200921924 九、發明說明： t發明所屬之技術領域3 發明領域 大致上本發明係關於光伏打電池領域及關於用於製造 5光伏打電池用途之鑄態矽之方法及裝置。本發明進—步係 關於可用於製造元件諸如光伏打電池及其它半導體元件之 新穎形式之鑄態矽。新穎矽具有單晶、近單晶、或雙晶結 構’可經由利用種晶之鑄造方法製造。 L先前技術3 10 發明背景 15 20 光伏打電池將光轉換成電流。光伏打電池最重要的測 量值之-為其將光能轉成電能的效率。雖然光伏打電也可 由多種半導體材料製造，但-般使用石夕，原因在於石夕容易 以合理價格取得，以及原因在於石夕具有用於製造光伏打電 池之電氣、物理及化學性質間之適當平衡。 於用於製造光伏打電池之 於誘導正性或負性導電類型之㈣料料混合用 從溶解區段拉出W ^ 摻雜劑），溶解然後藉 攸祕^拉H切心單晶 ^(Czoch^) ^ θ 石夕晶粒之晶粒大小而定，鎮、生〇 〇日日化，或依據個別 「晶碑」。於前述程序中，多晶石夕或複晶較鱗塊或 或镇塊切割成為薄基材，也^刀割或鑛割方法將鑄錠 被加工成光伏打電池。稱作4晶圓。‘然後此等晶圓可 用於製造光伏打電池之單晶料常係藉CZ法或FZ法 5 200921924 5 10 15 製造，一者為其中製造圓柱形結晶矽胚晶之方法。用於 法，胚晶由熔融矽之池中緩慢拉出。至於Fz&，固體材料 進給通過熔解區段，於熔解區段之另一側上再度固化。轉 此方式所製造之單晶矽胚晶含有雜質及缺陷之徑向分布， 諸如氧感應疊差缺陷（〇 S f )環及間隙簇晶或空位簇晶之「塽 渦」效應。即使存在有此等雜質及缺陷，單晶矽由於可用 於製造咼效率太陽能電池，故單晶矽通常為用於製造光伏 打電池之較财來源。但單㈣製造上比使用習知技術諸 如前述技術製造習知多晶矽之成本更昂貴。 習知用於製造光伏打電池之多晶石夕通常係藉鑄造方法 製造。用於製造習知多㈣之#造方法為光伏打技術業界 所已知。簡言之’於此等方法中，㈣石夕係容納於㈣諸 如石英㈣，以經控H切卻來允許其中所含之石夕結 晶化。結果所得多晶料塊通㈣切成具有截面約略等於 用來製造光傭電池之㈣尺寸L晶雜過鑛割或 以其它方式切割成為晶圓。藉此方式所製造 粒之黏聚體，此處，由此所製成之晶圓，晶粒相對於彼此 可有效隨機定向。 以 於習知多㈣或複⑽中，晶粒之隨就向造成難 20織構所得晶圓表面。織構經由減少光反射與改良通過電池 表面之光能吸收，用來改良办 又艮先伙打電池效率。此外，形成 於習知多Μ之晶粒間邊界的「紐結」容易錢晶或差排 線形式孕核結構缺陷。此等差排以及差排容易吸引的雜質 相信係造成由習知多㈣所製成之功能⑽伏打電池的電 200921924 快速復合的原因。可能造成電池效率的降低。由此 日日石夕所製成之光伏打電池通常具有比較由單晶石夕所製 造的相當的光伏打電池更低的效率，即使考慮於藉已知技 術所製造之單晶石夕中存在的缺陷之徑向分布亦如此。但因 5習知夕曰曰石夕之製造上相對簡單且製造成本較低，以及於電 池加工上缺陷的有效鈍化，故多晶石夕為用於製造光伏打電 池之較為廣泛使用之矽形式。 右干先前製造技術涉及使用供晶體成長的「冷壁」坩 禍。「冷壁」—詞係指存在於_上或㈣内之感應線 10圈為水冷式，也可有開槽，如此通常維持低於刚。d禍 壁可位在線圈與進料間之緊密附近。掛瑪壁之材料並非特 別絕熱，因此維持於已冷卻線圈間的熱平衡。因此於來自 掛禍壁之輕射無法預測石夕的加熱，原因在於於掛瑪中石夕的 感應熱表样係由被錢·而於㈣流動的電流所直接加 15熱。藉此方式，掛禍壁維持低於石夕溶點，故掛瑪壁被視為 熔融石夕更冷」。於感應加熱炼融石夕固化期間，冷掛堝壁 係用作為散熱座。鑄旋快速冷卻’判定係藉熱韓射至冷壁 之故。因此，初固化鋒快速變成實質上彎曲，於鑄鍵側邊 出現晶體孕核，朝向鑄鍵中心以對角線方向成長，破壞任 20何嘗式維持垂直且幾何上有序的種晶程序或實質上平坦之 固化鋒。 【聲明内容】 發明概要 如此處使用，「單晶石夕」係指全面具有一致的晶體定向 7 200921924 之單晶矽本體。進一步，習知多晶矽係指具有厘米級之晶 粒大小分布，有多個隨機定向之晶體位於鑄態矽本體内部 之結晶石夕。 進一步’如此處使用，「多晶矽」一詞係指於一個給定 5之鑄態石夕本體中具有微米級之晶粒大小及多個晶粒取向之 結晶矽。例如，晶粒典型具有約次微米至次毫米之大小平 均值(例如個別晶粒可能並非肉眼可見），以及全體晶粒取向 隨機分布。 又復，如此處使用’「近單晶石夕」一詞係指結晶石夕本體， 10具有單一全體一致晶體取向大於本體之約50%體積比，此 處，此專近早晶碎包含於多晶砍旁之单晶妙本體，咬包人 大型連續之一致矽晶體，其部分或全部含有其它晶體取向 之小型矽晶體’此處小型晶體占總體積超過5〇%。較佳， 近單晶石夕含有小型晶體不超過總體積之25%。更佳，近單 15 晶矽含有小型晶體不超過總體積之10%。又更佳，近單曰 石夕含有小型晶體不超過總體積之5%。 又復如此處使用’「雙晶石夕」一詞係指具有單一全體_ 致晶體取向大於或等於本體之50°/。體積比之石夕本體，以及 另一個一致晶體取向占本體體積之差額。例如，此種雙晶 20梦可包含具有一種晶體取向之單晶石夕本體於具有不同的晶 體取向組成結晶矽體積之差額部分之另一個單晶矽本體 旁。較佳，雙晶矽於同一矽本體内含有兩個分開區域，區 域之差異只在於其晶體取向。 但如此處使用，「幾何上有序多晶矽」（後文縮寫為「幾 200921924 何多晶矽」）一詞係指具有幾何上有序厘米級晶粒大小分 布，有多個有序晶體位於一個矽本體内部之根據本發明之 實施例之結晶矽。舉例言之，於幾何多晶矽中，各個晶粒 典型具有平均截面積約0.25平方厘米至約2,500平方厘米， - 5 高度可如同矽本體，例如高度可為垂直於截面平面之矽本 _ 體之維度，於幾何多晶矽本體内部之晶粒取向係根據預定 取向控制。垂直於幾何多晶矽之晶粒高度或長度之晶粒的 截面形狀典型係與形成該晶粒之種晶或部分種晶形狀相 同。較佳，晶粒之截面形狀為多角形。較佳多角形晶粒之 10 角隅係與三個不同晶粒之接面相對應。雖然於幾何多晶矽 本體内部之各個晶粒較佳包含有單一連續一致晶體取向遍 布該晶粒之矽，但一個或多個晶粒也含有小量不同取向之 小型矽晶體。例如，各個此種晶粒部分或全部含有其它晶 體取向之小型矽晶體，此處小型晶體占晶粒總體積不超過 15 25%，較佳不超過晶粒總體積之10%及更佳不超過晶粒總體 積之5%，又更佳不超過晶粒總體積之1%，及又更佳不超過 L 晶粒總體積之0.1%。 根據如具體說明及廣義說明之本發明，提供一種製造 鑄態矽之方法，包含：將熔融矽放置於一容器内與種晶模 20 型接觸，該容器具有一個或多個側壁加熱至至少矽之熔點 及至少一壁用於冷卻，其中該模型包含多個單晶矽種晶， 此處單晶矽種晶中之一或多者係以第一晶體取向排列，其 單晶矽種晶中之一者或多者係以第二晶體取向排列；以及 形成包含單晶矽之一區視需要可有至少兩個維度各自至少 9 200921924 約為ίο厘米之一固態本體。 根據本發明之一個實施例’也提供一種製造鑄態矽之 方法，包含：將矽進料放置接觸於至少一個表面上包含單 晶矽之一矽種晶模型，其中該模型包含多個單晶矽種晶， 5此處單晶矽種晶中之一或多者係以第一晶體取向排列，其 單晶石夕種晶中之一者或多者係以第二晶體取向排列；將該 矽進料及矽種晶模型加熱至矽熔點；控制加熱，使得該矽 種日日模型不會凡全溶解，該控制包含於於財禍内部其它位 置達到矽熔點後’於坩堝外側表面上測量維持約〇 ·丨t /分鐘 10或U下之ΔΤ ;以及—旦石夕種晶模型被部分炼解，經由冷卻 Λ夕而形成包含單晶石夕之一固態本體。 根據本發明之又一實施例，也提供不含或實質上不含 向习布的雜夤及缺陷且具有至少二維度各自至少約為25 厘米及一第三維度至少約為2〇厘米之—雙晶矽本體。 15 根據本發明之又另一實施例，也提供一種雙晶矽本 體具有約2χ1016原子/立方厘米至約5χ1〇η原子/立方厘米 之石反濃度，不超過5χ1〇π原子/立方厘米之氧濃度，至少為 10原子/立方厘米之氮濃度且具有至少二維度各自至少200921924 IX. INSTRUCTIONS: TECHNICAL FIELD OF THE INVENTION The present invention relates generally to the field of photovoltaic cells and to methods and apparatus for the manufacture of as-cast bismuth for use in photovoltaic cells. The present invention is directed to an as-cast article of the novel form that can be used to fabricate components such as photovoltaic cells and other semiconductor components. The novel ruthenium having a single crystal, a near single crystal, or a twin crystal structure can be produced by a casting method using seed crystals. L Prior Art 3 10 Background of the Invention 15 20 Photovoltaic cells convert light into electricity. The most important measurement of photovoltaic cells is the efficiency of converting light energy into electrical energy. Although photovoltaic power generation can also be made from a variety of semiconductor materials, the use of Shi Xi is generally used because Shi Xi is easy to obtain at a reasonable price, and because Shi Xi has an appropriate balance between electrical, physical and chemical properties for manufacturing photovoltaic cells. . For the production of photovoltaic cells to induce positive or negative conductivity type (four) material mixing to pull out W ^ dopant from the dissolution section), dissolve and then borrow the H-cutting single crystal ^ ( Czoch^) ^ θ Depending on the grain size of the Shixi crystal, the town and the oyster are daily, or according to individual "grains". In the foregoing procedure, the polycrystalline stone or the polycrystalline crystal is cut into a thin substrate than the scale or the town block, and the ingot is processed into a photovoltaic cell by a knife cutting or ore cutting method. Called 4 wafers. ‘These wafers that can be used to make photovoltaic cells are often manufactured by CZ or FZ 5 200921924 5 10 15 , one of which is the method of making cylindrical crystal enamels. For the method, the embryonic crystals are slowly pulled out from the pool of molten crucible. As for Fz&, the solid material feed passes through the melting section and solidifies again on the other side of the melting section. The single crystal germanium blast crystal produced by this method contains a radial distribution of impurities and defects, such as an oxygen enthalpy difference (〇 S f ) ring and a gap nucleus crystal or a vacancy cluster vortex effect. Even if such impurities and defects are present, single crystal germanium is generally a more valuable source for the manufacture of photovoltaic cells because it can be used to fabricate solar cells. However, the manufacture of a single (d) is more expensive than the fabrication of conventional polysilicon using conventional techniques such as those described above. It is known that polycrystalline stone used for the manufacture of photovoltaic cells is usually manufactured by a casting method. The method for manufacturing the conventional (four) is known in the photovoltaic industry. In short, in these methods, (4) Shi Xi is housed in (4) such as quartz (4), and controlled by H-cutting to allow the crystals contained therein to crystallize. As a result, the resulting polycrystalline block is cut (4) into a wafer having a cross-section approximately equal to the size of the (4) used to fabricate the photovoltaic cell or otherwise cut into a wafer. In this way, the cohesive particles are produced, where the wafers thus produced are effectively randomly oriented relative to each other. In the conventional (4) or complex (10), the grain is caused to cause the texture of the obtained wafer surface. The texture is improved by reducing light reflection and improving the absorption of light energy through the surface of the battery, and is used to improve the efficiency of the battery. In addition, the "knot" formed in the well-defined inter-grain boundary is prone to defects in the form of fertility in the form of a crystal or a poorly arranged line. The impurities and the impurities that are easily attracted by the difference are believed to cause the function of the (10) voltaic battery made by the conventional (4). May cause a decrease in battery efficiency. Therefore, the photovoltaic cells made by the day of the day are generally less efficient than the comparable photovoltaic cells manufactured by the single crystal, even if the single crystal produced by the known technology is present. The same is true for the radial distribution of defects. However, due to the relatively simple manufacturing and low manufacturing cost of the 5 Xi Xi Xi Shi Xi, and the effective passivation of defects in battery processing, the polycrystalline stone is a more widely used form for the manufacture of photovoltaic cells. . The right-hand manufacturing technique involves the use of "cold wall" for crystal growth. "Cold wall" - the word means that the induction line existing in _ or (4) is water-cooled or slotted, so it is usually kept below. The wall can be located close to the coil and the feed. The material of the wall is not particularly insulated, so it maintains the heat balance between the cooled coils. Therefore, it is impossible to predict the heating of Shi Xi from the light shot from the wall of the disaster. The reason is that the induction heat meter of the stone in the hang of the horse is directly heated by the current flowing by the money and (4). In this way, the wall of the wall is kept below the point of the Shi Xi, so the wall is considered to be colder on the melting stone. During the induction heating of the refining stone, the cold hanging wall is used as a heat sink. The rapid cooling of the casting spin was judged by the heat of the Han to the cold wall. Therefore, the initial solidification front quickly becomes substantially curved, crystal nucleation occurs on the side of the cast bond, and grows diagonally toward the center of the cast bond, destroying any of the 20 or the geometrically ordered seeding procedures or essence. A flat curing front. [Declaration] Summary of the Invention As used herein, "single crystal" refers to a single crystal crucible body with a uniform crystal orientation of 7 200921924. Further, the conventional polycrystalline germanium refers to a crystal size distribution having a centimeter level, and a plurality of randomly oriented crystals are located on the crystallized stone inside the as-cast body. Further, as used herein, the term "polycrystalline germanium" refers to a crystalline germanium having a micron-sized grain size and a plurality of grain orientations in a given 5th as-cast body. For example, the grains typically have an average size of about a submicron to a sub-millimeter (e.g., individual grains may not be visible to the naked eye), and the overall grain orientation is randomly distributed. Further, as used herein, the term "near single crystal stone" refers to a crystalline stone body, 10 having a single uniform crystal orientation greater than about 50% by volume of the body, where the near-early crystallite is contained herein. The single crystal body of the polycrystalline chopping, biting a large continuous uniform crystal, partially or completely containing other crystal oriented small germanium crystals. Here, the small crystals account for more than 5% of the total volume. Preferably, the near-single crystal contains a small crystal of no more than 25% of the total volume. More preferably, the nearly single crystal contains less than 10% of the total volume of the small crystal. Even better, near the single 曰 Shi Xi contains small crystals not more than 5% of the total volume. As used herein, the term "double-crystallite" means having a single overall crystal orientation greater than or equal to 50°/ of the body. The volume ratio is the difference between the body of the stone and the other uniform crystal orientation. For example, such a twin crystal may comprise a single crystal body having a crystal orientation adjacent to another single crystal germanium body having a difference in crystal orientation composition crystallization volume. Preferably, the twin bismuth contains two separate regions in the same raft, the difference being only in the crystal orientation. However, as used herein, the term "geometrically ordered polycrystalline germanium" (hereinafter abbreviated as "several 200921924 He polycrystalline germanium") refers to a geometrically ordered centimeter-scale grain size distribution with multiple ordered crystals located on a single body. Internal crystallization enthalpy according to an embodiment of the invention. For example, in a geometric polysilicon, each grain typically has an average cross-sectional area of from about 0.25 square centimeters to about 2,500 square centimeters, and -5 height may be the same as the body of the crucible, for example, the height may be perpendicular to the dimension of the cross-section plane. The grain orientation inside the geometric polycrystalline body is controlled according to a predetermined orientation. The cross-sectional shape of the crystal grains perpendicular to the crystal height or length of the geometric polycrystalline silicon is typically the same as the seed crystal or partial seed crystal shape forming the crystal grains. Preferably, the cross-sectional shape of the crystal grains is polygonal. The 10 隅 of the preferred polygonal grains corresponds to the junction of three different grains. Although each of the grains within the body of the geometric polycrystalline body preferably comprises a single continuous crystal orientation throughout the grain, the one or more grains also contain small amounts of small germanium crystals of different orientations. For example, each such crystal grain partially or completely contains other crystal-oriented small germanium crystals, where the small crystals occupy no more than 15 25% of the total grain volume, preferably no more than 10% of the total volume of the crystal grains, and more preferably do not exceed The total volume of the crystal grains is 5%, more preferably not more than 1% of the total volume of the crystal grains, and more preferably not more than 0.1% of the total volume of the L crystal grains. According to the invention as specifically described and broadly described, there is provided a method of making an as-cast crucible comprising: placing