an alloy thereof is used as the solvent metal.
10.如實施例1之方法，其中實施步驟(b)時同時攪動第一熔融液體。 10. The method of embodiment 1, wherein the step (b) is carried out while agitating the first molten liquid.
11.如實施例1之方法，其更包含步驟(b)使用一旋轉除氣器實施。 11. The method of embodiment 1, further comprising the step (b) of using a rotary degasser.
12.如實施例1之方法，其更包含在步驟(a)之後及在步驟(b)之前，冷卻第一熔融液體至低於液相線溫度。 12. The method of embodiment 1, further comprising cooling the first molten liquid to below the liquidus temperature after step (a) and prior to step (b).
13.如實施例1之方法，其中在步驟(a)之後及在步驟(b)之前，冷卻第一熔融液體至稍微高於液相線溫度。 13. The method of embodiment 1, wherein after step (a) and prior to step (b), the first molten liquid is cooled to a temperature slightly above the liquidus.
14.如實施例1之方法，其中在步驟(c)中，浮渣由第二熔融液體表面移除。 14. The method of embodiment 1, wherein in step (c), the dross is removed from the surface of the second molten liquid.
15.如實施例1之方法，其中在步驟(c)之後，第二熔融液體轉移至第二容器。 15. The method of embodiment 1, wherein after step (c), the second molten liquid is transferred to the second vessel.
16.如實施例1之方法，其中在步驟(d)中，冷卻第二熔融液體至高於固相線溫度並低於及液相線溫度。 16. The method of embodiment 1, wherein in step (d), the second molten liquid is cooled to above the solidus temperature and below the liquidus temperature.
17.如實施例1之方法，其中實施步驟(d)時同時攪動第二熔融液體。 17. The method of embodiment 1, wherein the second molten liquid is simultaneously agitated while performing step (d).
18.如實施例1之方法，其中步驟(e)藉由第一矽晶體傾倒第一母液而實施。 18. The method of embodiment 1, wherein step (e) is carried out by pouring the first mother liquor into the first cerium crystal.
19.如實施例1之方法，其中在步驟(e)之後及在步驟(f)之前，重複步驟(a)-(e)。 19. The method of embodiment 1, wherein steps (a)-(e) are repeated after step (e) and before step (f).
20.如實施例1之方法，其中在步驟(e)之後及在步驟(f)之前，重複步驟(a)、(c)、(d)及(e)。 20. The method of embodiment 1, wherein steps (a), (c), (d), and (e) are repeated after step (e) and before step (f).
21.如實施例1之方法，其中在步驟(g)的分離使用一濾器實施。 21. The method of embodiment 1, wherein the separating in step (g) is carried out using a filter.
22.如實施例1之方法，其中步驟(a)-(g)之至少一者進行多次。 22. The method of embodiment 1, wherein at least one of steps (a) - (g) is performed multiple times.
23.如實施例1之方法，其步驟(a)-(g)之每一者獨立進行多次。 23. The method of embodiment 1, wherein each of steps (a)-(g) is performed independently of a plurality of times.
24.如實施例1之方法，其中第一矽晶體包括約85wt.%至約98wt.%的矽。 24. The method of embodiment 1, wherein the first ruthenium crystal comprises from about 85 wt.% to about 98 wt.% ruthenium.
25.如實施例1之方法，其中清洗過的矽晶體包括約800ppm(wt.)至約2,000ppm(wt)的鋁(Al)。 25. The method of embodiment 1, wherein the washed ruthenium crystal comprises from about 800 ppm (wt.) to about 2,000 ppm (wt) aluminum (Al).
