JPH04193706A - Refining method for silicon - Google Patents
Refining method for siliconInfo
- Publication number
- JPH04193706A JPH04193706A JP32232090A JP32232090A JPH04193706A JP H04193706 A JPH04193706 A JP H04193706A JP 32232090 A JP32232090 A JP 32232090A JP 32232090 A JP32232090 A JP 32232090A JP H04193706 A JPH04193706 A JP H04193706A
- Authority
- JP
- Japan
- Prior art keywords
- silicon
- gas
- tuyere
- added
- blowing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 44
- 239000010703 silicon Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 16
- 238000007670 refining Methods 0.000 title claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000007664 blowing Methods 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 101100083507 Caenorhabditis elegans acl-2 gene Proteins 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract 1
- 239000001110 calcium chloride Substances 0.000 abstract 1
- 229910001628 calcium chloride Inorganic materials 0.000 abstract 1
- 235000011148 calcium chloride Nutrition 0.000 abstract 1
- 235000012255 calcium oxide Nutrition 0.000 abstract 1
- 239000000292 calcium oxide Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000008246 gaseous mixture Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000006698 induction Effects 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Silicon Compounds (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、主に太陽電池に用いる高純度シリコンの精製
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention mainly relates to a method for purifying high-purity silicon used in solar cells.
〈従来の技術〉
太陽電池に使用するシリコン中のＰ、Ｂ、Ｃ１Ｆｅ、
ＡＩ、 Ｔ＋などの不純物は少ない方がよく、シリコン
は高純度であることが望まれる。また、太陽電池が広く
利用されるためには、このシリコンを安価に量産するこ
とが必要である。<Prior art> P, B, C1Fe, in silicon used for solar cells,
It is better to have fewer impurities such as AI and T+, and it is desirable for silicon to have high purity. In addition, in order for solar cells to be widely used, it is necessary to mass-produce this silicon at low cost.
従来、この太陽電池用シリコンとして半導体用のシリコ
ンが用いられてきたが、高価なためより安価な製造法が
検討されている。例えば特開昭６３−２１８５０６号公
報にはプラズマを用いる精製方法が提案されている。Conventionally, silicon for semiconductors has been used as silicon for solar cells, but because it is expensive, cheaper manufacturing methods are being considered. For example, Japanese Patent Laid-Open No. 63-218506 proposes a purification method using plasma.
〈発明が解決しようとする課題〉
しかしながら、この方法では金属シリコンより除去しに
くいＢの除去ができ、量産も可能であるが、プラズマを
用いるため、高価な静ガスと電力の多量消費は避けられ
ず、精製コストの点で未だ問題があった。<Problem to be solved by the invention> However, although this method can remove B, which is difficult to remove than metal silicon, and can be mass-produced, it uses plasma, so expensive static gas and large amounts of electricity consumption cannot be avoided. First, there were still problems in terms of refining costs.
そこで、工業的により有利に太陽電池用のシリコンを製
造する技術の開発が望まれていた。Therefore, there has been a desire to develop a technology for industrially more advantageous production of silicon for solar cells.
本発明の目的は、上記問題点を解決し、より有利に高純
度の原料シリコンを大量に供給できるシリコンの精製方
法を提供することである。An object of the present invention is to provide a silicon refining method that can solve the above problems and more advantageously supply a large amount of highly pure raw material silicon.
〈課題を解決するだめの手段〉
本発明者らは、前記問題点を解決Ｊるため、基礎実験を
重ねた結果、シリコン中の炭素、ボ［Ｉンの除去にはシ
リコン浴の攪拌強化と、さらに加えるに、酸化性ガスと
の反応界面積の増加が重要な要因であることを知見し、
これに基づいて本発明を構成したものである。<Means to Solve the Problem> In order to solve the above-mentioned problem, the inventors of the present invention have conducted repeated basic experiments and found that strengthening the agitation of the silicon bath can be used to remove carbon and boron in silicon. In addition, we found that an increase in the reaction interface area with oxidizing gas was an important factor.
The present invention is constructed based on this.