a molten crucible in a container in contact with a seed mold 20 having one or more side walls heated to at least 矽The melting point and at least one wall are used for cooling, wherein the model comprises a plurality of single crystal germanium seed crystals, wherein one or more of the single crystal germanium seed crystals are arranged in a first crystal orientation, and the single crystal germanium is seed crystal One or more of the arrays are arranged in a second crystal orientation; and a solid body having at least two dimensions of at least 9 200921924 approximately ίο cm, as desired, may be formed. There is also provided, in accordance with an embodiment of the present invention, a method of making an as-cast crucible comprising: placing a crucible feed in contact with at least one surface comprising a single crystal germanium seed crystal model, wherein the mold comprises a plurality of single crystals a seed crystal, wherein one or more of the single crystal seed crystals are arranged in a first crystal orientation, and one or more of the single crystal seed crystals are arranged in a second crystal orientation; The crucible feed and the seed crystal model are heated to the melting point of the crucible; the heating is controlled so that the day-to-day model of the seed is not completely dissolved, and the control is included in the outer surface of the crucible after the other points in the interior of the financial disaster have reached the melting point of the crucible. Maintaining a ΔΤ of about 〇·丨t /min 10 or U; and the crystallization model is partially refined, and a solid body comprising a single crystal stone is formed by cooling. In accordance with yet another embodiment of the present invention, there are also provided dopants and defects that are free or substantially free of the fabric and have at least two dimensions of at least about 25 cm each and a third dimension of at least about 2 cm. Twin crystal body. According to still another embodiment of the present invention, there is also provided a bimorph body having a stone inverse concentration of about 2χ1016 atoms/cm 3 to about 5χ1〇η atoms/cm 3 , and no more than 5χ1〇π atoms/cm 3 of oxygen. a concentration of nitrogen concentration of at least 10 atoms/cm 3 and having at least two dimensions each at least
、、’勺為25厘米及一第三維度至少約為2〇厘米之一種雙晶 20 體。 I 根據本發明之又另一個實施例，也提供具有至少兩個 維度各自至少約為35厘米之一種連續鑄態單晶矽本體。 根據本發明之又另一實施例，提供一種太陽能電池， 包含：由實質上不含具有至少二維度各自至少約為25厘米 200921924 及一第三維度至少約為20厘米之一連續雙晶矽本體所製成 之一晶圓；於該晶圓中之一 p-n接面；於該晶圓之一表面上 之一任選的抗反射塗覆層；任選地，選自於一背場及一純 化層中之至少一層；以及於該晶圓上之導電接觸件。 5 根據本發明之又另一實施例，也提供一種太陽能電 池，包含：由一連續鑄態雙晶矽本體所製成之一晶圓，該 本體具有至少二維度其各自至少約為35厘米；於該晶圓中 之一p-n接面；於該晶圓之一表面上之一任選的抗反射塗覆 層；任選地，選自於一背場及一純化層中之至少一層；以 10 及於該晶圓上之導電接觸件。 根據本發明之又另一實施例，提供一種太陽能電池， 包含：由一連續鑄造雙晶矽本體所製成之一連續雙晶矽晶 圓，該晶圓具有至少一個維度其至少約為50毫米，以及該 本體具有至少二維度各自至少約為25厘米及一第三維度至 15 少約為20厘米；於該晶圓中之一p-n接面；於該晶圓之一表 面上之一任選的抗反射塗覆層；任選地，選自於一背場及 一鈍化層中之至少一層；以及於該晶圓上之導電接觸件。 根據本發明之又另一實施例，也提供一種晶圓，包含： 由不含或實質上不含徑向分布的雜質及缺陷之一連續雙晶 20 矽本體所形成之矽，該本體具有至少二維度各自至少約為 25厘米及一第三維度至少約為20厘米。 根據本發明之又另一實施例，也提供一種晶圓，包含： 由一連續鑄態雙晶矽本體所形成之矽，該晶圓具有至少一 個維度至少約為50毫米，以及該本體具有至少二維度各自 11 200921924 至少約為25厘米及一第三維度至少約為20厘米。 根據本發明之又另一實施例，也提供一種製造鑄態矽 之方法，包含：將熔融矽放置於一容器内與至少一個矽種 晶接觸，該容器具有一個或多個加熱至至少矽之熔點之側 5 壁以及至少一個用於冷卻之壁面；以及經由將該熔融矽冷 卻至控制結晶化，形成雙晶矽之一固態本體，視需要可具 有各自至少約為10厘米之至少兩個維度，該形成包括於熔 融矽邊緣形成一固-液界面，該界面至少初步係平行於該至 少一個冷卻壁，該界面係於冷卻期間經控制因而於增加熔 10 融矽與該至少一個冷卻壁間之距離之方向移動。 根據本發明之又另一實施例，也提供一種製造鑄態矽 之方法，包含：將熔融矽放置於一容器内與至少一個矽種 晶接觸，該容器具有一個或多個加熱至至少矽之熔點之側 壁，該至少一個矽種晶係排列成覆蓋容器之全體表面或實 15 質上全體表面積；以及經由冷卻該熔融矽至控制結晶化而 形成雙晶矽之固態本體，視需要可具有各自至少約為10厘 米之至少兩個維度。 本發明之額外特徵及優點將陳述於後文說明，由該說 明將更為彰顯或可經由本發明之實施例之實施而習得。本 20 發明之特徵及其它優點將藉由於書面說明及申請專利範圍 以及附圖特別指出之半導體元件結構及製造方法及製造裝 置實現與達成。 須瞭解前文大致說明及後文細節說明僅供舉例說明及 解釋之用，意圖僅提供如申請專利之本發明之解說。本發 12 200921924 明也包括如此處所述及請求專利之方法所製造之矽，以及 由此等矽所製成之晶圓及太陽能電池。 圖式簡單說明 附圖係組成且構成本說明書之一部分，舉例說明本發 - 5 明之實施例連同詳細說明部分用來解釋本發明之特徵、優 . 點及原理。附圖中： 第1圖顯示根據本發明之實施例於坩堝底面上之矽晶 種之排列實例； f 第2圖顯示根據本發明之實施例於坩堝底面上之矽晶 10 種之排列實例； 第3圖顯示使用具有單一晶體取向之種晶之鑄錠之剖 面圖； 第4圖顯示根據本發明之實施例使用種晶之一鑄錠之 剖面圖，其中部分種晶具有一個晶體取向，部分種晶具有 15 另一個晶體取向； 第5圖顯示根據本發明之實施例之方法實例；及 I 第6A-6G及7圖顯示根據本發明之實施例用於單晶矽 " 或雙晶矽之鑄造方法之實例。 【實施方式3 20 較佳實施例之詳細說明 現在將對本發明之實施例做細節說明，其實例係說明 於附圖。可能時，附圖中將使用相同或類似之元件符號來 表示相同或類似之部件。 於本發明之實施例中，溶融矽之結晶化係經由使用一 13 200921924 讀造方法崎。如 5 10 15 20 可經實作，因而控制於結晶切“，該鑄造方法 狀及取向。如此處使用，「禱造」—中之晶粒大小、形 盛裝熔融矽之模具或容器内冷卻=:矽係經由於用來 體例如炫融石夕將呈該液體放置於其而製成。由於液 處也預期可達成炫融石夕之冷卻 =的形狀’故此 具或容器内來約束叫舉例言二=只挪 化成形矽’此處固化係始 、坩堝内固 過導入炫體内部之^卻的異Γ 壁面，而非透 狀，钱… 坩堝可具有任何適當形 融石夕」： '圓柱形、或盒形。如此’根據本發明之熔 外;;序並非藉「抽拉」胚晶或薄帶而控制。此 至少模具、容器或_包括與炫融石夕接觸之 並接觸之☆ 細。如此處㈣，「熱㈣」係指與 ”接觸之炫融料溫或更熱之表 處理過程中維持固定。 車交佳，熱側壁面於石夕 單曰:據t發明之實施例，結晶化石夕可為連續單晶石夕、近 二:：:連續物、或具有已控制的晶粒取向㈣^ ^曰曰石夕。如此處使用，「連續多⑪」—詞係指單晶石夕， 人=本體為—個均質的單晶石夕本體而非由多個小塊石夕接 j 一起所形成之-個較大塊石夕。此外，如此處使用，「連 、,、邊何夕4」-詞係指幾何多晶秒此處财本體為一 個均質的幾何多晶石夕本體，而非多個小塊石夕接合在一起所 之广較大塊矽。此外，如此處使用「連續雙晶矽」 一縣指遍及全體只有兩個晶體取向之均質雙㈣本體， 14 200921924 而非分開的單晶⑦塊接合在—起所形成之—個雙晶石夕。 根據本發明，經由將期望之結晶石夕「晶種」收集物放 置於容器底部諸如可盛裝溶融石夕之石英掛禍底部而完成社 晶化。如此處使用，「晶種」一詞係指具有期望之晶體結構 5較佳為幾何成形之石夕塊，較佳其中至少—個剖面具有幾何 ^較佳為多面體形狀，較佳具有符合⑦塊置於其令之該 令器表面&種晶種可為單晶⑪塊或—塊幾何有序多晶 石夕，例如扁胚或水平截面切割或以其它方式得自單晶石夕鱗 鍵。根據本發明，晶種具有平行於其底面之一頂面，但非 1〇 然如此。例如，晶種可為一塊石夕，大小由約寬2毫米至約 寬3000毫米。例如晶種可為寬約10毫米至寬約毫米1 塊具有約1毫米至約1000毫米，較佳約5毫米至約50毫米之 厚度。晶種之適當大小及形狀可為求方便及鋪磚而選用。 容後詳述，鋪磚為石夕種晶例如於掛瑪底部或掛堝側面及底 15面中之一者或多者排列成預定之幾何取向或模型。較佳晶 種係覆蓋於整個掛禍表面位於其所在位置旁，因此當移動 種晶成長固化鋒遠離晶種時，掛禍截面之全體大小可維持 成為一致的幾何晶體。 然後允許炫融石夕冷卻，且於晶種存在下結晶化，較佳 係以炫融石夕冷部方式讓炫融石夕之結晶化係始於或低於固體 晶種之原先頂部錢佳向上前進遠離晶種 。於溶融發邊緣 之固液界面. 父佳係符合係於其中冷卻之容器之冷卻表 面諸如掛瑪表面。根據本發明之實施例’溶融石夕與結晶 化夕間之口液界面可於整個部件例如固化平坦之初始部 15 200921924 分或全部鑄造程序實 —邊緣^I::;實施例 而於加大軸料㈣冷卻面間之轉之方制，因 較佳維持實質平坦的固-液界面。 1動，同時 开^狀。例如，你田目士_ τ ? ί7表面之 質上平扭η ^底部之鋒可维拷^ 貝上，，固-液界面具有經控制之 實 =::半徑由邊 10 15 20 =控制來維持平均曲率半徑約為容口: ^二二固_液界面可經控制來維持曲率半徑至 約為容器寬度之四的界帶有曲率半徑至少 平平方㈣识 固·液界面具有曲率半徑於〇.7 = 通常大於2米，大於㈣水平維度之兩倍， 且較佳約為㈣水平維度之8倍至約Μ倍。 曰根據本發明之實施例，可形成單晶石夕、雙晶石夕或近單 晶石夕且較佳為禱態石夕之固態本體，較佳具有至少兩個維度 各自^勺為2〇厘米’例如一側至少約為20厘米，以及第 一^曰至ν約為1〇厘米。較佳，可形成單晶石夕、雙晶石夕或 近夺曰曰石夕且較佳為禱態石夕之固態本體較佳具有至少兩個 、准度各自至人約為30厘米，例如一側至少約為30厘米，以 及:：!持至少約為10厘米。更佳，可形成單晶石夕、雙晶 石夕或近早晶石夕且較佳為鑄態石夕之固態本體較佳具有至少 兩個維度各自至少約為塊米，例如—側至少約為35厘 米，以及第三維持至少約為10厘米。又更佳，可形成單晶 16 200921924 矽、雙晶矽或近單晶矽且較佳為鑄態矽之固態本體，較佳 具有至少兩個維度各自至少約為40厘米，例如一側至少約 為40厘米，以及第三維持至少約為20厘米。又更佳，可形 成單晶矽、雙晶矽或近單晶矽且較佳為鑄態矽之固態本 - 5 體，較佳具有至少兩個維度各自至少約為50厘米，例如一 _ 側至少約為50厘米，以及第三維持至少約為20厘米。又更 佳，可形成單晶矽、雙晶矽或近單晶矽且較佳為鑄態矽之 固態本體，較佳具有至少兩個維度各自至少約為60厘米， < 例如一側至少約為60厘米，以及第三維持至少約為20厘 10 米。又更佳，可形成單晶矽、雙晶矽或近單晶矽且較佳為 鑄態矽之固態本體，較佳具有至少兩個維度各自至少約為 70厘米，例如一側至少約為70厘米，以及第三維持至少約 為20厘米。根據本發明之實施例，可形成連續單晶矽、連 續雙晶矽或近單晶矽之一本體，其為不含或實質上不含徑 15 向分布的缺陷及/或雜質，且較佳具有至少二維度其各自至 少約為20厘米，及第三維度至少約為10厘米。較佳，可形 I 成連續單晶矽、連續雙晶矽或近單晶矽之一本體，其為不 ~ 含或實質上不含徑向分布的缺陷及/或雜質，且較佳具有至 少二維度其各自至少約為30厘米，及第三維度至少約為10 20 厘米。更佳，可形成連續單晶矽、連續雙晶矽或近單晶矽 之一本體，其為不含或實質上不含徑向分布的缺陷及/或雜 質，且較佳具有至少二維度其各自至少約為35厘米，及第 三維度至少約為10厘米。又更佳，可形成連續單晶矽、連 續雙晶矽或近單晶矽之一本體，其為不含或實質上不含徑 17 200921924 向刀布的缺及/或雜質，且較佳具有至少二維度其各自參 V、力為40厘米’及第三維度至少約為20厘米。又更隹，< 形成連續早晶石夕、連續雙晶石夕或近單晶石夕之一本體，其為 不含或實質上不含徑向分布的缺陷及/或雜質，且較隹具有 5至少二維度其各自至少約為50厘米，及第三維度至少約爲 20厘米。又更佳，可形成連續單晶石夕、連續雙晶石夕或近單 晶石夕之一本體，其為不含或實質上不含徑向分布的缺陷及/ 或雜質，且較佳具有至少二維度其各自至少約為_米， 及第一維度至；約為2〇厘米。又更佳’可形成連續單晶石夕、 10連續雙的矽或近單晶矽之一本體，其為不含或實質上不含 徑向分布的缺陷及/或雜質，且較佳具有至少二維度其各自 至少約為70厘米’及第三維度至少約為2〇厘米。 根據本發明所製造之铸態矽鑄錠之水平尺寸上限僅受 鑄造技術及掛禍製造技術所限而非受本發明方法本身所 15限。具有至少1平方米至至多4-8平方米之截面積之鑄錠可 根據本發明製造。同理’鑄錠之高度上限可能關係較長的 週期時間，而非鑄造方法的基礎。至多約50厘米至約8〇厘 米之鑄錠高度為可能。如此’根據本發明’連續單晶矽、 連續雙晶矽、或近單晶石夕之一本體可成功地成長為截面積 20約66厘米χ66厘米，連續單晶矽之矩形固體塊之體積至少為 33,750立方厘米。進一步，根據本發明，鑄態連續單晶矽、 連續雙晶矽、或近單晶矽之固態本體較佳係形成為至少有 兩個維度其各自大至鑄造容器之内部維度，及第三維度係 與鎿錠高度等高。舉例&之，若矽之鑄體為立方形或矩形 18 200921924 固體， 則前述维度可分別稱作為此種本體 高度。 之長度、寬度及 &田Μ於树明之實_之料崎軸 5 10 15 …I造具有特定晶粒邊界㈣隨機晶粒邊界及特定晶 粒大小之鑄態，此外，經由以全部晶種係定向於彼^目曰 同的相對方向’例如⑽)極方向係垂直於_底部及 ，方向係平行於矩形或方形截㈣如—側之方式來校準 曰曰種可獲得鑄態歡大型本體，該鑄態料或接近為單 晶石夕’其中此種鑄_之極方向係與晶種之極方向相同。 同理’其它極方向可能垂直於_底部。此外，晶種之排 列可能有多於—個極方向係垂直於㈣底部。例如排列可 ^括具有-個極方向係垂直於掛碼底部之晶種之中部，及 核燒該巾部且具有垂直於該卿底部之另—個極方向之晶 種之另-個「保護」部。此外，根據本發明之實施例，晶 種可排列成任-個共通財向或任兩個共通财向係垂直 於坩堝之底部。 當單晶耗藉習知域_池中抽拉圓柱形胚晶之習 t方法例如根據CZ法或取製造時，麟單㈣含有徑向 20刀布之雜貝及缺陷，諸如璇渦缺陷（由特有缺陷諸如空位及 自，間隙原子所形成)及〇SF環缺陷H满缺陷為間隙石夕原 子或工位可呈單—形式或群簇形式。此種義缺陷可藉X光 也形測里術檢測，且於矽中呈現「漩渦」。於優先酸蝕刻矽 用於描述缺陷後也可檢測。 根據習知CZ法或FZ法，於石夕内之氧原子之分布以及由 19 200921924 此等氧原子於砂内造成之缺陷之分布呈輕射狀。如此表示 排列成以中軸為中心呈對稱之環' 螺旋或條紋。〇SF環缺 陷為其特例，此處奈米級氧於經過抽拉之單晶石夕翁或石夕 胚晶内部沉激圓柱形帶狀之孕核疊差缺陷，結果導致由此 5種石夕所製成之晶圓上之圓形缺陷帶。此等帶可於優先酸敍 刻後於矽試樣中觀察得。 例如根據習知CZ法或邮例如從炫㈣池中抽拉出 圓柱形胚晶所得之單晶雜晶，由於抽拉法之旋轉對稱、 10 15 πl l、梯纟亥方法中特有的旋轉，出現漩渦缺陷及0SF 、生争I彳目反地’何經由根據本發明之實施例之鑄 、該方法不會呈現此種㈣缺陷及QSF環缺陷。 =紐於鑄造過財所摻混的缺陷大致上舰機分布於 又：渦所影響之成長界面’缺陷摻混於不具有 圓柱形對 之n㈣U及缺1^摻混於目化及冷料程巾跨鑄鍵 之4溫線大致上為平坦之方法。 所顯考f不时法於㈣成長4元件雜«度’下表! 所顯不之下列等級為廣為人考慮的特徵。, a spoon having a size of 25 cm and a third dimension of at least about 2 cm. In accordance with yet another embodiment of the present invention, a continuous as-cast single crystal germanium body having at least two dimensions each of at least about 35 cm is also provided. According to still another embodiment of the present invention, a solar cell is provided, comprising: substantially no continuous bimorph body having at least two dimensions of at least about 25 cm 200921924 and a third dimension of at least about 20 cm One of the wafers formed; one of the pn junctions in the wafer; an optional anti-reflective coating on one of the surfaces of the wafer; optionally, selected from a back field and a At least one layer of the purification layer; and a conductive contact on the wafer. According to still another embodiment of the present invention, a solar cell is provided, comprising: a wafer made of a continuous as-cast twin-crystal body, the body having at least two dimensions of at least about 35 cm each; a pn junction in the wafer; an optional anti-reflective coating on one of the surfaces of the wafer; optionally, at least one layer selected from a back field and a purification layer; 10 and conductive contacts on the wafer. According to still another embodiment of the present invention, a solar cell is provided, comprising: a continuous twin wafer wafer made of a continuous cast twin germanium body, the wafer having at least one dimension of at least about 50 mm And the body has at least two dimensions of at least about 25 cm and a third dimension to 15 less than about 20 cm; one of the pn junctions in the wafer; one of the surfaces of the wafer is optional An anti-reflective coating; optionally, selected from at least one of a back field and a passivation layer; and a conductive contact on the wafer. According to still another embodiment of the present invention, there is also provided a wafer comprising: a crucible formed of a continuous twin crystal 20 矽 body having no or substantially no radial distribution of impurities and defects, the body having at least The two dimensions are each at least about 25 cm and the third dimension is at least about 20 cm. According to still another embodiment of the present invention, a wafer is provided, comprising: a crucible formed by a continuous as-cast bimorph body having at least one dimension of at least about 50 mm, and the body having at least The two dimensions respective 11 200921924 are at least about 25 cm and a third dimension is at least about 20 cm. According to still another embodiment of the present invention, there is also provided a method of making an as-cast crucible comprising: placing a molten crucible in a container in contact with at least one seed crystal having one or more heats to at least a side wall 5 of the melting point and at least one wall for cooling; and forming a solid body of one of the twins by cooling the molten crucible to control crystallization, optionally having at least two dimensions of at least about 10 cm each Forming includes forming a solid-liquid interface at the edge of the molten crucible, the interface being at least initially parallel to the at least one stave, the interface being controlled during cooling to increase the melting of the melt and the at least one stave Move in the direction of the distance. According to still another embodiment of the present invention, there is also provided a method of making an as-cast crucible comprising: placing a molten crucible in a container in contact with at least one seed crystal having one or more heats to at least a side wall of the melting point, the at least one seed crystal system arranged to cover the entire surface of the container or the entire surface area of the solid; and a solid body formed by cooling the molten crucible to control crystallization to form a twin crystal, optionally having respective At least two dimensions of at least about 10 cm. The additional features and advantages of the invention will be set forth in the description which follows. The features and other advantages of the present invention will be realized and attained by the written description and the appended claims. It is to be understood that the following general description and the following detailed description are for the purpose of illustration and explanation only The present invention also includes wafers and solar cells fabricated as described herein and as claimed in the patented method. BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a In the drawings: FIG. 1 shows an example of arrangement of twin crystals on the bottom surface of a crucible according to an embodiment of the present invention; f FIG. 2 shows an example of arrangement of ten crystals on the bottom surface of a crucible according to an embodiment of the present invention; Figure 3 is a cross-sectional view showing an ingot using a seed crystal having a single crystal orientation; and Figure 4 is a cross-sectional view showing an ingot in which a seed crystal is used in accordance with an embodiment of the present invention, in which a part of the crystal has a crystal orientation, and a part thereof The seed crystal has 15 another crystal orientation; Fig. 5 shows an example of a method according to an embodiment of the present invention; and I 6A-6G and 7 show a single crystal crucible " or twin crucible according to an embodiment of the present invention. An example of a casting method. [Embodiment 3] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments embodiments Wherever possible, the same or similar reference In an embodiment of the invention, the crystallization of the molten enthalpy is via the use of a 13 200921924 reading method. For example, 5 10 15 20 can be implemented, and thus controlled by crystal cutting, the casting method shape and orientation. As used herein, "prayer" - the size of the crystal grain, the shape of the mold containing the melting crucible or the cooling in the container = The lanthanum is produced by placing the liquid on it for use in a body such as a glazed stone. Since the liquid is also expected to achieve the shape of the cooling of the glazed stone ' 故 故 故 故 故 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器^ But the difference is the wall, not the transparency, the money... 