26.如實施例1至25任一者之方法，其中矽由鋰(Li)、硼(B)、鈉(Na)、鈦(Ti)、鐵(Fe)、鎂(Mg)、釩(V)、鋅(Zn)、磷(P)、硫(S)、鉀(K)、鈣(Ca)、鍶(Sr)、氯(Cl)、鉻(Cr)、錳(Mn)、鋁(Al)、砷(As)、銻(Sb)、鎵(Ga)、銦(In)、鎳(Ni)及銅(Cu)之至少一者純化。 26. The method of any one of embodiments 1 to 25, wherein the lanthanum is composed of lithium (Li), boron (B), sodium (Na), titanium (Ti), iron (Fe), magnesium (Mg), vanadium (V) ), zinc (Zn), phosphorus (P), sulfur (S), potassium (K), calcium (Ca), strontium (Sr), chlorine (Cl), chromium (Cr), manganese (Mn), aluminum (Al At least one of arsenic (As), antimony (Sb), gallium (Ga), indium (In), nickel (Ni), and copper (Cu) is purified.
27.如實施例1之方法，其中清洗過的矽晶體包括少於約9ppm(wt)的磷(P)及少於約3ppm(wt)的硼(B)。 27. The method of embodiment 1, wherein the washed ruthenium crystals comprise less than about 9 ppm by weight phosphorus (P) and less than about 3 ppm (wt) boron (B).
28.如實施例18至19任一者之方法，其中清洗過的矽晶體包括少於約4ppm(wt)的磷(P)及少於約2ppm(wt)的硼(B)。 The method of any one of embodiments 18 to 19, wherein the washed ruthenium crystals comprise less than about 4 ppm by weight of phosphorus (P) and less than about 2 ppm by weight of boron (B).
29.如實施例1至28任一者之方法，其中可獲得至少約100公噸/年清洗過的矽晶體。 29. The method of any of embodiments 1 to 28, wherein at least about 100 metric tons per year of washed cerium crystals are obtained.
30.如實施例1至29任一者之方法，其中該方法少於約24小時下實施。 The method of any one of embodiments 1 to 29, wherein the method is carried out in less than about 24 hours.
31.如實施例1之方法，其更包含處理清洗過的晶體以能充分提供太陽能電池、太陽能板、晶圓或積體電路。 31. The method of embodiment 1, further comprising treating the cleaned crystal to provide sufficient solar cell, solar panel, wafer or integrated circuitry.
32.如實施例31之方法，其中該處理該清洗過的矽晶體的步驟包含至少一：(a)真空處理，(b)熔渣處理，(c)氣體注入，以至少一氧、水、氫及氬；(d)方向性固化，及(e)使用清洗過的矽晶體為用於矽烷/Siemen氣體製程的原材料。 32. The method of embodiment 31, wherein the step of treating the cleaned germanium crystal comprises at least one of: (a) vacuum processing, (b) slag treatment, (c) gas injection, at least one oxygen, water, Hydrogen and argon; (d) directional solidification, and (e) use of cleaned ruthenium crystals as starting materials for the decane/Siemen gas process.
33.如實施例1至32任一者之方法，其更包含純化該清洗過的矽晶體以提供太陽能級矽，其可與其他矽混合以提供太陽能板級矽。 33. The method of any of embodiments 1 to 32, further comprising purifying the cleaned ruthenium crystal to provide a solar grade ruthenium that can be mixed with other ruthenium to provide solar panel grade ruthenium.
34.一種純化矽的方法矽，該方法包括：(a)由原料矽及一溶劑金屬形成第一熔融液體，該溶劑金屬為選自銅、錫、鋅、銻、銀、鉍、鋁、鎘、鎵、銦、鎂、鉿、其合金、及其組合；(b)冷卻第一熔融液體以形成第一矽晶體及第一母液；(c)分離第一矽晶體及第一母液；(d)將第一矽晶體與可溶解溶劑金屬的酸、鹼、醇或化學品接觸，以提供清洗過的矽晶體及使用過的酸；及(e)分離清洗過的矽晶體及使用過的酸。 34. A method of purifying hydrazine, the method comprising: (a) forming a first molten liquid from a raw material cerium and a solvent metal selected from the group consisting of copper, tin, zinc, antimony, silver, antimony, aluminum, and cadmium. , gallium, indium, magnesium, strontium, alloys thereof, and combinations thereof; (b) cooling the first molten liquid to form the first cerium crystal and the first mother liquid; (c) separating the first cerium crystal and the first mother liquid; Contacting the first ruthenium crystal with an acid, base, alcohol or chemical that dissolves the solvent metal to provide cleaned ruthenium crystals and used acid; and (e) separating the cleaned ruthenium crystals and used acid .