ずなわぢ、本発明は、１３、Ｃ，Ｐ、 Ｆｅ、へ１等の
不純物元素を含むシリコンを底部にガス吹込め羽Ｌ１を
有するシリカを主成分とする容器内で溶融し、該羽口か
らＡｒ若しくはＨ□又はこれらの混合ガスを吹込むこと
を特徴とするシリコンの精製方法であり、さらに望まし
くは、上記吹込みガスにＨ□０、ＣＯ□及び／又は０□
ガスを添加することであり、またあるいはさらに、ｌｌ
Ｃｌを添加することもできる。In the present invention, silicon containing impurity elements such as 13, C, P, Fe, and 1 is melted in a container mainly composed of silica having gas injection vanes L1 at the bottom, and the tuyere A method for refining silicon characterized by blowing Ar, H□, or a mixed gas thereof, more preferably H□0, CO□ and/or 0□ into the blown gas.
adding gas, and/or in addition, ll
Cl can also be added.
また、羽口から吹込まれるガスにＳｉＯ□、ＣａＯ１Ｃ
ａＣＩ□及びＣａＦ２の各粉末から選ばれた１種以上を
添加することもできる。In addition, SiO□, CaO1C are added to the gas blown from the tuyere.
It is also possible to add one or more selected from powders of aCI□ and CaF2.
く作 用〉
第１図は本発明を実施する際に用いる基本的な装置を示
したもので、Ｂ、Ｃ，Ｐ、Ｆｅ、ＡＩなどの不純物を１
ｐｐｍ以上含む金属シリコン２を、底部にガス吹込み
羽口（ガス吹込み孔）３を有するシリカあるいはシリカ
を主成分とする容器Ｉ内でシリコンの融点以上の温度に
加熱して溶融し、底部に設けた羽口より計、Ｈ□などの
不活性ガス、あるいはこれにｆ（２０、ＣＯ□、又は少
量の０２などの酸化性ガスを混合したガスを吹込むこと
ができるように構成されている。４は誘導力ｉｊ熱コイ
ル、６はガス排出用フードである。Figure 1 shows the basic equipment used to carry out the present invention, which removes impurities such as B, C, P, Fe, and AI.
Metallic silicon 2 containing ppm or more is heated to a temperature higher than the melting point of silicon to melt it in a silica or silica-based container I having a gas blowing tuyere (gas blowing hole) 3 at the bottom. The structure is such that an inert gas such as H□ or a gas mixed with an oxidizing gas such as f(20, CO□, or a small amount of 02) can be blown into the tuyere provided in the tuyere. 4 is an induction heat coil, and 6 is a gas exhaust hood.
このように容器底部よりガスを吹込むことで、容器内の
シリコンは停滞域を形成ゼす、浴全体が強く攪拌される
と同時に、浴中を上昇するガス気泡とシリコンの界面が
反応界面となるため、反応を非常に速く進行さ・けるこ
とができる。またシリコン中の炭素、ボロンは、このよ
・うな方法では酸化物ガスの形で除去されると考えられ
るが、シリカ又はシリカを主成分とする容器を用いるこ
よで、容器より反応に必要な酸素が供給されると同時に
、容器より他の不純物が混入するのを防くごとができる
。また、反応をより速く進めるには、底部より吹込むガ
スに、Ｈ□０、ＣＯ２及び／又は少量の酸素などの酸化
性ガスを混入することで有利に進めることができる。By blowing gas from the bottom of the container, the silicon in the container forms a stagnation area.At the same time, the entire bath is strongly stirred, and the interface between the gas bubbles rising in the bath and the silicon becomes a reaction interface. Therefore, the reaction can proceed very quickly. Carbon and boron in silicon are thought to be removed in the form of oxide gas by such a method, but by using silica or a container mainly composed of silica, the oxygen necessary for the reaction can be removed from the container. At the same time, it is possible to prevent other impurities from entering the container. In addition, in order to advance the reaction more quickly, it is advantageous to mix an oxidizing gas such as H□0, CO2 and/or a small amount of oxygen into the gas blown in from the bottom.
また、特に原料Ｓｉ中のＢ濃度が高い場合には、底部羽
口より吹込まれるガスにＳｉｎ、、Ｃａｂ、 ＣａＣｌ
□、（：ａＦｅの一種以上の混合物をわ）末で添加する
ことで、Ｂの除去が有利に促進される。In addition, especially when the B concentration in the raw material Si is high, the gas blown from the bottom tuyere contains Sin, Cab, CaCl.
The removal of B is advantageously promoted by adding a mixture of one or more of □, (:aFe) at the end.