坩埚 can have any suitable shape of the melting stone eve: 'cylindrical, or box-shaped. Thus, the melting according to the present invention;; the order is not controlled by "drawing" the blast or thin strip. At least the mold, the container or the _ includes the ☆ fine contact with the glazed stone. As shown here (4), "Hot (4)" means that it is kept fixed during the treatment of the contact with the material temperature or heat. The car is good, the hot side wall is in Shi Xidan: According to the embodiment of the invention, crystallization Fossil eve can be continuous single crystal eve, near two::: continuous matter, or has a controlled grain orientation (four) ^ ^ 曰曰石夕. As used herein, "continuously 11" - the word refers to single crystal In the evening, the person = the body is a homogeneous single crystal stone body rather than a large piece of stone formed by a plurality of small pieces of stone. In addition, as used herein, "Lian, 、, 边何夕4" - the word refers to the geometric polycrystalline seconds where the financial body is a homogeneous geometric polycrystalline stone corpus, rather than a plurality of small pieces It is a large block. In addition, as used herein, "continuous twin bismuth" a county refers to a homogeneous double (four) body with only two crystal orientations throughout, 14 200921924 instead of a separate single crystal 7 blocks joined together - a twin-crystal . According to the present invention, crystallization is accomplished by placing a desired crystallized "seed" collection on the bottom of the container, such as a quartz-filled bottom that can hold a molten stone. As used herein, the term "seed" refers to a stone block having a desired crystal structure 5, preferably geometrically shaped, preferably at least one of the sections having a geometry, preferably a polyhedral shape, preferably having 7 pieces. Placed on the surface of the actuator & seed crystals may be a single crystal block or a block of geometrically ordered polycrystalline stone, such as a flat embryo or a horizontal section cut or otherwise obtained from a single crystal stone . According to the invention, the seed crystal has a top surface parallel to one of its bottom surfaces, but this is not the case. For example, the seed crystal can be a piece of stone, ranging in size from about 2 mm wide to about 3,000 mm wide. For example, the seed crystal may have a thickness of from about 10 mm to about 1 mm wide and from about 1 mm to about 1000 mm, preferably from about 5 mm to about 50 mm. The appropriate size and shape of the seed crystal can be selected for convenience and paving. As described in detail later, the paving is arranged in a predetermined geometric orientation or model for one or more of the bottom of the hangma or the side of the hangar and the bottom 15 of the hang. The preferred seed system covers the entire surface of the hazard at its location, so that when the seed crystal grows and solidifies away from the seed crystal, the overall size of the cross-section can be maintained as a uniform geometric crystal. Then, it is allowed to cool and cool, and crystallize in the presence of seed crystals. It is preferable to make the crystallization of the smelting stone stalks start or fall below the original top of the solid crystals. Move up and away from the seed crystal. The solid-liquid interface at the edge of the melted hair. The parental system conforms to the cooling surface of the container in which it is cooled, such as a rug surface. According to an embodiment of the present invention, the mouth-to-liquid interface between the molten stone and the crystallization can be applied to the entire part, for example, the flat portion 15 of the curing flat, 200921924, or the entire casting process, the edge-edge: The rotation of the shaft (4) between the cooling surfaces is preferred to maintain a substantially flat solid-liquid interface. 1 move, open at the same time. For example, the surface of your field _ τ ί7 surface is flat and twisted η ^ the bottom of the bottom can be copied on the shell, the solid-liquid interface has a controlled real =:: radius is controlled by the edge 10 15 20 = Maintaining the average radius of curvature is approximately the mouth: ^22. The solid-liquid interface can be controlled to maintain the radius of curvature to about four of the container width with a radius of curvature of at least square (4). The liquid interface has a radius of curvature at 〇 .7 = usually greater than 2 meters, greater than twice the horizontal dimension of (4), and preferably about 8 times to about Μ times the horizontal dimension of (4). According to an embodiment of the present invention, a solid body of single crystal, twin or near single crystal, and preferably a solid body of prayer, may be formed, preferably having at least two dimensions of 2 The centimeter' is, for example, at least about 20 cm on one side, and from about 1 cm to about 1 cm. Preferably, the solid body which can form a single crystal stone, a double crystal stone or a near celestial stone, and preferably a prayer state, preferably has at least two, each having a degree of approximating to about 30 cm, for example The side is at least about 30 cm, and the ::! holds at least about 10 cm. More preferably, the solid body which can form a single crystal stone, a double crystal stone or a near-early crystal spar, and preferably a cast stone, preferably has at least two dimensions each of at least about a block of meters, for example, at least about It is 35 cm, and the third is maintained at least about 10 cm. Still more preferably, a solid body of single crystal 16 200921924 矽, twin 矽 or near single crystal 矽 and preferably as cast tantalum may be formed, preferably having at least two dimensions each of at least about 40 cm, such as at least about one side. It is 40 cm, and the third is maintained at least about 20 cm. Still more preferably, a solid crystal body of a single crystal germanium, a twin germanium or a near single crystal germanium and preferably an as-cast germanium may be formed, preferably having at least two dimensions each of at least about 50 cm, for example, a side At least about 50 cm, and the third is maintained at least about 20 cm. Still more preferably, a solid body of single crystal germanium, twin germanium or near single crystal germanium and preferably as cast tantalum may be formed, preferably having at least two dimensions each of at least about 60 centimeters, < It is 60 cm, and the third is maintained at least about 20 cents and 10 meters. Still more preferably, a solid body of single crystal germanium, twin germanium or near single crystal germanium and preferably as cast tantalum may be formed, preferably having at least two dimensions each of at least about 70 centimeters, such as at least about 70 on one side. The centimeter, and the third is maintained at least about 20 cm. According to an embodiment of the present invention, a body of continuous single crystal germanium, continuous twin germanium or near single crystal germanium may be formed, which is free or substantially free of defects and/or impurities distributed in a 15 direction, and is preferably There are at least two dimensions each of at least about 20 cm, and a third dimension of at least about 10 cm. Preferably, the shape I is a body of a continuous single crystal germanium, a continuous twin germanium or a near single crystal germanium, which is a defect and/or an impurity which does not contain or substantially does not contain a radial distribution, and preferably has at least The two dimensions are each at least about 30 cm and the third dimension is at least about 10 20 cm. More preferably, a body of continuous single crystal germanium, continuous twin germanium or near single crystal germanium may be formed, which is free or substantially free of radial distribution defects and/or impurities, and preferably has at least two dimensions Each is at least about 35 cm and the third dimension is at least about 10 cm. Further preferably, a body of continuous single crystal germanium, continuous twin germanium or near single crystal germanium may be formed, which is free or substantially free of defects and/or impurities of the diametrical cloth, and preferably has At least two dimensions of their respective V, force of 40 cm ' and a third dimension of at least about 20 cm. Further, < forming a body of continuous early quartz, continuous twin or near single crystal, which is free or substantially free of radial distribution defects and/or impurities, and is relatively Having at least two dimensions of at least about 50 cm each, and a third dimension of at least about 20 cm. Still more preferably, a continuous single crystal stone, a continuous twin crystal or a single crystal single body is formed, which is free or substantially free of radial distribution defects and/or impurities, and preferably has At least two dimensions each of at least about _ meters, and a first dimension to; about 2 〇 cm. Still more preferably, a body of continuous single crystal, 10 consecutive double or nearly single crystal, which is free or substantially free of radial distribution defects and/or impurities, and preferably has at least The two dimensions are each at least about 70 cm' and the third dimension is at least about 2 cm. The upper limit of the horizontal dimension of the as-cast tantalum ingot produced in accordance with the present invention is limited only by the casting technique and the manufacturing technique of the crash, and is not limited by the method itself. Ingots having a cross-sectional area of at least 1 square meter up to 4-8 square meters can be made in accordance with the present invention. Similarly, the upper height limit of the ingot may be related to a longer cycle time than the basis of the casting method. An ingot height of up to about 50 cm to about 8 cm is possible. Thus, according to the present invention, one of the continuous single crystal germanium, the continuous twin germanium, or the near single crystal rock can be successfully grown into a cross-sectional area of about 20 cm to about 66 cm, and the volume of the rectangular solid block of the continuous single crystal crucible is at least It is 33,750 cubic centimeters. Further, according to the present invention, the solid body of as-cast continuous single crystal germanium, continuous twin germanium, or near single crystal germanium is preferably formed into at least two dimensions each of which is as large as the inner dimension of the casting container, and the third dimension It is the same height as the bismuth ingot. For example, if the cast body is a cuboid or rectangular 18 200921924 solid, the aforementioned dimensions may be referred to as such a body height, respectively. Length, width, and & Μ Μ 树 树 树 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The direction is oriented to the opposite direction of the same object 'for example (10)), the polar direction is perpendicular to the bottom of the _ bottom, and the direction is parallel to the rectangular or square cut (four) as the side to calibrate the scorpion to obtain the cast large body The as-cast material is nearly the same as the direction of the pole of the seed crystal. Similarly, the other pole directions may be perpendicular to the bottom of the _. In addition, the arrangement of the seed crystals may have more than one pole direction perpendicular to the bottom of the (four). For example, the arrangement may include another portion of the seed crystal having a pole direction perpendicular to the bottom of the hanging code, and a seed crystal having a core burning portion and having another polarity direction perpendicular to the bottom of the crystal. "unit. Moreover, in accordance with embodiments of the present invention, the seed crystals may be arranged in any one of the common fiscal directions or any two common fiscal lines perpendicular to the bottom of the crucible. When the single crystal consumes the conventional method of pulling the cylindrical embryonic crystal in the pool, for example, according to the CZ method or the manufacturing method, the Lindan (4) contains the miscellaneous shells and defects of the radial 20 knife, such as the vortex defect ( The defects are caused by characteristic defects such as vacancies and self-interstitial atoms, and 〇 SF ring defects. The full defects of the SF ring atoms may be in the form of a single-form or a cluster. This kind of defect can be detected by X-rays and the "swirl" in the sputum. For preferential acid etching, it can also be used to describe defects. According to the conventional CZ method or the FZ method, the distribution of the oxygen atoms in the stone eve and the distribution of the defects caused by the oxygen atoms in the sand of 19 200921924 are lightly projected. This means that the ring is a spiral or a stripe that is symmetrical about the center axis. The 〇SF ring defect is a special case. Here, the nano-scale oxygen sinks the cylindrical band-shaped pregnancy-nuclear stacking defect inside the single-crystal stone or the stone-like embryonic crystal, which results in the five kinds of stones. A circular defect strip on a wafer made in the evening. These bands can be observed in the sputum samples after preferential acid characterization. For example, according to the conventional CZ method or the postal single crystal crystal obtained by drawing the cylindrical blast crystal from the Hyun (four) pool, due to the rotational symmetry of the drawing method, the unique rotation in the 10 15 πl l method, the Tiehai method, Vortex Defects and Omissions Occurs. Why does the process according to embodiments of the present invention not exhibit such (4) defects and QSF ring defects. = New Zealand's defects in the casting of the financial assets are generally distributed on the ship: the growth interface affected by the vortex' defect is mixed with n (four) U and lack of 1^ mixed with the meshing and cold material The 4 temperature line of the towel cross-casting key is substantially flat. The test is not from time to time (4) growing 4 components of the following «degrees of the following table! The following levels are not considered to be widely considered.