35.如實施例34之方法，其中在步驟(a)中，藉由高於液相線溫度之加熱以形成第一熔融液體。 35. The method of embodiment 34, wherein in step (a), the first molten liquid is formed by heating above a liquidus temperature.
36.如實施例34之方法，其中在步驟(a)中，使用冶金級矽，其具有磷量為低於60ppmw及硼量為低於15 ppmw。 36. The method of embodiment 34, wherein in step (a), a metallurgical grader having a phosphorus content of less than 60 ppmw and a boron amount of less than 15 is used. Ppmw.
37.如實施例34之方法，其中在步驟(a)中，矽的使用量為在約20wt.%至約60wt.%間。 37. The method of embodiment 34, wherein in step (a), the amount of rhodium used is between about 20 wt.% and about 60 wt.%.
38.如實施例34之方法，其中在步驟(a)中，使用鋁或其合金為溶劑金屬且使用量為約40wt.%至約80wt.%。 38. The method of embodiment 34, wherein in step (a), aluminum or an alloy thereof is used as the solvent metal and is used in an amount from about 40 wt.% to about 80 wt.%.
39.如實施例34之方法，其中在步驟(b)中，冷卻第二熔融液體至稍微高於固相線溫度及低於液相線溫度。 39. The method of embodiment 34, wherein in step (b), the second molten liquid is cooled to a temperature slightly above the solidus temperature and below the liquidus temperature.
40.如實施例34之方法，其中步驟(c)藉由自第一矽晶體傾倒第一母液而實施。 40. The method of embodiment 34, wherein step (c) is carried out by pouring the first mother liquor from the first cerium crystal.
41.如實施例34之方法，其中鋁與第一矽晶體接觸，及熔融以提供後續之第二熔融液體。 41. The method of embodiment 34 wherein the aluminum is contacted with the first tantalum crystal and melted to provide a subsequent second molten liquid.
42.如實施例34之方法，其中在步驟(e)的分離步驟使用一濾器實施。 42. The method of embodiment 34 wherein the separating step of step (e) is carried out using a filter.
43.如實施例34之方法，其中步驟(a)-(e)之至少一者進行多次。 43. The method of embodiment 34, wherein at least one of steps (a)-(e) is performed multiple times.
44.如實施例34之方法，其步驟(a)-(e)之每一者獨立進行多次。 44. The method of embodiment 34, wherein each of steps (a)-(e) is performed multiple times independently.
45.如實施例34之方法，其中第一矽晶體包括約85wt.%至約99wt.%的矽。 45. The method of embodiment 34, wherein the first ruthenium crystal comprises from about 85 wt.% to about 99 wt.% ruthenium.
46.如實施例34之方法，其中清洗過的矽晶體包括約500ppm(wt.)至約2,000ppm(wt)的鋁(Al)。 46. The method of embodiment 34, wherein the washed ruthenium crystals comprise from about 500 ppm (wt.) to about 2,000 ppm (wt) aluminum (Al).