本発明では、このようにして、反応時間を短くして有利
にシリコン中のＣ１■３を除去できるが、シリコン中の
Ｐ、ＡＩなどのガスとして除去し易い成分も同時にシリ
コンより除去できる。またＦｅを除去するには該吹込み
ガスに少量のＨＣｌを添加し、蒸気圧の高い鉄の塩化物
を生成させ、これをガスとともに系外に除去することで
達成できる。In the present invention, in this way, C1-3 in silicon can be advantageously removed by shortening the reaction time, but components that are easily removed as gases such as P and AI in silicon can also be removed from silicon at the same time. Further, Fe can be removed by adding a small amount of HCl to the blown gas to generate iron chloride having a high vapor pressure, and removing this from the system together with the gas.
これらの処理は、Ｓｉの融点以上の温度で行われるが、
作業性、反応速度の点より１４５０〜１６５０’Ｃの範
囲が望ましい。These treatments are performed at a temperature above the melting point of Si,
From the viewpoint of workability and reaction rate, a range of 1450 to 1650'C is desirable.
〈実施例〉
第１図に示す装置出回じ構造を有する装置を用いてシリ
コンの精製を行った。容器はシリカ製の容器を用い、底
部に１ｍｍφの孔径の羽口３木を設けている。８ｋｇの
金属シリコンを該容器内で誘導加熱により１５５０’Ｃ
に加熱溶解し、２５ＮＩ／ｍｉｎで静ガスを底部羽口よ
り吹込んだ。原料として用いた金属シリコン中の不純物
含有量ならびに処理後のシリコン中の不純物含有量を表
１に示す。<Example> Silicon was purified using an apparatus having the apparatus circulation structure shown in FIG. The container is made of silica, and three tuyeres with a hole diameter of 1 mm are provided at the bottom. 8 kg of metallic silicon was heated to 1550'C by induction heating in the container.
The mixture was heated and dissolved, and static gas was blown in from the bottom tuyere at 25 NI/min. Table 1 shows the impurity content in the metal silicon used as a raw material and the impurity content in the silicon after treatment.
実施例１は吹込みガスにＡｒ、実施例２はＨ□、実施例
３はＡｒとＨ３、を用いたときの結果である。実施例４
．５．６は各々計ガスにＨ□０５％、ＣＯ□ ２％、０
□Ｏ２０５％を添力Ｈシたときの結果で、これらガスの
添加により不純物の除去速度はより大きくなることがわ
かる。The results were obtained when Ar was used as the blown gas in Example 1, H□ was used in Example 2, and Ar and H3 were used in Example 3. Example 4
．． 5.6 is H□05%, CO□2%, 0 in each meter gas.
□The results are obtained when 05% O2 is added to H. It can be seen that the impurity removal rate is increased by adding these gases.
実施例７ば実施例４の条件にフラ・ンクスとじて５ｉＯ
ｚ／ＣａＯ（］ ： １ ）の混合粉末を２．０ ｇ
／ｍｉｎで吹込んだときの結果で、実施例８はＳｉＯ□
／ＣａＣｌ□／ＣａＦｚ （１： １ ： Ｉ）の混合
粉末を２．０ｇ／ｍｉｎで吹込んだときの結果である。Example 7 The conditions of Example 4 were combined with 5iO.
2.0 g of mixed powder of z/CaO(]: 1)
Example 8 shows the results when blowing at a rate of /min.
These are the results when a mixed powder of /CaCl□/CaFz (1:1:I) was injected at 2.0 g/min.
この処理では、処理後シリコン浴を静置してフラックス
とシリコンの分離を図ることが必要であったが、反応は
最も早く進行した。In this treatment, it was necessary to leave the silicon bath still after treatment to separate the flux and silicon, but the reaction proceeded most quickly.
実施例９は上記結果ではシリコン中のｌ？ｅが除去でき
ないため、実施例１の＾ｒガスにＨ０１ガスを１％添加
したときの結果で、Ｆｅ分の除去も行われた。In Example 9, the above results show that l? Since e could not be removed, the result was when 1% H01 gas was added to the ^r gas in Example 1, and Fe was also removed.
本発明の実施例では、表１かられかるように、シリコン
中のＦｅ、ＡＩの除去は必ずしも太陽電池用として十分
な量まで低減されないが、これは処理後に一方向凝固な
ど通常の処理方法を併用することで十分な結果を得るこ
とができる。すなわち、実施例４で処理したシリコンを
、１ｍｍ／ｍｉｎの速度で一方向に凝固させたシリコン
鋳塊の中央部より切り出した多結晶シリコン基板を用い
た太陽電池では、Ｈ％の変換効率が得られた。In the examples of the present invention, as can be seen from Table 1, the removal of Fe and AI from silicon is not necessarily reduced to a sufficient amount for solar cells, but this is because ordinary treatment methods such as unidirectional solidification are not used after treatment. Sufficient results can be obtained by using them together. That is, in a solar cell using a polycrystalline silicon substrate cut from the center of a silicon ingot made by solidifying silicon treated in Example 4 in one direction at a rate of 1 mm/min, a conversion efficiency of H% was obtained. It was done.