氮 <1χ1014 <5xl014 >1χ1015 20 200921924 CZ鑄旋可製造成有低抵5xl〇”原子/立方厘米氧，但不 會更低。藉由蓄意摻雜，於FZ及CZ鑄錠中之碳及氮濃度玎 升阿’但摻雜不超過此等技術中之固體溶解度極限(如同鑄 造材料）’經摻雜的鑄錠未曾製成超過2〇厘米直徑大小。相 5反地，鑄錠由於離型塗層及爐熱區段之設計，典型係以碳 及氮超飽和。結果，由於液相孕核及成長緣故廣泛存在有 已沉澱的氮化物及碳化物。此外，鑄態單晶矽已經根據本 lx月之實把例製造成具有如前文報告之雜質含量及高達 50x50x20立方厘米及6〇χ6〇χ5立方厘米之大小。此等維度僅 1〇供舉例說明之用，不可視為本發明之鑄造法之上限。 例如，有關雜質含量，於根據本發明之鑄態矽中，以 約1-5x1017原子/立方厘米（約1χ1〇17原子/立方厘米至約 5x10原子/立方厘米之表示法）之溶碳濃度，約2_>1〇17原 子/立方厘米之溶氧濃度，及約l-5xl〇15原子/立方厘米之溶 15氮?辰度為佳。根據本發明之實施例，可形成具有至少兩個 維度各自至少約為2〇厘米例如一邊至少約為2〇厘米及第三 維度至少約為10厘米之單晶矽、雙晶矽、或近單晶矽較佳 為鑄態矽之固態本體，具有約Μχ1〇17原子/立方厘米之溶 碳濃度，約2-3xl〇i7原子/立方厘米之溶氧濃度，及約 2〇 1-5)(10)5原子/立方厘米之溶氮濃度。紹圭，可形成具有至 、兩個、准度各自至少約為3〇厘米例如一邊至少約為π厘米 及第三維度至少約為10厘米之單晶矽、雙晶矽、或近單晶 矽較佳為鑄態矽之固態本體，具有約l-5xl〇n原子/立方厘 米之溶碳濃度，約2-3xl〇i7原子/立方厘米之溶氧濃度，及 21 200921924 约 1-5χ1015 仏，可形成具有 邊至少約為35厘 雙晶矽、或近單 原子/立方厘米之溶氮濃度。更佳， 至少兩個維度各自至少約為35厘米例如一邊 米及第二維度至少約為丨〇厘米之單晶矽、 晶石夕較佳為鑄態石夕之固態本體，具有m_5xi〇n原子/立方 5厘米之溶碳濃度，約2_3xl〇”原子/立方厘米之溶氧濃度， 及約1-5χ1015原子/立方厘米之溶氮濃度。又更佳，可形成 具有至少兩個維度各自至少約為娜米例如—邊至少約為 40厘米及第三維度至少約為聰米之單㈣、雙晶石夕、或 近單晶矽較佳為鑄態矽之固態本體，具有約〗_5><1〇17原子/ 1〇立方厘米之溶碳濃度，約2-3xl〇n原子/立方厘米之溶氧濃 度，及約1-5χ1015原子/立方厘米之溶氮濃度。又更佳可 形成具有至少兩個維度各自至少約為5〇厘米例如一邊至少 約為50厘米及第三維度至少約為2〇厘米之單晶矽、雙晶 矽、或近單晶矽較佳為鑄態矽之固態本體，具有約卜5^〇17 15原子/立方厘米之溶碳濃度，約2-3xl017原子/立方厘米之溶 氧濃度，及約1-5χ1015原子/立方厘米之溶氮濃度。又更佳， 可形成具有至少兩個維度各自至少約為60厘米例如一邊至 少約為60厘米及第三維度至少約為20厘米之單晶矽、雙晶 矽、或近單晶矽較佳為鑄態矽之固態本體，具有約丨_5><1〇17 20原子/立方厘米之溶碳濃度，約2-3xl017原子/立方厘米之溶 氧濃度’及約1-5x1015原子/立方厘米之溶氮濃度。又更佳， 可形成具有至少兩個維度各自至少約為70厘米例如一邊至 少約為70厘米及第三維度至少約為20厘米之單晶矽、雙晶 矽、或近單晶矽較佳為鑄態矽之固態本體，具有約1-5χ1017 22 200921924 原子/立方厘米之溶碳濃度，約2_3xl，子/立方厘米之溶 氧濃度，及約1-5χ1015原子/立方厘米之溶氮濃度。 根據本發明之實施爿，可形成不含或實質上不含徑向 分布的缺陷及/或雜質之連續單晶⑦、連續雙晶⑦、或^單 5晶石夕之-本體，較佳具有各自至少約為聰米之至少兩個 維度及至少約為10厘米之一第三維度，具有約^^心原子 /立方厘米之溶破濃度，約2_3χ1()17原子/立方厘米之溶氧濃 度’及約1-5X1015原子/立方厘米之溶氮濃度。較佳，可形 成不含或實質上不含徑向分布的缺陷及/或雜質之連續單 晶石夕、連續雙晶石夕、或近單晶石夕之一本體，具有各自至少 約為30厘米之至少兩個維度及至少約為_米之一第三維 度，具有約l-5xl017原子/立方厘米之溶碳;農度，約2初 原子7立方厘米之溶氧濃度，及約1-5χ1015原子/立方厘米之 溶氮濃度。更佳，可形成不含或實質上不含徑向分布的缺 陷及/質之連續單㈣、賴雙晶[錢單晶妙之一 本體具有各自至少約為35厘米之至少兩個維度及至少約 為10厘米之一第三維度，具有約原子/立方厘米之 溶碳濃度，約2-3xl〇17原子/立方厘米之溶氧濃度，及約 1-5χ1015原子/立方厘米之溶氮濃度。又更佳，可形成不含 20或實質上不含徑向分布的缺陷及/或雜質之連續單晶矽、連 續雙晶石夕、或近單晶石夕之一本體，具有各自至少約為萄 米之至少兩個維度及至少約為2〇厘米之一第三維度，具有 約1-5χ1017原子/立方厘米之溶碳濃度，約2_3χΐ〇η原子/立方 厘米之溶氧濃度，及約原子/立方厘米之溶氮濃 23 200921924 度。又更佳，可形成不含或實質上不含徑向分布的缺陷及/ 或雜貝之連續單晶;5夕 '連續雙晶石夕、或近單晶石夕之一本體， 具有各自至少約為50厘米之至少兩個維度及至少約為2〇厘 米之一第三維度，具有約卜5><1〇17原子/立方厘米之溶碳濃 5度，約2-3x1017原子/立方厘米之溶氧濃度，及約1-5χ1015 原子/立綠米之輯濃度。又更佳，可形成不含或實質上 不含徑向分布的缺陷及/或雜質之連續單晶矽、連續雙晶 矽或近單sa矽之一本體，具有各自至少約為6〇厘米之至 少兩個維度及至少約為20厘米之—第三維度，具有約 10 15xlG原子/立方厘米之溶碳濃度，約2_3_17原子/立方厘 米之溶氧濃度’及約…俨原子/立方厘米之溶氮濃度。 又更L彳形成不含或實質上不含徑向分布的缺陷及/或雜 質之連續單晶石夕、連續雙晶石夕、或近單晶石夕之一本體，具 有各自至少約為70厘米之至少兩個維度及至少約為職米 U之-第三维度，具有w_5xiQl7原子/立方厘米之溶碳濃 度，約2-3Χΐ〇Π原子/立方厘米之溶氧濃度，及約 原子/立方厘米之溶氮濃度。 20 根據本發明之實施例製造^有前述雜質濃度之禱態 之水平尺寸上限僅由鑄造技術及掛㈣造技術決 連續雙晶石夕、或 二：非由本發明方法本身決定。如此，根據本發明可形 成/、有前述雜質濃度之鑄態連續單晶矽 固態本體，較佳具有至少兩個維度各自_ 棧之内部維度’及第三維度係與鑄錠等 石夕之鱗體為立謂核形關，顺麟度可分別稱作為 24 200921924 此種鑄體之長度、寬度、及高度。 根據本發明用於鑄造程序之晶種可具有任何期望之尺 寸及形狀，但適合為單晶矽、雙晶矽、近單晶矽、或幾何 有序多晶矽之幾何形狀塊，諸如方形、矩形、六角形、菱 5 形、或八角形矽塊。可成形來方便鋪磚，或可以邊對邊放 置或「鋪磚」且隨形於期望模型中之坩堝底部。也根據本 發明之實施例，晶種可置於坩堝之一側或多側上包括全部 各側上。例如經由將結晶矽來源諸如單晶矽胚晶鋸割成為 具有期望形狀之塊狀物可獲得此種晶種。晶種也可經由藉 10 根據本發明之方法製造之連續單晶矽、連續雙晶矽、近單 晶矽、或連續幾何多晶矽之試樣切割成形，讓用於隨後鑄 造程序之晶種可由初始鑄造程序製造。如此，例如連續單 晶矽、連續雙晶矽、或近單晶矽切割或以其它方式得自連 續單晶矽、連續雙晶矽、或近單晶矽之鑄錠之扁胚可用作 15 為隨後鑄造的樣板。此種種晶可具有晶種放置於其中之坩 堝或其它容器之一側諸如底部之尺寸及形狀或實質上為該 尺寸及形狀。用於單晶鑄造，較佳有儘可能少數晶種覆蓋 坩堝底部以防摻混入缺陷。用於單晶鑄造，也較佳有具有 兩種不同晶體取向諸如（100)及（m)之預定晶種排列覆蓋 20 坩堝底部。較佳，種晶排列包括具有（100)極方向垂直於坩 堝底部之一中部，及具有（111)極方向垂直於坩堝底部且環 繞中部之另一個晶種「保護」部。如此，晶種可具有晶種 置於其中來執行根據本發明之鑄造方法之坩堝或容器之一 或多側諸如底部之尺寸及形狀或實質上該尺寸及形狀。 25 200921924 現在將說明根據本發明之若〜 法及裝置。但須瞭解並非唯 ^施则於製造石夕之方 方法。 x康本發明之原理形成矽之 參一第1圖，晶種100置於—個 5 10 15 20 如石英職底m種以相有底且有壁之_ιι〇諸 塊大型連續取向之扁胚12()。另彳肖緊密赴鄰因而形成- 向緊密础鄰因而形成於所製造之石夕係以預先選定之錯誤取 小之特定晶粒邊界。 夕中具有蓄意選定晶粒大 例如用於幾何多晶矽之鑄造，少 之截面晶粒大小且較佳為;^所得結晶化幾何多晶石夕 小及形狀及晶粒高=:=:等於或近似於晶種大 多晶石夕種晶例如以切割或q ^之料度。若幾何 之幾何多㈣扁胚係❹種“ _=6线=多晶錢鍵 得幾何多晶歡截面晶粒大 ""幾何夕晶砍，則所 晶石夕晶種中之晶粒大小及形狀。=形狀將近似於幾何多 如此’以切割或以豆它方 式得自幾何多_鑄錠之幾何多㈣扁胚可為「幾何多晶 石夕種晶」（有稱作為「幾何有序多晶㈣晶」），且可作為隨 後幾何多晶销造之樣板。此種種晶可具有晶種放置於立 中之_或其它容$—_如底叙尺寸及魏或實質上 該尺寸及雜。當此種種晶用於本發明方法時，所得幾何 多晶石夕較纟具有與晶種中之晶粒相同或實質上相同之尺寸 及形狀。 晶種100可經鋪碑且較佳放置成實質上覆蓋掛禍11〇的 全體底面。也較佳坩堝110具有離型塗覆層諸如由二氧化 26 200921924 夕氮化石夕、或液體囊封劑所製成之離型塗層來協助由坩 堝110移除έ士曰k 〜、，、QBa化秒。此外’晶種可包含具有一期望晶體取 @或兩個不同期望晶體取向厚約3毫米至約100毫米之單晶 夕扁胚雖然晶種100之特定數目及尺寸顯示於第1圖，但 見、°曰技藝人士顯然易知依據用途而定，可增減晶種之數目 及尺寸。 參照第2圖，呈現晶種300及310之其它排列之平面圖。 於第2圖中，晶種300及310係置於一個有底及有壁坩堝（圖 中未顯不）諸如第1圖所示之坩堝110之底部，因而讓晶種於 1〇兩個不同晶體取向緊密毗鄰來覆蓋或接近完全覆蓋有底及 有壁掛禍底面之全寬320。根據本發明，晶種300及310可為 單晶石夕塊。較佳晶種300具有（100)晶體取向，而晶種310具 有（1Π)晶體取向，讓其個別之極向係垂直於坩堝110之底 面。如第2圖所示，一串列（in)晶種310選擇性放置而環繞 15 —串列（丨㈨）晶種300。晶種310顯示於第2圖，具有（111)極 向垂直於坩堝110之底面，原因在於相信（111)晶體取向可提 供低能成長鋒，晶種310可能有其它晶體取向。較佳晶種300 具有與晶種310不同之晶體取向。雖然於第2圖顯示特定數 目及尺寸之晶種300及310，但熟諳技藝人士顯然易知依據 20用途而定’可改變晶種之晶體取向。舉例言之，兩串列晶 種300及310中之一者可為單一單晶矽扁胚。換言之，晶種 300為單晶（ι00)矽由一串列（111)晶種31〇所環繞之單一扁 胚’或任何其它替代組合來覆蓋坩堝110底部。當製造具有 此種特別選定之晶種排列以及隨後晶粒邊界排列時，較佳 27 200921924 晶粒邊界接面只有二個晶粒邊界會合於一個給定角隅，顯 示於第2圖之種晶排列。如此，晶種3〇〇可置於掛禍底面， 晶種310可置於坩堝底面之未被晶種3〇〇所占據的周邊區。 就使用晶種300及310所鑄造之矽鑄錠將於後文參照第3、4 5 及6G圖作說明。 根據第1-2圖揭示之晶種佈局圖（或模型），例如石夕進料 (圖中未顯示）隨後可導入坩堝11〇於晶種10〇、300及/或31〇 上方然後'熔解。另外，炫融矽可導入坩堝11〇。於另一個實 例中，坩堝110可首先調整至極為接近矽熔點或高達矽熔 10點，然後導入溶融石夕。根據本發明之實施例，石夕薄層可於 固化開始前溶解。 然後，於前文討論之任一實例中，坩堝110經冷卻，藉 此藉例如固體散熱座材料將熱輻射至周圍而從坩堝110底 部（及側面，唯有於晶種也鋪磚於側面時)移除熱量，同時仍 15然她熱至坩堝110之開放頂部。如此，導入熔解矽，晶種維 持固體，雜之方向性g]化造成柱狀晶粒之向上成長。藉 此方式，所得矽鑄錠將模擬矽晶種100或300及310之晶體取 向。所得鑄錠例如可切成水平扁胚來用作為其它鑄造過程 之曰B種層。扁胚例如可具有用於鑄造之坩堝或其它容器一 20表面諸如底面之尺寸及形狀或實質上該尺寸及形狀。例 如有一個扁胚可用於鑄造程序。如此用於成形矽之坩 禍中之種晶取向可選擇為特別影響所得石夕鎮鍵所得晶體結 構之最終控制晶體結構。 與本發明之貫施例相反’已知鑄造法涉及由完全熔解 28 200921924 之石夕塊直接固化來以未經 控制之太？V植44·炙μ D . iNitrogen <1χ1014 <5xl014 >1χ1015 20 200921924 CZ casting can be made to have a low atomic/cubic centimeter oxygen, but not lower. By deliberate doping, in FZ and CZ ingots The carbon and nitrogen concentrations soared, but the doping did not exceed the solid solubility limit of these technologies (like casting materials). The doped ingots were not made more than 2 cm in diameter. Phase 5 reversed, ingots Due to the design of the release coating and the hot section of the furnace, it is typically supersaturated with carbon and nitrogen. As a result, precipitated nitrides and carbides are widely present due to liquid phase pregnancy and growth.矽 has been manufactured according to the actual case of this month to have the content of impurities as reported above and up to 50x50x20 cubic centimeters and 6〇χ6〇χ5 cubic centimeters. These dimensions are only for illustrative purposes and cannot be considered as The upper limit of the casting method of the invention. For example, the impurity content is expressed in the as-cast bismuth according to the present invention at about 1-5 x 1017 atoms/cm 3 (about 1 χ 1 〇 17 atoms/cm 3 to about 5 x 10 atoms/cm 3 ). Carbon concentration A dissolved oxygen concentration of about 2_> 1 〇 17 atoms/cm 3 , and a dissolved 15 nitrogen atom of about 1 - 5 x 1 〇 15 atoms / cm 3 is preferred. According to an embodiment of the present invention, it may be formed to have at least two dimensions. Single crystal germanium, twin germanium, or near single crystal germanium, each having at least about 2 cm, such as at least about 2 cm on one side and at least about 10 cm in the third dimension, is preferably a solid body of as-cast tantalum, having about溶1〇17 atom/cm3 of dissolved carbon concentration, about 2-3xl〇i7 atom/cm3 of dissolved oxygen concentration, and about 2〇1-5)(10)5 atom/cm3 of dissolved nitrogen concentration. It is preferred to form single crystal germanium, twin germanium, or near single crystal germanium having up to two, each having a degree of at least about 3 cm, such as at least about π cm on one side and at least about 10 cm in the third dimension. The solid body of the as-cast crucible has a dissolved carbon concentration of about 1-5 x 1 〇n atoms/cm 3 , a dissolved oxygen concentration of about 2-3 x 1 〇 i 7 atoms/cm 3 , and 21 200921924 about 1-5 χ 1015 仏, which can be formed. Having a nitrogen concentration of at least about 35 centimeters of twins, or near a single atom per cubic centimeter. More preferably, at least Each of the dimensions is at least about 35 cm, for example, one side of the rice and the second dimension is at least about 丨〇cm. The single crystal 矽, the spar eve is preferably a solid body of the as-cast stone, having m_5xi〇n atoms/cubic 5 cm. The dissolved carbon concentration, a dissolved oxygen concentration of about 2_3xl 〇 atom/cm 3 , and a dissolved nitrogen concentration of about 1-5 χ 1015 atoms/cm 3 . Still more preferably, it is preferred to form a single (four), twin-crystal, or near-single-crystal crucible having at least two dimensions each of at least about nanometers, for example, at least about 40 centimeters, and a third dimension of at least about Congmi. The solid body of the as-cast crucible has a dissolved carbon concentration of about _5 > 1 〇 17 atoms / 1 〇 cubic centimeter, a dissolved oxygen concentration of about 2-3 x 1 〇 n atom / cubic centimeter, and about 1-5 χ 1015 atoms. / cubic centimeter of dissolved nitrogen concentration. Still more preferably, it is preferred to form single crystal germanium, twin germanium, or near single crystal germanium having at least two dimensions each of at least about 5 cm, such as at least about 50 cm on one side and at least about 2 cm in the third dimension. The solid body of the as-cast crucible has a dissolved carbon concentration of about 5 5 〇 17 15 atoms/cm 3 , a dissolved oxygen concentration of about 2-3 x 1 017 atoms/cm 3 , and a dissolved nitrogen of about 1-5 χ 1015 atoms/cm 3 . concentration. Still more preferably, it is preferred to form single crystal germanium, twin germanium, or near single crystal germanium having at least two dimensions each having at least about 60 centimeters, for example, at least about 60 centimeters on one side and at least about 20 centimeters in a third dimension. The solid body of the as-cast crucible has a dissolved carbon concentration of about 丨5_1; <1〇17 20 atoms/cm 3 , a dissolved oxygen concentration of about 2-3 x 1 017 atoms/cm 3 'and about 1-5 x 1015 atoms/cm 3 . The concentration of dissolved nitrogen. Still more preferably, it is preferred to form a single crystal germanium, a twin germanium, or a near single crystal germanium having at least two dimensions each of at least about 70 centimeters, such as at least about 70 centimeters on one side and at least about 20 centimeters in a third dimension. The solid body of the as-cast crucible has a dissolved carbon concentration of about 1-5 χ 1017 22 200921924 atoms/cm 3 , a dissolved oxygen concentration of about 2_3xl, sub/cm 3 , and a dissolved nitrogen concentration of about 1-5 χ 1015 atoms/cm 3 . According to an embodiment of the present invention, a continuous single crystal 7, a continuous twin crystal 7, or a single 5 spinel-body having no or substantially no radial distribution of defects and/or impurities may be formed, preferably having Each having at least about two dimensions of Congmi and a third dimension of at least about 10 cm, having a dissolved concentration of about ^3 atoms/cm 3 , and a dissolved oxygen concentration of about 2_3χ1 () 17 atoms/cm 3 . 