47.如實施例1至46任一者之方法，其中矽由鋰(Li)、硼(B)、鈉(Na)、鈦(Ti)、鐵(Fe)、鎂(Mg)、釩(V)、鋅 (Zn)、磷(P)、硫(S)、鉀(K)、鈣(Ca)、鍶(Sr)、氯(Cl)、鉻(Cr)、錳(Mn)、鋁(Al)、砷(As)、銻(Sb)、鎵(Ga)、銦(In)、鎳(Ni)及銅(Cu)之至少之一者純化。 47. The method of any of embodiments 1 to 46, wherein the ruthenium consists of lithium (Li), boron (B), sodium (Na), titanium (Ti), iron (Fe), magnesium (Mg), vanadium (V) ), zinc (Zn), phosphorus (P), sulfur (S), potassium (K), calcium (Ca), strontium (Sr), chlorine (Cl), chromium (Cr), manganese (Mn), aluminum (Al), arsenic Purification of at least one of (As), bismuth (Sb), gallium (Ga), indium (In), nickel (Ni), and copper (Cu).
48.如實施例34之方法，其中清洗過的矽包括少於約15ppm(wt)的磷(P)及少於約5ppm(wt)的硼(B)。 48. The method of embodiment 34, wherein the washed ruthenium comprises less than about 15 ppm (wt) phosphorus (P) and less than about 5 ppm (wt) boron (B).
49.如實施例1至48任一者之方法，其中獲得至少約100公噸/年之清洗過的矽晶體。 49. The method of any of embodiments 1 to 48, wherein at least about 100 metric tons per year of washed cerium crystals are obtained.
50.如實施例1至49任一者之方法，其中該方法在少於約24小時內實施。 50. The method of any one of embodiments 1 to 49, wherein the method is carried out in less than about 24 hours.
51.如實施例34至50任一者之方法，其更包含純化該清洗過的矽晶體以提供太陽能級矽，其可與其他矽混合以提供太陽能板級矽。 51. The method of any of embodiments 34 to 50, further comprising purifying the cleaned ruthenium crystal to provide a solar grade ruthenium that can be mixed with other ruthenium to provide solar panel grade ruthenium.
52.如實施例1至51任一者之方法，其更包含純化該清洗過的矽晶體以提供太陽能級矽，其可與其他矽混合以提供太陽能板級矽。 52. The method of any of embodiments 1 to 51, further comprising purifying the cleaned ruthenium crystal to provide a solar grade ruthenium that can be mixed with other ruthenium to provide solar panel grade ruthenium.
53.如實施例52之方法，其中純化清洗過的矽晶體以提供太陽能級矽，其包含下列至少一者：(a)真空處理，(b)熔渣處理，(c)以至少一氧、水、氫或氬之氣體注入；(d)方向性固化，及(e)使用清洗過的矽晶體為用於矽烷/Siemen氣體製程的原材料。 53. The method of embodiment 52, wherein the cleaned ruthenium crystals are purified to provide a solar grade ruthenium comprising at least one of: (a) vacuum treatment, (b) slag treatment, (c) at least one oxygen, Gas, hydrogen or argon gas injection; (d) directional solidification, and (e) use of cleaned ruthenium crystals as raw materials for the decane/Siemen gas process.
54.一種純化矽的方法矽，該方法包括： (a)從原料矽及鋁形成第一熔融液體(b)將第一熔融液體與第一氣體接觸，以提供浮渣及第二熔融液體；(c)分離浮渣及第二熔融液體；(d)冷卻第二熔融液體以形成第一矽晶體及第一母液；(e)分離第一矽晶體及第一母液；(f)可選擇地以與溶劑金屬熔融第一矽晶體並重複步驟(a)-(e)；(g)將第一矽晶體與可溶解溶劑金屬的酸、鹼、醇或化學品接觸，以提供清洗過的矽晶體及使用過的酸；及(h)分離清洗過的矽晶體及使用過的酸，其足以提供純化矽晶體；(i)熔融純化矽晶體，其足以提供一矽熔融物；(j)將矽熔融物與第二氣體接觸；及(k)方向性固化矽熔融物。 54. A method of purifying hydrazine, the method comprising: (a) forming a first molten liquid from the raw material bismuth and aluminum (b) contacting the first molten liquid with the first gas to provide scum and a second molten liquid; (c) separating the scum and the second molten liquid; d) cooling the second molten liquid to form the first tantalum crystal and the first mother liquid; (e) separating the first tantalum crystal and the first mother liquid; (f) optionally melting the first tantalum crystal with the solvent metal and repeating the step ( a)-(e); (g) contacting the first ruthenium crystal with an acid, a base, an alcohol or a chemical that dissolves the solvent metal to provide washed ruthenium crystals and used acid; and (h) separating and cleaning The ruthenium crystal and the used acid are sufficient to provide purified ruthenium crystals; (i) melt-purify the ruthenium crystals sufficient to provide a ruthenium melt; (j) contact the ruthenium melt with the second gas; and (k) Directionally solidified 矽 melt.