以上のように、本発明ではプラズマを使用しないため、
プラズマ発生のためのＡｒガス、電力が不要であるなど
、経済的にも有利な結果が得られている。As described above, since plasma is not used in the present invention,
Economically advantageous results have been obtained, such as no need for Ar gas or electricity for plasma generation.
〈発明の効果〉
本発明は、従来複雑な工程により製造される半導体用シ
リコンを用いていた太陽電池に対して、冶金的手法によ
り低コストかつ量産製の高い原料シリコン製造技術を提
供したもので、これにより将来のエネルギー問題に対し
て自然エネルギー（太陽エネルギー）を安価に利用でき
る道を拓くものである。<Effects of the Invention> The present invention provides a low-cost, mass-produced, and high-quality raw material silicon manufacturing technology using a metallurgical method for solar cells that conventionally used semiconductor-grade silicon manufactured through complicated processes. This will pave the way for the inexpensive use of natural energy (solar energy) to solve future energy problems.
また、Ｓｉ合金など他の産業に対しても高純度の原料シ
リコンを安価に製造できることになり、Ｓｉ合金分野の
発展にも貢献し得る技術である。Furthermore, it is possible to produce high-purity raw material silicon at low cost for other industries such as Si alloys, and this technology can also contribute to the development of the Si alloy field.
また、本発明の説明ではＳｉの溶融に誘導加熱を用いた
が、抵抗加熱や他の一般的に用いられる加熱方法のいず
れを用いＣも、本発明の範囲から逸脱するものではない
。Further, although induction heating is used to melt Si in the description of the present invention, resistance heating or any other commonly used heating method may be used without departing from the scope of the present invention.
第１図は本発明方法に用いられる装置の説明図である。 １・・・容 器、 ２・・・熔融シリコン、 ３・・・ガス吹込み羽口、 ４・・・誘導加熱コイル、 ５・・・ガス導入口、 ６・・・ガス排出用フード。 特許出願人 川崎製鉄株式会社 第１図 ガス FIG. 1 is an explanatory diagram of an apparatus used in the method of the present invention. 1... Container, 2...Melted silicon, 3...Gas injection tuyere, 4...induction heating coil, 5...Gas inlet, 6...Gas exhaust hood. Patent applicant: Kawasaki Steel Corporation Figure 1 gas
Claims (1)
コンを底部にガス吹込み羽口を有するシリカを主成分と
する容器内で溶融し、該羽口からＡｒ若しくはＨ＿２又
はこれらの混合ガスを吹込むことを特徴とするシリコン
の精製方法。 ２、羽口から吹込まれるガスに酸化性のＨ＿２Ｏ、ＣＯ
＿２及び／又はＯ＿２ガスを添加することを特徴とする
請求項１記載のシリコンの精製方法。 ３、羽口から吹込まれるガスにＨＣｌを添加することを
特徴とする請求項１又は２記載のシリコンの精製方法。 ４、羽口から吹込まれるガスにＳｉＯ＿２、ＣａＯ、Ｃ
ａＣｌ＿２及びＣａＦ＿２の各粉末から選ばれた１種以
上を添加することを特徴とする請求項１、２又は３記載
のシリコンの精製方法。[Claims] 1. Silicon containing impurity elements such as B, C, P, Fe, and Al is melted in a container mainly composed of silica and has a gas injection tuyere at the bottom. A silicon purification method characterized by blowing Ar, H_2, or a mixed gas thereof. 2. Oxidizing H_2O, CO in the gas blown from the tuyere
The method for refining silicon according to claim 1, characterized in that _2 and/or O_2 gas is added. 3. The method for refining silicon according to claim 1 or 2, characterized in that HCl is added to the gas blown through the tuyere. 4. SiO_2, CaO, C in the gas blown from the tuyere
The method for refining silicon according to claim 1, 2 or 3, characterized in that one or more selected from each powder of aCl_2 and CaF_2 is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32232090A JPH04193706A (en) | 1990-11-28 | 1990-11-28 | Refining method for silicon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32232090A JPH04193706A (en) | 1990-11-28 | 1990-11-28 | Refining method for silicon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04193706A true JPH04193706A (en) | 1992-07-13 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32232090A Pending JPH04193706A (en) | 1990-11-28 | 1990-11-28 | Refining method for silicon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04193706A (en) |
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| US5961944A (en) * | 1996-10-14 | 1999-10-05 | Kawasaki Steel Corporation | Process and apparatus for manufacturing polycrystalline silicon, and process for manufacturing silicon wafer for solar cell |