'And a dissolved nitrogen concentration of about 1-5X1015 atoms/cm3. Preferably, a continuous monocrystalline, continuous twin-crystal, or near-single-crystal body having no or substantially no radially distributed defects and/or impurities may be formed, each having at least about 30 At least two dimensions of centimeters and at least about one third dimension of _m, having a dissolved carbon of about 1-5 x 1 017 atoms/cm 3 ; agronomic degree, a dissolved oxygen concentration of about 2 initial atoms of 7 cubic centimeters, and about 1 5溶1015 atoms/cm3 of dissolved nitrogen concentration. More preferably, a continuous single (four) or bismuth crystal having no or substantially no radial distribution of defects and/or quality may be formed. [One of the bodies of the money crystal has at least two dimensions of at least about 35 cm and at least about The third dimension of 10 cm has a dissolved carbon concentration of about atom/cm 3 , a dissolved oxygen concentration of about 2-3 x 1 〇 17 atoms/cm 3 , and a dissolved nitrogen concentration of about 1-5 χ 1015 atoms/cm 3 . Further preferably, a continuous single crystal germanium, a continuous twintite, or a near single crystal stone having no or substantially no radial distribution of defects and/or impurities may be formed, each having at least about At least two dimensions of the rice and a third dimension of at least about 2 cm, having a dissolved carbon concentration of about 1-5 χ 1017 atoms/cm 3 , a dissolved oxygen concentration of about 2 _ 3 χΐ〇η atoms/cm 3 , and about atoms / cubic centimeter of dissolved nitrogen concentration 23 200921924 degrees. Further preferably, a continuous single crystal having no or substantially no radial distribution of defects and/or miscellaneous shells may be formed; 5 ' 'continuous bimorphs, or a single monolithic body, each having at least At least two dimensions of about 50 cm and a third dimension of at least about 2 cm, having a carbon concentration of about 5 degrees <1〇17 atoms/cm 3 , about 2-3 x 1017 atoms/cubic The dissolved oxygen concentration of centimeters, and the concentration of about 1-5 χ 1015 atoms / green rice. Still more preferably, a body of continuous single crystal germanium, continuous twin germanium or near single sa having no or substantially no radial distribution of defects and/or impurities may be formed, each having at least about 6 cm. At least two dimensions and at least about 20 cm - the third dimension, having a dissolved carbon concentration of about 10 15 x 1 G atom / cubic centimeter, a dissolved oxygen concentration of about 2_3 - 17 atoms / cubic centimeter ' and a solution of about ... atom / cubic centimeter Nitrogen concentration. Further, L 彳 forms a continuous single crystal slab, continuous twin slab, or near single crystal slab having no or substantially no radial distribution of defects and/or impurities, each having at least about 70 At least two dimensions of centimeters and at least approximately the third dimension of the job-U, having a dissolved carbon concentration of w_5xiQl7 atoms/cm 3 , a dissolved oxygen concentration of about 2-3 Χΐ〇Π atoms/cm 3 , and about atoms/cubic The concentration of dissolved nitrogen in centimeters. 20 The upper limit of the horizontal dimension of the prayer state in which the concentration of the aforementioned impurities is produced according to an embodiment of the present invention is determined only by the technique of casting and the technique of hanging (4). Continuous twinite, or two: not determined by the method itself. Thus, according to the present invention, an as-cast continuous single crystal germanium solid body having the aforementioned impurity concentration can be formed, preferably having at least two dimensions of each of the internal dimensions of the stack and the third dimension and the ingot of the ingot The body is defined as the nuclear shape, and the length can be referred to as the length, width, and height of the 24 200921924. The seed crystal used in the casting process according to the present invention may have any desired size and shape, but is suitable as a geometric block of single crystal germanium, twin germanium, near single crystal germanium, or geometrically ordered polycrystalline germanium, such as square, rectangular, Hexagon, diamond 5-shaped, or octagonal block. It can be shaped to facilitate paving, or it can be placed side-by-side or "tiled" and conforms to the bottom of the desired model. Also in accordance with embodiments of the present invention, the seed crystals may be placed on one or more sides of the crucible including all sides. Such seed crystals can be obtained, for example, by sawing a source of crystalline germanium, such as a single crystal germanium, into a block having a desired shape. The seed crystal can also be cut and formed by a sample of continuous single crystal germanium, continuous twin germanium, near single crystal germanium, or continuous geometric polycrystalline germanium manufactured by the method of the present invention, so that the seed crystal used for the subsequent casting process can be initially Casting process manufacturing. Thus, for example, continuous single crystal germanium, continuous twin germanium, or nearly single crystal germanium cut or otherwise obtained from continuous single crystal germanium, continuous twin germanium, or near single crystal germanium ingots can be used as 15 For the subsequent casting of the model. Such seed crystals may have the size and shape of one side of the crucible or other container in which the seed crystal is placed, such as the bottom, or substantially the size and shape. For single crystal casting, it is preferred to have as few crystal seeds as possible covering the bottom of the crucible to prevent incorporation of defects. For single crystal casting, it is also preferred to have a predetermined seed arrangement having two different crystal orientations such as (100) and (m) covering the bottom of the crucible. Preferably, the seed crystal arrangement comprises a "protective" portion having a (100) pole direction perpendicular to one of the bottoms of the crucible and a seed crystal having a (111) pole direction perpendicular to the bottom of the crucible and surrounding the middle portion. As such, the seed crystals may have a size or shape or substantially the size and shape in which one or more sides of the crucible or container, such as the bottom, are seeded to perform the casting method according to the present invention. 25 200921924 The method and apparatus according to the present invention will now be described. However, it is necessary to understand that it is not the only method of making Shi Xi. x Kang's principle of the invention forms the first picture of the 矽 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Embryo 12 (). In addition, the close neighbors form a close-knit relationship, thus forming a specific grain boundary that is formed by the pre-selected error. In the evening, deliberately selected grains are large, for example, for the casting of geometric polycrystalline germanium, with a small cross-sectional grain size and preferably; ^ obtained crystallized geometric polycrystalline stone small and shape and grain height =: =: equal or approximate For the seed crystals, most of the crystals are crystallized, for example, by cutting or q ^. If the geometry of the geometry is more than four (four) flat germline ❹ " _ = 6 lines = polycrystalline money key geometry polycrystalline Huan section grain large" " geometric ceremonial cut, then the crystal grain in the crystal Size and shape. = Shape will be similar to geometry. 'It's made by cutting or by bean. It's made from geometry. _ Ingot geometry. (4) Flat embryo can be "geometric polycrystalline stone seed crystal" (called "geometry" Ordered polycrystalline (tetra) crystals), and can be used as a model for subsequent geometric polycrystalline fabrication. Such seed crystals may have seed crystals placed in the center or other contents such as bottom size and Wei or substantially the size and impurities. When such seed crystals are used in the process of the present invention, the resulting geometric polycrystalline spine has the same or substantially the same size and shape as the grains in the seed crystal. The seed crystal 100 can be monumentally placed and preferably placed to substantially cover the entire bottom surface of the catastrophe. It is also preferred that the crucible 110 has a release coating such as a release coating made of dialysis 26 200921924, or a liquid encapsulant to assist in removing the gentleman k from the crucible 110, QBa is second. In addition, the seed crystal may comprise a single crystal singular embryo having a desired crystal orientation of @ or two different desired crystal orientations of from about 3 mm to about 100 mm. Although the specific number and size of the seed crystal 100 are shown in Figure 1, see , ° 曰 skilled people obviously know that depending on the use, can increase or decrease the number and size of the crystal. Referring to Figure 2, a plan view of other arrangements of seed crystals 300 and 310 is presented. In Fig. 2, the seed crystals 300 and 310 are placed in a bottomed and walled (not shown) such as the bottom of the crucible 110 shown in Fig. 1, thus allowing the seed crystal to be different in 1 The crystal orientations are closely adjacent to cover or near the full width 320 of the fully covered bottomed and walled bottom surface. According to the present invention, the seed crystals 300 and 310 may be single crystal blocks. Preferably, the seed crystal 300 has a (100) crystal orientation, and the seed crystal 310 has a (1 Å) crystal orientation such that its individual polar orientation is perpendicular to the bottom surface of the crucible 110. As shown in Fig. 2, a series of in (in) seed crystals 310 are selectively placed to surround the 15-string (丨(9)) seed crystal 300. Seed crystal 310 is shown in Figure 2 with (111) polar perpendicular to the bottom surface of crucible 110 because it is believed that the (111) crystal orientation can provide a low energy growth front and the seed crystal 310 may have other crystal orientations. Preferred seed crystal 300 has a different crystal orientation than seed crystal 310. Although the seed crystals 300 and 310 of a particular number and size are shown in Fig. 2, it will be apparent to those skilled in the art that the crystal orientation of the seed crystal can be changed depending on the purpose of the application. For example, one of the two series of crystals 300 and 310 can be a single single crystal squamous embryo. In other words, the seed crystal 300 is a single crystal (ι00), a single spheroid surrounded by a series of (111) seed crystals 31 ’ or any other alternative combination to cover the bottom of the crucible 110. When fabricating such a specially selected seed crystal arrangement and subsequent grain boundary alignment, preferably 27 200921924 grain boundary junctions have only two grain boundaries that meet a given angle 隅, as shown in Figure 2 arrangement. In this way, the seed crystal 3〇〇 can be placed on the bottom surface of the catastrophe, and the seed crystal 310 can be placed on the bottom surface of the crucible which is not occupied by the seed crystal 3〇〇. The tantalum ingots cast using the seed crystals 300 and 310 will be described later with reference to Figures 3, 4 5 and 6G. The seed layout (or model) disclosed in Figures 1-2, such as the Shixi feed (not shown), can then be introduced into the top 10, 300 and/or 31〇 and then 'melted . In addition, Hyun Rong can be imported into 坩埚11〇. In another example, the crucible 110 can be first adjusted to be very close to the melting point of the crucible or up to 10 o'clock, and then introduced into the molten stone. According to an embodiment of the present invention, the thin layer of the stone can be dissolved before the curing starts. Then, in any of the examples discussed above, the crucible 110 is cooled, whereby the heat is radiated to the surroundings by, for example, a solid heat sink material from the bottom of the crucible 110 (and the side, only when the seed crystal is also tiled to the side) Remove the heat while still 15 she is hot to the open top of the 坩埚110. In this way, the molten crucible is introduced, the seed crystal maintains the solid, and the directionality of the miscellaneous g] causes the columnar crystal grains to grow upward. In this way, the resulting tantalum ingot will simulate the orientation of the crystals of the seed crystals 100 or 300 and 310. The resulting ingot can be cut, for example, into horizontal flats for use as a layer B of other casting processes. The slab may, for example, have the size and shape or substantially the size and shape of the surface of the crucible or other container 20 for casting. For example, there is a flat embryo that can be used in the casting process. The seed crystal orientation thus used for forming the crucible can be selected to specifically affect the final controlled crystal structure of the crystal structure obtained by the obtained Shi Xizhen bond. Contrary to the embodiment of the present invention, the casting method is known to involve direct solidification of the fused block of the fully melted 28 200921924 to be uncontrolled. V plant 44·炙μ D. i