55.如實施例54之方法，其中產生一錠。 55. The method of embodiment 54, wherein one ingot is produced.
56.如實施例55之方法，其更包含除去錠的頂部。 56. The method of embodiment 55, further comprising removing the top of the ingot.
57.如實施例56之方法，其中該去除包含傾一部份熔融錠的頂部。 57. The method of embodiment 56 wherein the removing comprises topping a portion of the molten ingot.
58.如實施例55之方法，其更包含方向性固化錠或梨晶，其足以形成多晶錠或單晶梨晶。 58. The method of embodiment 55, further comprising a directional solidified ingot or pear crystal sufficient to form a polycrystalline ingot or a single crystal pear crystal.
59.如實施例54之方法，其中該第二氣體包含氧或氧及一鈍氣之混合物。 59. The method of embodiment 54, wherein the second gas comprises a mixture of oxygen or oxygen and an inert gas.
60.如實施例54之方法，其中該第一氣體包含氯或氯及一鈍氣之混合物。 60. The method of embodiment 54, wherein the first gas comprises a mixture of chlorine or chlorine and a blunt gas.
61.如實施例1之方法，其更包含過濾第二熔融液體。 61. The method of embodiment 1, further comprising filtering the second molten liquid.
62.如實施例54之方法，其更包含過濾矽熔融物。 62. The method of embodiment 54, further comprising filtering the cerium melt.
本發明所描述之方法可以任何熟於化學、治金及材料科學技術領域人士所知的應用技術實施。 The methods described herein can be practiced in any application technology known to those skilled in the art of chemistry, metallurgy, and materials science.
所有的文獻、專利及專利申請案為併入本案做為參考。雖然在前述說明書中已以特定本發明之較佳實施例清楚描述本發明，且為說明之目的已詳述許多細節，熟於此技人士可瞭解本發明易於完成其他的實施例且其等在本說明書中描述的細節可在未偏離本發明技術思想下變化。 All documents, patents and patent applications are incorporated herein by reference. Although the present invention has been described in detail with reference to the preferred embodiments of the preferred embodiments of the invention, The details described in the specification can be changed without departing from the technical idea of the invention.
102‧‧‧原料矽 102‧‧‧ Raw materials矽
103‧‧‧溶劑金屬 103‧‧‧Solvent metal
104‧‧‧第一熔融液體 104‧‧‧First molten liquid
106‧‧‧第一氣體 106‧‧‧First gas
108‧‧‧第二熔融液體 108‧‧‧Second molten liquid
110‧‧‧浮渣 110‧‧‧ scum
112‧‧‧冷卻 112‧‧‧cooling
114‧‧‧第一矽晶體 114‧‧‧First crystal
116‧‧‧第一母液 116‧‧‧First mother liquor
117‧‧‧再使用(可選擇) 117‧‧‧Re-use (optional)
119‧‧‧可溶解鋁(Al)之酸、鹼、醇或化學品 119‧‧‧Solubility of aluminum (Al) acids, bases, alcohols or chemicals
121‧‧‧沖洗過之矽晶體 121‧‧‧ rinsed crystals
123‧‧‧使用過的酸 123‧‧‧Used acid
125‧‧‧分離 125‧‧‧Separation
127‧‧‧純化矽晶體 127‧‧‧ Purified 矽 crystal
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