| WO2002016265A1 (en) * | 2000-08-21 | 2002-02-28 | Astropower, Inc. | Method and apparatus for purifying silicon |
| JP2003002629A (en) * | 2001-06-21 | 2003-01-08 | Sharp Corp | Method and apparatus for purifying fused silicon |
| FR2827592A1 (en) * | 2001-07-23 | 2003-01-24 | Invensil | Process for preparing photovoltaic quality silicon comprises oxygen or chlorine refining, re-melting, transfer of molten silicon to plasma refining in crucible furnace, refining under plasma and pouring into mold under controlled atmosphere |
| JP2006104030A (en) * | 2004-10-07 | 2006-04-20 | Sharp Corp | Method of purifying silicon |
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- 1990-11-28 JP JP32232090A patent/JPH04193706A/en active Pending
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| US5961944A (en) * | 1996-10-14 | 1999-10-05 | Kawasaki Steel Corporation | Process and apparatus for manufacturing polycrystalline silicon, and process for manufacturing silicon wafer for solar cell |
| WO2002016265A1 (en) * | 2000-08-21 | 2002-02-28 | Astropower, Inc. | Method and apparatus for purifying silicon |
| US6632413B2 (en) | 2000-08-21 | 2003-10-14 | Astropower, Inc. | Method for purifying silicon |
| JP2003002629A (en) * | 2001-06-21 | 2003-01-08 | Sharp Corp | Method and apparatus for purifying fused silicon |
| FR2827592A1 (en) * | 2001-07-23 | 2003-01-24 | Invensil | Process for preparing photovoltaic quality silicon comprises oxygen or chlorine refining, re-melting, transfer of molten silicon to plasma refining in crucible furnace, refining under plasma and pouring into mold under controlled atmosphere |
| WO2003010090A1 (en) * | 2001-07-23 | 2003-02-06 | Invensil | Medium purity metallurgical silicon and method for preparing same |
| WO2003014019A1 (en) * | 2001-07-23 | 2003-02-20 | Invensil | High purity metallurgical silicon and method for preparing same |
| JP2004537491A (en) * | 2001-07-23 | 2004-12-16 | アンヴァンシル | High-purity metallic silicon and its smelting method |
| US8034151B2 (en) | 2004-03-03 | 2011-10-11 | Nippon Steel Corporation | Method for removing boron from silicon |
| JP2006104030A (en) * | 2004-10-07 | 2006-04-20 | Sharp Corp | Method of purifying silicon |
| US7615202B2 (en) | 2005-03-07 | 2009-11-10 | Nippon Steel Materials Co., Ltd. | Method for producing high purity silicon |
| JP5210167B2 (en) * | 2006-09-29 | 2013-06-12 | 信越化学工業株式会社 | Method for purifying silicon |
| WO2008035799A1 (en) | 2006-09-29 | 2008-03-27 | Shin-Etsu Chemical Co., Ltd. | Method for purification of silicon, silicon, and solar cell |
| JP2009114026A (en) * | 2007-11-07 | 2009-05-28 | Shin Etsu Chem Co Ltd | Method for refining metal silicon |
| US8003546B2 (en) | 2008-12-16 | 2011-08-23 | Samsung Electronics Co., Ltd. | Method of growing silicon and method of manufacturing solar cell using the same |
| JP2009062275A (en) * | 2008-12-24 | 2009-03-26 | Showa Denko Kk | Purification method of silicon |
| CN103771419A (en) * | 2014-01-10 | 2014-05-07 | 黑河合盛光伏科技有限公司 | Method for removing boron in polycrystalline silicon |
| CN106185948A (en) * | 2016-07-11 | 2016-12-07 | 厦门大学 | A kind of industrial silicon slag making dephosphorization process |
| CN106185948B (en) * | 2016-07-11 | 2018-12-11 | 厦门大学 | A kind of industrial silicon slag making dephosphorization process |
| CN106744977A (en) * | 2016-12-09 | 2017-05-31 | 永平县泰达废渣开发利用有限公司 | A kind of graphite furnace lifting method of the molten silicon of utilization induction furnace |
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