一糊向於孕核涉及差排簇晶或差排 差排及差排容易吸引的雜質造成電載子的 决逮復合以及作為光伏打材料效能的快速降級。如此，根 康本毛月之實施例’小心計劃及種晶規則晶粒邊界網絡用 ^單晶碎或雙晶歡鑄造完成，讓晶粒尺寸、形狀及取向 肖白選擇來最大化次要載子壽命及雜質的獲得，同時最小 〇化結構缺陷。 於設置個別晶種1 〇〇、或3〇〇及31〇替代使用多個單晶石夕 種晶之替代例中，切割或以其它方式得自於先前單晶石夕、 雙晶矽、或近單晶矽鑄造中所製造之鑄錠之矽截面或矽扁 15胚可用作為單一種晶用於根據本發明鑄造單晶矽、雙晶 夕或近單晶矽。此種單一種晶可具有與用來進行鑄造之 坩堝或其它容器表面相同尺寸及形狀，或實質上相同尺寸 及形狀。例如，取自於使用第2圖所示晶種佈局圖或模型所 形成之矽鑄錠之單一種晶可用於隨後之鑄造程序。前述任 何晶種排列也適用於鑄造單晶矽固態本體、雙晶矽固態本 之0 s* ' 或近卓晶石夕固態本體’此處種晶也置於时塌底面上或 底面及側面上。 參照第3圖，顯示於鑄態矽400之鑄錠固化後通過坩堝 110中心之縱剖面圖。第3圖中線A-A之平面圖係對應於第2 圖所示之晶種佈局圖或模型。於第3圖所示之實例中，如第 29 200921924 2圖之平面所示，（1〇〇)晶種3〇〇係置於坩堝n〇之底面上但 (11 l)sa種並未包圍（1〇〇)晶種。於本實例中所得石夕4〇〇 #錢係與掛禍表面接觸，該等表面可用作為於鱗造程序之 固化期期間不同晶粒取向之晶體成長之多個孕核位置。例 5如坩堝110之彎曲角隅410可用作為多晶矽區420成長之孕 核位置，該成長將競爭得自（100)晶種300之（1〇〇)單晶矽區 430之孕核及成長。於鑄造期間，多晶輕侵入晶種3〇〇， 所得鑄錠4〇〇為部分單晶矽及部分多晶矽。（1〇〇)單晶矽 與多晶石夕區420間之分界係以線44〇說明，顯示多晶石夕區42〇 1〇如何由位於角隅41〇之孕核位置向上成長。如此，由於隨機 取向粒例如由坩堝HQ之側壁隨機取向晶粒之競爭橫向 晶粒成長’（100)單晶石夕區43〇之孕核及成長被溶姓。 進步參考第3圖，於鑄造完成後，所得鑄態矽4〇〇之 鑄錠切成五列晶磚450及二側板46〇。側板46〇典型為多晶矽 I5且含有於禱造期間從掛禍11〇壁擴散之雜質。如此側板· 可被移出’用作祕後製造程序之進料。若期望鎿造(100) 單晶矽，則第3圖所示五塊晶碑45〇中只有三者將含(獅)單 晶矽。兩塊晶磚450及二側板46〇將只含多晶矽，或含有多 晶石夕與單晶石夕的組合，如線440通過其中之晶磚45〇指示。 2〇如此，鑄鍵400中之（100)單晶石夕區43〇之體積產量將因多晶 矽區420之體積而減少。 參照第4圖，顯示於鑄態石夕敎4〇〇固化後通過掛禍110 中心之縱剖面圖。第4圖之、線A-A之平面圖同樣係相當於第2 圖所示之晶種佈局圖或模型。於第4圖所示實例中，使用第 30 200921924 2圖所不晶種細及31〇之排％，（⑽）晶種綱置於掛禍HQ 底面上’（111)晶種31〇包圍（1〇〇)晶種3〇〇。於本實例中部 刀所知矽鑄錠400接觸坩堝表面，包括坩堝11〇之彎曲角隅 410 ’其可用作為多晶珍區42()成長之孕核位置。（in)單晶 5矽區510之孕核及成長將與多晶石夕區42〇之成長競爭且最終 限制多晶矽區420之成長量。 如此於鑄造期間，多晶矽區420之成長受（111)單晶矽區 510對（111)晶種310上⑴1)單晶石夕區510之競爭成長所限。 (111)單晶矽區510與多晶矽區420間之分界以線44〇顯示，說 10明多晶矽區420之成長如何受到（HI)單晶矽區510由於晶種 310之孕核位置的向外成長所限。同理，（111)單晶矽區51〇 與（100)單晶石夕區430間之分界以線520顯示，說明由（in)晶 種31〇成長之（111)單晶矽區51〇之晶粒與由（100)晶種3〇〇成 長之（100)單晶矽區430交錯。所得鑄錠400於側板460只含有 15多晶矽區42〇。如此高品質（100)及（111)單晶矽雙晶含於鑄 態石夕400之鑄錠之區430及區510。（111)單晶矽區510之孕核 及成長限制由坩堝110側壁之隨機取向晶粒之競爭性橫向 晶粒成長。 進一步參考第4圖，於鑄造完成後，所得鑄態矽400鑄 20 鍵切成五列晶磚450及二側板460。含有多晶矽區420之側板 460被移開且可用作為隨後鑄造程序之進料。如此，第4圖 所示之全部五塊晶磚450將含有單晶矽或雙晶矽，中央三塊 晶磚450含（1〇〇)單晶矽，外側兩塊晶磚含高品質部分（100) 及部分（111)取向之雙晶矽。因此藉（111)單晶矽區510之成 31 200921924 5 10 15 20 4圖^區42G之體積而減少多晶奴數量。如此於第 圖人所示實例中，得自第2圖所示晶種佈局圖或模型之禱態 石各有抗多晶碎成長之緩衝層，且改良每财鑄鏡之單晶 ::數量。相信原因係來自於⑴1)晶_中之㈤)晶 °之低此里成長鋒，其將比於㈣丨㈣隅彻之隨機 °夕曰a碎之孕核及成長S快速孕核及成長。 第5圖為流程圖顯示根據本發明之珍之製法實例。根據 方法刪始於兩種晶體取向諸如（1GG)及（11G)之單晶 :種晶用於單晶矽之成長，以及排列單晶矽種晶於坩堝:曰 5曰—個晶體取向之種晶係設置成圍繞另-個晶體取向之種 =(步驟_)。另外㈣職其它方式得自單㈣或雙晶石夕 之單扇胚可用作為單一種晶。其次，石夕進料添加至 ”尚(步驟61G)。然後㈣從頂部加熱，掛瑪底部從底部冷 郃(被動或主動；參考步，騎5)。於轉期間，監視石夕之炫 解I1自來追縱與控制gji界面之位置（步驟㈣）。允許石夕之 炫解階段進行至部分單晶㈣晶熔解為止(步驟625)。—旦 期望部分單晶树晶已經轉，結束炫解階段，開始晶體 成長階段(步驟630)。讓晶體之成長於_内單向垂直持續 至石夕結晶化完划步,_35)。最後，移㈣㈣受進一步加 工處理（步驟640)。 如第6A圖所示，矽進料2〇〇例如可以兩種方式之一導入 3種晶220之时祸210内部。於第-方式，掛禍21〇以固態石夕 進料200载荷至滿載’適合呈習知尺寸之厚塊，載滿的掛蜗 21〇置於鑄造站（圖中未顯示）。 32 200921924 如第6B圖所示，掛堝210中之熱輪廓資料係設定為时禍 110之矽進料頂端加熱至熔解，底部經主動或被動冷卻來維 持於坩堝210底部之晶種220之固相，亦即當進料200熔解時 晶種不會漂浮。固態散熱座材料230接觸坩堝210底部用來 5 輻射熱至水冷式壁。例如散熱座材料230可為固態石墨塊， 較佳具有與坩堝底部相等或更大的維度。根據本發明，例 如，當使用具有底面為66厘米χ66厘米之坩堝時，散熱座材 料可為66厘米χ66厘米χ20厘米。坩堝210之側壁較佳並未以 任何方式冷卻，只要晶種220係只位於坩堝21〇底部上即 10可。若晶種220係位於坩堝210之底部及側部，則散熱座材 料230將置於坩堝210之底部及側部上用來維持期望的熱輪 廓資料。 矽進料200之溶解相經密切監視來追蹤已溶解的矽與 晶種間之界面位置。較佳熔解2 4 〇 (第6 Β圖所示）進行至全部 15進料矽200 (但晶種22〇除外）完全熔解為止，隨後晶種220經 卩刀炫解。舉例s之’可密切控制加熱，於坩禍之其它位 置之達到發熔點後，於时堝外側面測量，經由維持約為 o·1 c/刀鐘讓晶種220不會完全溶解。較佳，經由維持^約 為0.05C/分鐘可密切控制加熱，於掛堝之其它位置之達到 20矽炫點後，於_外側面測量。例如根據本發明，ΔΤ可於 禍’、大塊;5墨間之i^外侧面上測量，可將浸桿插入 於炫體24G内測量炼體溫度俾便計算已經溶解之晶種22〇部 分。 第6C圖所示，部分25〇顯示於溶體携下方之晶種2如 33 200921924 總厚度之已熔解部分。於晶種220之一部分250已經於熔體 240下方熔解後，快速結束熔解階段，開始晶體成長階段， 其中於坩堝210頂部之加熱減少及/或於散熱座材料23〇底 部之冷卻增加。作為此種方法之實例’第6D圖所示圖表舉 5例說明部分250晶種220之熔解呈時間之函數變化。如第6D 圖所示，具有初始厚度約5厘米至6厘米之部分晶種徐缓熔 解至恰留下固％晶種2厘米下方。舉例言之，可密切控制加 熱，於坩堝之其它位置之達到矽熔點後，於坩堝外側面（例 如透過安裝於冷卻區段之熱偶）測量，經由維持ΔΤ約為〇1 10 °C/分鐘讓晶種220不會完全熔解。較佳，經由維持ΔΤ約為 0.05C/分鐘可密切控制加熱，於坩堝之其它位置之達到矽 熔點後，於坩堝外側面測量。此時，快速結束熔解階段， 開始晶體成長階段，由於圖表縱座標上測得之固體厚度之 比較性升高指示。 15 如第6Ε圖所示，部分25〇顯示於熔體240下方之晶種220 總厚度之已熔解部分。於部分25〇晶種22〇於熔體24〇下方已 經熔解後，快速結束熔解階段及開始晶體成長階段，其中 於坩堝210頂部之加熱減少及/或於散熱座材料230底部之 冷卻心加。然後如第6F圖所示，種晶成長於坩堝210内部持 20續為單向及垂直方向成長，同時經散熱座230抽出熱量直到 矽結晶化完成為止。較佳實質平坦之固-液界面285由坩堝 210底面向上傳播遠離底面。當坩堝21〇内部之頂至底熱梯 度均勻時，晶體成長完成後，鑄造週期結束。然後整個縳 錠280冷卻至室溫。用於單晶矽之鑄造，此種晶種單向成長 34 200921924 產生禱造單晶石夕290之連續固態本體。 如第6G圖所示’例如根據第2圖之晶種佈局圖或模型， 種晶成長於掛禍210内部縱向持續至矽結晶化完成為止。當 坩堝210内部之頂至底熱梯度均平時，鑄造週期結束。然 5後，整個鑄錠260緩慢冷卻至室溫。用於單晶矽及雙晶矽之 鑄造，如第6G圖所示，使用（111)晶種31〇環繞（1〇〇)晶種3〇〇 之％繞杈型（如第2圖所示）製造例如於由其中可孕核及成長 之個別⑴1)晶種上之（m)取向之晶粒270。 藉此方式，高 叩貝（111)及（1〇〇)晶體取向單晶矽之雙晶占據大部分或較 °佳實質上大部分鑄錠260之體積。 於另一方法中，如第7圖所示，矽進料2〇〇可首先於分 ^隔間或分開熔體容器300熔解。晶種22〇可或可未由頂部 部分熔解，隨後熔融進料3〇5透過熔解管3丨〇内部，隨後如 b參照第6B-6G圖之說明進行冷卻及成長。於另一個實施例 15中，石夕種晶可置於賴210之壁面上（圖中未顯示），種晶可 由掛禍210之側面及底部進行成長，如前文說明。另外，石夕 進料200係於與掛禍210分開之溶體容器·内炼解，且同 2掛禍210加熱至;^之溶點，加熱係控制成晶種不會 2〇 μ炫解。§日日種220部分炫解時，炼融進料305可由炼體 容器300轉移入㈣210 ’開始冷卻及結晶化。如此，根據 本發明之實施例，部分結晶化妙之固態本體可包括晶種 220。另外，於炼體導入前，晶種可維持完全固態。於此種 情況下，溶體容器300内之炫_加熱超過魅，當導入超 熱液體時，超熱液體允許熔解部分晶種。 35 200921924 於二階段式铸造站中，諸如第7圖所示，炫融進料305 將由炼體容器3_下，著陸於晶種220上，於固化期間獲 付結晶性。另外，溶解可於中央溶體容器扇進行其進給 固化賴之分散式配置，諸如一套或多套_21〇 (圖中: 5顯不）。根據本發明之實施例，固化坩堝可與於坩堝側部及 底部之任-丨或二者上之晶種22〇對齊校準。此種辦法之某 些優點包括：炫解系統與固化系統分離，允許各缚造步驟 之最適化更優異；矽之半連續熔解，此處新材料之熔解以 規則方式出現，視需要維持坩堝之供應來源；頂部矽結成 10礦渣（及底部矽可能排放）’同時固化站由熔體中央進料，提 升起始矽材料之純度；以及允許熔體容器300與熔融進料 305達成平衡，不再變成為雜質的顯著來源。 如此於鑄錠260或280已經藉前述方法之—鑄造後，所 得鑄錠可進一步藉切斷鑄錠底部或另一個截面加工處理， 15使用切斷部分作為隨後鑄造回合之單晶矽或多晶矽晶種來 形成根據本發明之單晶石夕、雙晶石夕、或近單晶石夕本體，以 及其中此種單晶晶種之大小及形狀為用於隨後鑄造回合之 坩堝底部之相同大小及形狀，其餘鑄錠可被切成晶磚及晶 圓用於加工成為光伏打電池。另外，整個鑄旋例如可切成 20水平扁胚用作為未來鑄造回合於多個鑄造站之種晶。 於根據本發明之實施例之方法所使用之矽進料可含有 諸如選自於一表單之一種或多種摻雜劑，該表單包括：硼、 鋁、鋰、鎵、磷、銻、砷、及鉍。此等摻雜劑之總量可為 以原子百分比計每百萬份約0·01份(ppma)至約2 ppma。此種 36 200921924 摻雜劑之總量可為約0.01 ppma至約2 ppma。較佳，矽中之 摻雜劑數量為由矽所製成之晶圓具有電阻率約〇.1至約5〇 歐姆-厘米，較佳約0.5至約5.〇歐姆-厘米。另外，具有適當 液相之其它材料可使用此處揭示之方法及裝置鑄造。例如 5 鍺、砷化鎵、矽鍺、藍寶石、及多種其它ΙΠ-V或II-VI材料 以及金屬及合金可根據本發明之實施例鑄造。 下列實施例為符合本發明之實施例之實驗結果。此等 實例僅供舉例說明本發明之實施例而絕不可解譯為囿限本 發明之範圍。 10 實例1 时禍之準備：坩堝置於包含兩層之支載結構上。支載 結構之底層為尺寸8〇厘米χ8〇厘米χ2.5厘米之固體同模模 製石墨板支載一複合層。上複合層具有内區，其為尺寸6〇 厘米x60厘米χΐ·2厘米之導熱同模模製石墨板，各邊係由厚 15 I.2厘米之10厘米絕熱石墨纖維周長所環繞。藉此方式，複 合層完全覆蓋底層。 晶種之準備：得自MEMC公司之純左奇拉斯基(cz)矽 之胚晶（單晶矽）含0.3 ppma,，使用鑽石塗覆帶鋸順著縱向 切割’因而每邊測得140毫米之正方形截面。所得單晶石夕塊 20使用相同鋸通過截面切割成為厚約2厘米至約3厘米之扁 胚。此等扁胚用作為單晶石夕種晶或「晶種」。維持石夕胚晶之 (100)晶相學極取向。然賴得單㈣扁胚㈣於石英时塌 底部，扁胚之（_方向向上，⑽)方向維持平行於㈣^ 一邊。石英㈣具有邊長68厘米之方形截面及深約4〇厘 37 200921924 米。扁胚排列於坩堝底部，縱向維度係平行於坩堝底部， 側部接觸而於坩堝底部上形成單一完整的扁胚層。 鑄造：坩堝載荷以晶種板，然後於室溫填充至總重265 千克固態矽進料。加入少數高度摻硼矽晶圓來提供足量硼 5 獲得總鑄錠掺雜約為0.3 ppma。經填裝後之坩堝首先以石墨 載板環繞，石墨載板停靠在支載結構之絕熱部上，然後載 荷入用來鑄造多晶矽之原位熔解/方向性固化鑄造站。熔解 程序係經由將電阻加熱器加熱至約1550°C進行，加熱器係 組配成由頂開始加熱，藉開啟絕緣體共6厘米讓熱輻射出至 10 底部。此種配置造成熔解係以頂-底方向朝向坩堝底部進 行。通過底部之被動式冷卻，如藉熱偶監視，造成種晶於 熔點維持固態。熔解程度係藉石英浸桿每10分鐘降入熔體 内部測量。浸桿高度與於鑄造站中由空坩堝所得測量值比 對來測定剩餘固態材料之高度。經由浸桿測量，首先進料 15 熔解，然後允許熔解相只連續至留下約1.5厘米種晶高度為 止。此時，加熱功率降至溫度設定值1500°C，來自底部之 輻射藉開啟絕緣體至12厘米增加輻射。固化開始前，額外1 毫米或2毫米種晶熔解，藉浸桿測量值觀察得。然後種晶單 晶成長進行至固化步驟結束。鑄造週期之成長階段及其餘 20 部分係以一般參數進行，此處頂至底之熱梯度均平化，然 後整個鑄錠缓慢冷卻至室溫。鑄態矽產物為66厘米χ66厘米 X 2 4厘米鑄錠。與晶種一致之結晶度區始於底部且隨形於未 熔解材料邊緣，由該處當開始成長時朝向坩堝壁橫向向外 成長，朝向結晶化終點穩定成為常數大小。目測檢驗由鑄 38 200921924 =之晶碑各面發現單㈣構。 準備.製備晶種層，始於18千克方形〇〇〇)板用 之霜芸底。^齊校準，提供58厘米x58厘米及厚2_3厘米 豆"區此等板共同放置於更大的方形，取中於坩堝。 /、人此方形由厚2厘米之(Ul)取向總晶種層所圍繞，讓晶種 層共形成631+χ63ϋ#之方形。 10 鑄造：含晶種之坩煱填裝以矽至總重265千克，置於鑄 造站。如實例1進行鑄造，監視處理程序，確保通過熔解終 點及固化起點晶種層維持完好。所得鑄錠切成12.5厘米晶 磚之5x5格狀。光學檢驗晶磚之晶體結構，顯示（111)晶體作 為緩衝層，防止隨機孕核晶粒之入侵（100)體積内部。 如此根據本發明之貫施例及前述實例，石夕可為铸阵連 續單晶矽、鑄態雙晶矽、或鑄態近單晶矽之本體，較佳大 15致上不含或不含徑向分布的缺陷諸如OSF缺陷及/或旋渦缺 陷，且較佳，該本體之至少二維度較佳至少約為1〇厘米， 較佳至少約為20厘米，更佳至少約為30厘米，又更佳至少 約為40厘米，又更佳至少約為50厘米，又更佳至少約為6〇 厘米，及最佳至少約為70厘米。最佳，此種石夕本體之第二 20維度至少約為5厘米，較佳至少約為15厘米，及最佳至少約 為20厘米。>5夕本體可為至單一本體之一個分開塊狀物，或 可含於或全部或部分包圍於其它碎内部。石夕本體較佳係成 形為至少有二維各自之大小如同鑄造容器之内部維度。如 此處揭示，本發明之實施例可用於藉簡單且具有成本效益 39 200921924 之禱造方法來製造早晶妙、雙晶石夕、或近早晶碎之大型本 根據本發明之實施例由矽製成之晶圓適合為薄型晶圓 且可用於光伏打電池。此外，晶圓可為η塑或p型。例如， 5 晶圓可為約10微米厚至約700微米厚。此外’用於光伏打電 池之晶圓較佳具有擴散長度（LP)大於晶圓厚度⑴。例如， LP對t之比適合至少為0.5。例如至少約為1·1或至少約為2。 擴散長度為小量載子(諸如於ρ型材料中之電子）與大量載子 (Ρ型材料中之電洞）復合前可擴散之平均距離。LP係透過關 1〇係式Lp=(Di:)1/2與小量載子壽命τ相關，此處D為擴散常數。 擴散長度可藉多項技術測定，諸如光子束感應電流技術或 表面光伏打技術測定。例如參考「太陽能電池基礎」，作者 A. Fahrenbmch及R.Bube，學術出版社，1983年9〇1〇2頁， 有關如何測量擴散長度之說明。 15 20 晶圓具有約100毫米至約600毫米之寬度。較佳晶圓肩 有至少一個維度至少約為50毫米。由本發明之矽製成之羞 圓以及結果藉本發明所製成之光伏打電池例如具有約^ 方厘米至約細平方厘米之表面積。晶圓之正面較佳經織 構化。例如晶圓可使用化學㈣、或雷射 械銘刻來織構化。若使用具有（⑽)極取向之晶圓 可經蝕刻而形成各向異性織構化表面，係經古： 例如約贼至約啊歷經約1〇分鐘至約12〇分鐘二-㈣化鈉水溶液中處理晶圓進行_。水㈣_ ^ 40 200921924 5 10 15 i 20 如此，使用根據本發明之鑄態矽鑄錠製造之晶圓可製 造太陽能電池，經由將鑄態矽之固態本體切片來形成至少 一片晶圓；視需要可於晶圓表面上進行清潔程序；視需要 可於該表面上進行織構步驟；例如經由摻雜該表面而形成 p-n接面；視需要可沉積抗反射塗層於該表面上；視需要例 如可藉鋁燒結步驟而形成選自於背場及鈍化層中之至少一 層；以及於晶圓上形成導電接觸件。鈍化層為與裸晶圓表 面界面繫結於表面原子之懸垂鍵之一層。石夕上鈍化層之實 例包括氮化矽、二氧化矽及非晶矽。此層通常比丨微米更 薄，可透光或用作為抗反射層。 於使用例如P型矽晶圓製造光伏打電池之典型—般程 序中’晶圓於-側暴露於適當η摻雜劑來於晶圓正面或光接 收側上形成-發光層及ρ_η接面。典型地，η型層或發光層 之形成料，_由❹技藝界財狀㈣諸如化學沉 積或物理沉積’首先沉積讀雜劑於㈣晶圓之正面上，如 此沉積後，η摻雜劑例如魏逐人⑪晶圓正面内部進—步^ 散η摻雜劑至晶圓表面。「逐入」步驟常見將晶圓暴露於高 溫達成。藉此於η型層與ρ型石夕晶圓基材間之邊界區形成 接面。於师誠其它摻雜來形成發光層之前，晶圓表面 可經織構化。為了進—步改良光吸收，任選的抗反射塗覆 層諸如氮切典魏用於晶圓正面，偶賴時提供表面及/ 或本體同時鈍化。 為了利用Ρ·η接面暴露於光能所產生的電位光 池典型設有導電正面接觸件於晶圓之正面上及導電背面接 41 200921924 但二接觸件可位於晶圓背側上。此 或多種高度導電性金屬所製成，因 實質上不〜/ 例之太陽能電池可包含由不含或 、3倥向分布缺陷之連續單晶矽、雙晶矽、$ 晶石夕本體所製成之叉_、或近早 «各自本體可如前文說明，例如至 米之第三雄/ 個維度及至少約為20厘 10 反射声;2 ’日日日_部之ρ_η接面，晶圓表面之任選的抗 _具有選自於背場及鈍化層中之至少；及 二圓ί::電接點此處該本體可不含或實質上不含旋渦 缺^及不含或實質上不含OSF缺陷。 15 20 觸件於晶圓之背面上， 種接觸件典型係由—種 此典型為不透明。 f ;人士顯然易知可未悖離本發明之範圍或精髓 一結構及方法做出多項修改及變化。例如，所揭 =有關形成單“之製程及方法也適•形成雙晶石夕或 近早晶㈣其組合。此外，雖然於此處已經說日歸之鑄造， 但未挣離本㈣之_及_可_其它铸财料及非 金屬結晶材料。例如發明人預期涵蓋根據本發明之實施例 =其它材料之缚造，諸如钟化鎵、碎鍺、氧化銘、氮化錄、 氧化鋅、硫化鋅、坤化鎵銦、録化銦、錯、鋪氧化物、 鑭系元素氧化物、氧化鎂、及其它半導體、氧化物、及與 液相之金屬間化合物。由考慮此處揭示之本發明之說明書 及實務’熟諳技藝人士顯,然易知其它本發明之實施例。意 圖說明書及實例僅視為舉例說明之用，本發明之真諦範圍 及精髓係由如下申請專利範圍指示。 42 200921924 L圖式簡單說明3 第1圖顯示根據本發明之實施例於坩堝底面上之矽晶 種之排列實例； 第2圖顯示根據本發明之實施例於坩堝底面上之矽晶 5 種之排列實例； 第3圖顯示使用具有單一晶體取向之種晶之鑄錠之剖 面圖； 第4圖顯示根據本發明之實施例使用種晶之一鑄錠之 剖面圖，其中部分種晶具有一個晶體取向，部分種晶具有 10 另一個晶體取向； 第5圖顯示根據本發明之實施例之方法實例；及 第6A-6G及7圖顯示根據本發明之實施例用於單晶矽 或雙晶矽之鑄造方法之實例。 【主要元件符號說明】 100...晶種 260…雜 110...坩堝 270...晶粒 120...扁胚 280…麟 2〇α·.矽進料 285...實質上平坦固-液界面 210…坩堝 290...鑄態單晶矽 220...晶種 300、310...晶種 230...散熱座材料 300…熔體容器 240...熔體 305...熔融進料 250...已熔解部分 310·.·熔解管 43 200921924 320...全寬 460...側板 400...鑄態矽鑄錠 510···(111)單晶矽區 410...彎曲角隅 520·.·分界線 420...多晶石夕區 600...方法 430...單晶矽區 605-640...方法步驟 450...晶磚 44A paste toward the pregnancy involves the inclusion of poorly arranged clusters or poorly arranged discharges and impurities that are easily attracted by the discharges, resulting in the arrest of the charge carriers and the rapid degradation of the effectiveness of the photovoltaic materials. In this way, the example of Genkang Maoyue's careful planning and seeding regular grain boundary network is completed by single crystal or double crystal casting, so that the grain size, shape and orientation are selected to maximize the secondary load. Sub-life and impurity acquisition, while minimizing structural defects. In the alternative of setting a single seed crystal 1 〇〇, or 3 〇〇 and 31 〇 instead of using a plurality of single crystal saplings, cutting or otherwise obtained from the previous single crystal slab, twin bismuth, or The crucible section or crucible 15 of the ingot produced in the near single crystal crucible casting can be used as a single crystal for casting single crystal germanium, twin crystal or near single crystal germanium according to the present invention. Such a single crystal may have the same size and shape, or substantially the same size and shape as the surface of the crucible or other container used for casting. For example, a single crystal taken from a tantalum ingot formed using the seed map or model shown in Figure 2 can be used in subsequent casting procedures. Any of the foregoing seed arrangements can also be applied to the casting of a single crystal solid body, a twin crystal solid body of 0 s* ' or a near-cellocrystalline solid body. Here, the seed crystal is also placed on the bottom surface or the bottom surface and the side surface. . Referring to Fig. 3, there is shown a longitudinal section through the center of the crucible 110 after the ingot of the as-cast crucible 400 is solidified. The plan view of line A-A in Fig. 3 corresponds to the seed layout or model shown in Fig. 2. In the example shown in Fig. 3, as shown in the plane of Fig. 29 200921924 2, the (1〇〇) seed crystal 3〇〇 is placed on the bottom surface of the 坩埚n〇 but the (11 l) sa species are not surrounded. (1〇〇) seed crystal. In the present example, the stone is in contact with the surface of the catastrophe, and the surfaces can be used as a plurality of nucleation sites for crystal growth of different grain orientations during the curing period of the scaly process. Example 5, such as the bend angle 410 of 坩埚110, can be used as the growth site for the growth of the polycrystalline germanium region 420, which will compete for the pregnancy and growth of the (100) single crystal germanium region 430 of the (100) seed crystal 300. During the casting, the polycrystalline light invades the seed crystal 3〇〇, and the obtained ingot 4〇〇 is a partial single crystal germanium and a partial polycrystalline germanium. The boundary between (1〇〇) single crystal 矽 and polycrystalline stone 420 is illustrated by line 44〇, which shows how the polycrystalline stone area 42〇 1〇 grows up from the pregnancy position of the angle 隅41〇. Thus, since the randomly oriented grains are, for example, the transverse grain growth of the grains randomly oriented by the sidewalls of the 坩埚HQ, the (100) single crystal stone region 43 〇 孕 及 及 及 及 及 及 及 及 及 。 。. For the improvement, referring to Fig. 3, after the casting is completed, the obtained ingot of as-cast 矽4〇〇 is cut into five columns of crystal bricks 450 and two side plates of 46 〇. The side plates 46 are typically polycrystalline iridium I5 and contain impurities that diffuse from the wall during the prayer. Such a side panel can be removed as a feed for the post-secret manufacturing process. If it is desired to fabricate (100) single crystal germanium, only three of the five crystal ingots 45 shown in Figure 3 will contain (lion) monocrystalline germanium. The two bricks 450 and the two side panels 46 will contain only polycrystalline germanium or a combination of polycrystalline stone and single crystal, as indicated by the line 440 passing through the brick 45. 2. Thus, the volumetric production of the (100) single crystal stone region 43 in the cast bond 400 will be reduced by the volume of the polycrystalline germanium region 420. Referring to Fig. 4, it is shown in the longitudinal section of the center of the smashing 110 after the solid state of the as-cast stone. The plan view of line A-A in Fig. 4 is also equivalent to the seed layout or model shown in Fig. 2. In the example shown in Fig. 4, using the 30th 200921924 2 map of the seedless fine and 31% of the row %, ((10)) crystal seed is placed on the bottom surface of the hazard HQ '(111) seed crystal 31〇 surrounded ( 1〇〇) Seed crystal 3〇〇. In the middle of the example, the ingot 400 is in contact with the surface of the crucible, including the bend angle 410 of the crucible, which can be used as the pronuclear position for the growth of the polycrystalline area 42(). (in) Single crystal The nucleus and growth of the 矽5 510 will compete with the growth of the polycrystalline slab 42 and eventually limit the growth of the polycrystalline 420. Thus, during casting, the growth of the polycrystalline germanium region 420 is limited by the competitive growth of the (111) single crystal germanium region 510 versus the (111) seed crystal 310 (1) 1) single crystal stone region 510. The boundary between the (111) single crystal germanium region 510 and the polycrystalline germanium region 420 is shown by line 44, and how the growth of the polycrystalline germanium region 420 is affected by the (HI) single crystal germanium region 510 due to the outer position of the seed crystal 310 Growth is limited. Similarly, the boundary between the (111) single crystal germanium region 51〇 and the (100) single crystal stone region 430 is shown by line 520, indicating that the (111) single crystal germanium region grown by (in) seed crystal 31〇 is 51〇. The grains are interdigitated with the (100) single crystal germanium region 430 grown by (100) seed crystals. The resulting ingot 400 contains only 15 polycrystalline germanium regions 42 in the side plate 460. Such high quality (100) and (111) single crystal germanium twins are contained in zone 430 and zone 510 of the cast ingot of cast stone 400. The (111) single crystal germanium region 510 has a pronuclear growth and growth limitation due to the competitive lateral grain growth of the randomly oriented grains of the sidewalls of the crucible 110. Referring further to Fig. 4, after the casting is completed, the obtained as-cast 矽400 cast 20-bond is cut into five rows of crystal bricks 450 and two side plates 460. The side panels 460 containing the polycrystalline crucible region 420 are removed and can be used as a feed to the subsequent casting process. Thus, all five bricks 450 shown in FIG. 4 will contain single crystal germanium or twin twins, and the central three bricks 450 contain (1 inch) single crystal germanium, and the outer two bricks contain high quality portions ( 100) and a portion (111) oriented twin bismuth. Therefore, the number of polycrystalline slaves is reduced by the volume of the (111) single crystal germanium region 510 31 200921924 5 10 15 20 4 . Thus, in the example shown by the figure, the prayer stone obtained from the seed crystal layout diagram or the model shown in Fig. 2 has a buffer layer resistant to polycrystalline growth, and the single crystal of each of the cast mirrors is improved: . I believe that the reason comes from (1) 1) crystal _ middle (five) crystals ° low in this growth front, which will be more random than (four) 丨 (four) ° 曰 曰 曰 碎 孕 孕 孕 孕 孕 孕 孕 孕 孕 孕 孕 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及Fig. 5 is a flow chart showing an example of the manufacturing method according to the present invention. According to the method, single crystals of two crystal orientations such as (1GG) and (11G) are used: seed crystals are used for the growth of single crystal germanium, and crystals of single crystal germanium are arranged in the order of 坩埚:曰5曰-crystal orientation The crystal system is arranged to surround the other crystal orientation = (step _). In addition, (4) other methods are available from single (four) or double crystal slab single fan embryos can be used as a single crystal. Secondly, Shi Xi feed is added to “Shang (step 61G). Then (4) heating from the top, the bottom of the hanging horse is cold from the bottom (passive or active; reference step, ride 5). During the turn, monitor the Shi Xizhi I1 is used to track and control the position of the gji interface (step (4)). Allow the Shi Xizhi dazzling stage to proceed until some of the single crystal (four) crystals are melted (step 625). - It is expected that part of the single crystal tree has turned, ending In the solution phase, the crystal growth phase is started (step 630). Let the crystal grow in _ unidirectionally and continue until crystallization is completed, _35). Finally, shift (4) (4) is further processed (step 640). As shown in Fig. 6A, the crucible feed 2 can be introduced into the interior of the three crystals 220, for example, in one of two ways. In the first mode, the crucible is 21 〇, the solid Shishi feed 200 load to full load 'suitable A thick piece of conventional size is placed in the casting station (not shown). 32 200921924 As shown in Figure 6B, the thermal profile data in the hanging raft 210 is set to 110. The top of the feed is heated to melt, and the bottom is maintained by active or passive cooling. The solid phase of the seed crystal 220 at the bottom of the 210, that is, the seed crystal does not float when the feed 200 is melted. The solid heat sink material 230 contacts the bottom of the crucible 210 for 5 radiant heat to the water-cooled wall. For example, the heat sink material 230 may be solid. The graphite block preferably has a dimension equal to or greater than the bottom of the crucible. According to the present invention, for example, when a crucible having a bottom surface of 66 cm χ 66 cm is used, the heat sink material may be 66 cm χ 66 cm χ 20 cm. Preferably, the side walls are not cooled in any manner, as long as the seed crystal 220 is located only on the bottom of the crucible 21, ie 10. If the seed crystal 220 is located at the bottom and sides of the crucible 210, the heat sink material 230 will be placed on the crucible 210. The bottom and sides are used to maintain the desired thermal profile data. The dissolved phase of the feed 200 is closely monitored to track the interfacial position between the dissolved tantalum and the seed. Better melting 2 4 〇 (Fig. 6 Shown) until all 15 feeds 矽 200 (except for seed crystal 22〇) are completely melted, and then seed crystal 220 is smashed by a file. For example, 'can closely control heating, reach other positions in the disaster After melting point According to the outer side measurement, the seed crystal 220 is not completely dissolved by maintaining about o·1 c/knife clock. Preferably, the heating can be closely controlled by maintaining the pressure of about 0.05 C/min. After the position reaches 20 矽 点, it is measured on the outer side. For example, according to the present invention, ΔΤ can be measured on the outer side of the ^ 、, the large piece; 5 between the inks, and the dipstick can be inserted into the glare 24G. After measuring the temperature of the refining body, the 22 〇 portion of the seed crystal which has been dissolved is calculated. As shown in Fig. 6C, part 25 〇 is shown in the melted portion of the total thickness of the seed crystal 2 under the solution such as 33 200921924. After a portion 250 has been melted below the melt 240, the melting phase is quickly terminated and the crystal growth phase begins, with reduced heating at the top of the crucible 210 and/or increased cooling at the bottom of the heat sink material 23 crucible. As an example of such a method, the graph shown in Fig. 6D shows that the melting of the portion 250 seed crystal 220 is a function of time. As shown in Fig. 6D, a portion of the seed crystal having an initial thickness of about 5 cm to 6 cm was slowly melted to just under 2 cm of the solid crystal seed. For example, the heating can be closely controlled, measured at the outer side of the crucible after reaching the melting point of the crucible, for example, by the thermocouple mounted on the cooling section, by maintaining ΔΤ about 101 10 °C/min. The seed crystal 220 is not completely melted. Preferably, the heating is closely controlled by maintaining a ΔΤ of about 0.05 C/min, and is measured on the outer side of the crucible after reaching the 矽 melting point at other positions of the crucible. At this point, the melting phase is quickly terminated and the crystal growth phase is initiated, as indicated by the comparative increase in solid thickness measured on the ordinate of the graph. 15 As shown in Fig. 6, a portion 25〇 shows the melted portion of the total thickness of the seed crystal 220 below the melt 240. After the portion of the 25 seed crystal 22 has been melted under the melt 24, the melting phase is quickly terminated and the crystal growth phase is started, wherein the heating at the top of the crucible 210 is reduced and/or the cooling core at the bottom of the heat sink material 230 is added. Then, as shown in Fig. 6F, the seed crystal grows in the interior of the crucible 210 and continues to grow in the unidirectional direction and the vertical direction, while the heat is extracted through the heat sink 230 until the crystallization of the crucible is completed. Preferably, the substantially flat solid-liquid interface 285 is propagated upwardly from the bottom surface of the crucible 210 away from the bottom surface. When the top to bottom heat gradient of the 坩埚21〇 is uniform, the casting cycle ends after the crystal growth is completed. The entire ingot 280 is then cooled to room temperature. For the casting of single crystal crucibles, the unidirectional growth of such crystals 34 200921924 produces a continuous solid body of praying single crystal eve 290. As shown in Fig. 6G, for example, according to the seed crystal layout diagram or model of Fig. 2, the seed crystal grows in the longitudinal direction of the smashing 210 until the crystallization is completed. The casting cycle ends when the top-to-bottom thermal gradient inside the crucible 210 is flat. After 5, the entire ingot 260 was slowly cooled to room temperature. For the casting of single crystal bismuth and twin bismuth, as shown in Fig. 6G, use (111) seed crystal 31 〇 around (1 〇〇) seed crystal 3 〇〇 % 杈 type (as shown in Figure 2 The (m) oriented grains 270 on the seed of the individual (1) 1) seed crystals which are fertile and growable are produced, for example. In this way, the twin crystals of the high-order mussels (111) and (1) crystal-oriented single crystal germanium occupy most or more than substantially the volume of the ingot 260. In another method, as shown in Figure 7, the ruthenium feed 2 can be first melted in the compartments or separately from the melt vessel 300. The seed crystal 22 may or may not be melted by the top portion, and then the molten feed 3〇5 is passed through the inside of the melting tube 3, and then cooled and grown as described with reference to Figures 6B-6G. In another embodiment 15, the Shiyue seed crystal can be placed on the wall of the Lai 210 (not shown), and the seed crystal can be grown from the side and bottom of the sabot 210 as previously described. In addition, Shi Xi Feed 200 is in the solution container separated from the hazard 210, and is heated and cooled to the same point; the melting point of the ^ is controlled, and the heating system is controlled to form a seed crystal. . § When the day 220 is partially distracted, the refining feed 305 can be transferred from the refining vessel 300 to (4) 210 ′ to begin cooling and crystallization. Thus, in accordance with an embodiment of the present invention, a partially crystalline solid body can include seed crystals 220. In addition, the seed crystal can remain completely solid before the introduction of the refining body. In this case, the dazzle_heating in the solution container 300 exceeds the charm, and when the superheated liquid is introduced, the superheated liquid allows the partial seeding to be melted. 35 200921924 In a two-stage casting station, such as shown in Figure 7, the slick feed 305 will be landed on the seed crystal 220 from the refining vessel 3_ and will be crystallized during curing. In addition, the dissolution can be carried out in a distributed configuration in which the central solution container fan is subjected to feed curing, such as one or more sets of _21 〇 (in the figure: 5). In accordance with an embodiment of the present invention, the cured crucible can be aligned with the seed crystal 22〇 on either or both sides of the crucible and the bottom. Some of the advantages of this approach include: separation of the dazzling system from the curing system, allowing for optimum optimization of the various bonding steps; semi-continuous melting of the crucible, where the melting of the new material occurs in a regular manner, as needed The source of supply; the top slag is 10 slag (and the bottom sputum may be discharged)' while the solidification station is fed from the center of the melt to increase the purity of the starting ruthenium material; and allows the melt vessel 300 to balance with the molten feed 305, no longer Become a significant source of impurities. Thus, after the ingot 260 or 280 has been cast by the foregoing method, the obtained ingot can be further processed by cutting the bottom of the ingot or another cross section, 15 using the cut portion as a single crystal crucible or polycrystalline twin after the subsequent casting round. Forming a single crystal, a double crystal, or a near single crystal body according to the present invention, and wherein the size and shape of the single crystal seed are the same size for the bottom of the crucible for subsequent casting and Shape, the remaining ingots can be cut into tiles and wafers for processing into photovoltaic cells. Alternatively, the entire casting spin can be cut into 20 horizontal flats for use as seed crystals for future casting rounds at multiple casting stations. The ruthenium feed used in the method according to embodiments of the present invention may contain, for example, one or more dopants selected from a form including: boron, aluminum, lithium, gallium, phosphorus, antimony, arsenic, and bismuth. The total amount of such dopants may range from about 0. 01 parts per million (ppma) to about 2 ppma per million by atom. The total amount of such 36 200921924 dopants can range from about 0.01 ppma to about 2 ppma. Preferably, the amount of dopant in the crucible is such that the wafer made of tantalum has a resistivity of from about 0.1 to about 5 ohm-cm, preferably from about 0.5 to about 5. ohm-cm. In addition, other materials having a suitable liquid phase can be cast using the methods and apparatus disclosed herein. For example, 5 Å, gallium arsenide, antimony, sapphire, and various other bismuth-V or II-VI materials, as well as metals and alloys, can be cast in accordance with embodiments of the present invention. The following examples are experimental results consistent with examples of the invention. The examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention. 10 Example 1 Preparation for the disaster: The crucible is placed on a supporting structure containing two layers. The bottom layer of the supporting structure is a solid layer of the same mold molded graphite plate with a size of 8 cm, 8 cm, 2.5 cm. The upper composite layer has an inner zone which is a thermally conductive co-molded graphite plate having a size of 6 cm x 60 cm χΐ 2 cm, each side being surrounded by a perimeter of 10 cm of adiabatic graphite fibers having a thickness of 15 I.2 cm. In this way, the composite layer completely covers the bottom layer. Preparation of seed crystals: The pure gerberyl (cz) eutectic (single crystal sputum) from MEMC contains 0.3 ppma, and is cut along the longitudinal direction using a diamond coated band saw' thus 140 Square cross section of millimeters. The resulting single crystal block 20 is cut by a cross section into a slab having a thickness of about 2 cm to about 3 cm using the same saw. These spheroids are used as single crystal or "seed". Maintain the (100) crystal phase polar orientation of the Shixi embryo. However, the single (four) flat embryo (4) collapses at the bottom of the quartz, and the direction of the flat embryo (_direction upward, (10)) remains parallel to the (four)^ side. Quartz (4) has a square section with a side length of 68 cm and a depth of about 4 37 37 200921924 m. The spheroids are arranged at the base of the ridge, the longitudinal dimension is parallel to the base of the ridge, and the sides are in contact to form a single intact blast layer on the base of the ridge. Casting: The crucible was loaded with a seed plate and then filled at room temperature to a total weight of 265 kg of solid helium feed. A small number of highly boron-doped germanium wafers were added to provide sufficient boron 5 to achieve a total ingot doping of approximately 0.3 ppma. The filled crucible is first surrounded by a graphite carrier plate that rests on the insulating portion of the support structure and then loaded into an in situ melting/directional solidification casting station for casting the polycrystalline crucible. The melting process is carried out by heating the resistance heater to about 1550 ° C. The heater is assembled to start heating from the top, and the heat is radiated out to the bottom of 10 by opening the insulator a total of 6 cm. This configuration causes the melting to proceed in the top-bottom direction toward the bottom of the crucible. Passive cooling through the bottom, such as by thermocouple monitoring, causes the seed crystal to remain solid at the melting point. The degree of melting is measured by dropping the quartz dipstick into the melt every 10 minutes. The height of the dipstick is compared to the measured value obtained from the open space in the casting station to determine the height of the remaining solid material. The feed 15 was first melted by dipstick measurement, and then the melted phase was allowed to continue only to a depth of about 1.5 cm. At this point, the heating power drops to a temperature set point of 1500 ° C, and the radiation from the bottom increases the radiation by opening the insulator to 12 cm. An additional 1 mm or 2 mm seed crystal melts before curing begins, as observed by dipstick measurements. The seed crystal growth is then carried out until the end of the curing step. The growth phase of the casting cycle and the remaining 20 parts are carried out with general parameters, where the top-to-bottom thermal gradient is flattened and the entire ingot is slowly cooled to room temperature. The as-cast tantalum product was 66 cm χ 66 cm X 2 4 cm ingot. The crystallinity region consistent with the seed crystal starts at the bottom and follows the edge of the unmelted material, and grows toward the lateral direction of the crucible wall as it begins to grow, and becomes stable toward the end point of the crystallization. The visual inspection was found by casting 38 200921924 = the single (four) structure of each face of the crystal. Preparation. Prepare the seed layer, starting with a frosted bottom of 18 kg square plate. ^ Qi calibration, providing 58 cm x 58 cm and a thickness of 2_3 cm Beans " District These boards are placed together in a larger square, taken in 坩埚. /, the square is surrounded by a 2 cm thick (Ul) oriented total seed layer, so that the seed layer forms a square of 631 + χ 63 ϋ #. 10 Casting: Filled with seed crystals to a total weight of 265 kg, placed in the casting station. Casting was carried out as in Example 1, and the treatment procedure was monitored to ensure that the seed layer was maintained intact by the end of melting and the starting point of solidification. The resulting ingot was cut into 5 x 5 lattices of 12.5 cm crystal bricks. Optical inspection of the crystal structure of the crystal tile shows that the (111) crystal acts as a buffer layer to prevent random (100) volume of the internal cavity. Thus, according to the embodiment of the present invention and the foregoing examples, Shi Xi may be a body of continuous single crystal germanium, as-cast twin germanium, or as-cast single crystal germanium, preferably 15 or less. Radially distributed defects such as OSF defects and/or vortex defects, and preferably, the body preferably has at least two dimensions of at least about 1 cm, preferably at least about 20 cm, more preferably at least about 30 cm. More preferably, it is at least about 40 cm, more preferably at least about 50 cm, still more preferably at least about 6 cm, and most preferably at least about 70 cm. Preferably, the second dimension of the stone body is at least about 5 cm, preferably at least about 15 cm, and most preferably at least about 20 cm. > The 5th body may be a separate mass to a single body, or may be contained in all or part of other broken interiors. The Shixi body is preferably shaped to have at least two dimensions each of which is the same as the inner dimension of the cast container. As disclosed herein, embodiments of the present invention can be used to fabricate large crystals of early crystals, twin crystals, or near-early crystals by a simple and cost-effective method of prayer, 2009 200924, according to an embodiment of the present invention. The finished wafer is suitable for thin wafers and can be used for photovoltaic cells. In addition, the wafer can be either η plastic or p-type. For example, 5 wafers can be from about 10 microns thick to about 700 microns thick. Further, the wafer used for the photovoltaic cell preferably has a diffusion length (LP) greater than the wafer thickness (1). For example, the ratio of LP to t is suitable to be at least 0.5. For example, it is at least about 1.1 or at least about 2. The diffusion length is the average distance that can be spread before a small number of carriers (such as electrons in a p-type material) and a large number of carriers (holes in a bismuth material) are combined. The LP system is related to the small carrier lifetime τ by the L1 = (Di:) 1/2, where D is the diffusion constant. The diffusion length can be determined by a number of techniques, such as photon beam induced current technology or surface photovoltaic technology. See, for example, "Solar Cell Basis," by A. Fahrenbmch and R. Bube, Academic Press, 1983, pp. 1〇2, 2, for instructions on how to measure the length of diffusion. The 15 20 wafer has a width of from about 100 mm to about 600 mm. Preferably, the wafer shoulder has at least one dimension of at least about 50 mm. The shim produced by the crucible of the present invention and the photovoltaic cell produced by the present invention have, for example, a surface area of from about square centimeters to about fine square centimeters. The front side of the wafer is preferably textured. For example, wafers can be textured using chemical (4), or laser inscriptions. If an wafer having a ((10)) polar orientation can be etched to form an anisotropic textured surface, it is: for example, about thief to about 啊, after about 1 minute to about 12 minutes, a sodium-(tetra) sodium solution Processing wafers in _. Water (4) _ ^ 40 200921924 5 10 15 i 20 Thus, a solar cell can be fabricated using the wafer fabricated from the as-cast bismuth ingot according to the present invention, and at least one wafer is formed by slicing the solid body of the as-cast crucible; Performing a cleaning process on the surface of the wafer; performing a texturing step on the surface as needed; for example, by doping the surface to form a pn junction; optionally depositing an anti-reflective coating on the surface; Forming at least one layer selected from the back field and the passivation layer by an aluminum sintering step; and forming a conductive contact on the wafer. The passivation layer is a layer of dangling bonds that are bonded to the surface of the bare wafer to the surface atoms. Examples of the passivation layer on Shi Xi include tantalum nitride, hafnium oxide and amorphous germanium. This layer is typically thinner than 丨 microns and can be permeable or used as an anti-reflective layer. In a typical procedure for fabricating a photovoltaic cell using, for example, a P-type germanium wafer, the wafer is exposed to the appropriate η dopant on the side to form a light-emitting layer and a p-n junction on the wafer front side or the light-receiving side. Typically, the n-type layer or the formation of the luminescent layer, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Wei Renren's 11 wafer front side is internally stepped into the η dopant to the wafer surface. The “step-in” step is common to expose the wafer to high temperatures. Thereby, a junction surface is formed between the n-type layer and the boundary region between the p-type silicon wafer substrate. The surface of the wafer can be textured prior to the other doping to form the luminescent layer. In order to further improve light absorption, an optional anti-reflective coating such as nitrogen is used on the front side of the wafer to provide simultaneous surface and/or bulk passivation. In order to utilize the Ρ·η junction exposed to light energy, the potential photocell is typically provided with a conductive front contact on the front side of the wafer and a conductive back surface. 41 200921924 However, the two contacts may be located on the back side of the wafer. The solar cell of the one or more highly conductive metals may be composed of a continuous single crystal germanium, a twin crystal germanium, or a crystallite body which is substantially free from or distributed in the direction of the 3倥 direction.成之叉_, or near early «the respective body can be as described above, for example, to the third male / dimension of the meter and at least about 20 PCT 10 reflection sound; 2 'day _ _ _ _ _ _ _ _ _ _ The optional anti-surface of the surface has at least one selected from the group consisting of the back field and the passivation layer; and the two circles: the electrical contact where the body may be free or substantially free of vortex defects and/or not or substantially Contains OSF defects. 15 20 The contacts are on the back side of the wafer, and the contacts are typically opaque. It is obvious to those skilled in the art that many modifications and variations can be made in the structure and method of the invention. For example, it is also known that the process and method for forming a single sheet are also suitable for forming a combination of twin or near-early crystal (four). In addition, although it has been said here that it has been cast, it has not earned this (4). And other materials and non-metallic crystalline materials. For example, the inventors intend to cover the invention according to the embodiment of the invention = other materials such as gallium, gallium, oxidized, nitrided, zinc oxide, sulfide Zinc, indium gallium indium, indium, fault, oxide, lanthanide oxide, magnesium oxide, and other semiconductors, oxides, and intermetallic compounds with liquid phase. Consider the invention disclosed herein The specification and the examples of the present invention are well-known to those skilled in the art. The description and examples are intended to be illustrative only, and the true scope and essence of the invention are indicated by the following claims. 42 200921924 L BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing an arrangement example of a seed crystal on a bottom surface of a crucible according to an embodiment of the present invention; and FIG. 2 is a view showing five kinds of twin crystals on the bottom surface of a crucible according to an embodiment of the present invention. Example 3 shows a cross-sectional view of an ingot using a seed crystal having a single crystal orientation; and FIG. 4 shows a cross-sectional view of an ingot using a seed crystal according to an embodiment of the present invention, in which a part of the crystal has a crystal orientation , a portion of the seed crystal has 10 another crystal orientation; FIG. 5 shows an example of a method according to an embodiment of the present invention; and FIGS. 6A-6G and 7 show an example for a single crystal germanium or twin crystal according to an embodiment of the present invention. Examples of casting methods. [Main component symbol description] 100... seed crystal 260... miscellaneous 110...坩埚270...die 120...flat embryo 280...lin 2〇α·.矽feed 285. .. substantially flat solid-liquid interface 210...坩埚290...cast single crystal crucible 220...seed 300,310...seed 230...heat sink material 300...melt container 240.. Melt 305...melt feed 250...melted portion 310·.melting tube 43 200921924 320...full width 460...side plate 400...cast slab ingot 510···( 111) single crystal germanium region 410...bending angle 隅520·.·demarcation line 420...polycrystalline stone night region 600...method 430...single crystal germanium region 605-640...method step 450 ...crystalline brick 44