JPH10182133A - Refining of silicon - Google Patents
Refining of siliconInfo
- Publication number
- JPH10182133A JPH10182133A JP8347803A JP34780396A JPH10182133A JP H10182133 A JPH10182133 A JP H10182133A JP 8347803 A JP8347803 A JP 8347803A JP 34780396 A JP34780396 A JP 34780396A JP H10182133 A JPH10182133 A JP H10182133A
- Authority
- JP
- Japan
- Prior art keywords
- silicon
- container
- graphite
- refining
- releasing agent
- 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.)
- Withdrawn
Links
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)
- Photovoltaic Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は太陽電池用シリコン
を対象として電子ビーム加熱により真空中でＰ，Ａｌ，
Ｃａ等の不純物除去を行う際に用いるシリコン精製方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to silicon for photovoltaic cells, which is obtained by heating P, Al,
The present invention relates to a silicon purification method used for removing impurities such as Ca.
【０００２】[0002]
【従来の技術】近年エネルギー源の多様化の要求から太
陽光発電がエネルギー源として脚光をあび、低価格発電
装置の実用化に向け研究開発が盛んに行われている。こ
のような状況の中で、太陽電池用原料としてシリコンは
最も汎用されやすい材料であり、しかも、動力用電力供
給に使われる材料として結晶系シリコンが最も重要視さ
れている。2. Description of the Related Art In recent years, photovoltaic power generation has been in the spotlight as an energy source due to the demand for diversification of energy sources, and research and development are being actively conducted toward the practical use of low-cost power generation devices. Under these circumstances, silicon is the most commonly used material as a raw material for solar cells, and crystalline silicon is regarded as the most important material used for power supply for power.
【０００３】太陽電池用原料として用いられるシリコン
の純度は９９．９９９９％（６Ｎ）以上が必要とされ、
シリコン中に含有される不純物の濃度はｐｐｍオーダー
以下まで低減する必要がある。従来、市販の金属シリコ
ン（純度９９．５％）から上記高純度シリコンを製造す
るには、Ｐ、Ａｌ、Ｃａ等の不純物元素を電子ビーム溶
解により短時間で同時に除去可能なことが知られてい
る。[0003] The purity of silicon used as a raw material for solar cells must be 99.9999% (6N) or more.
It is necessary to reduce the concentration of impurities contained in silicon to the order of ppm or less. Conventionally, in order to manufacture the high-purity silicon from commercially available metal silicon (purity: 99.5%), it has been known that impurity elements such as P, Al, and Ca can be simultaneously removed in a short time by electron beam melting. I have.
【０００４】電子ビーム溶解によるＰ、Ａｌ、Ｃａ等の
不純物の蒸発除去の利点を生かして電子ビームを加熱源
とし、短時間にＰ、Ａｌ、Ｃａ等の不純物を除去する技
術が開発され、さらに、従来シリコン精製容器として水
冷坩堝が使用れていたが、熱効率が低いのでこれを改善
し黒鉛容器を用いることにより溶融シリコンの高温化す
なわち上記不純物除去速度のさらなる向上を図る技術が
開発された。A technique for removing impurities such as P, Al, and Ca in a short time by using an electron beam as a heat source has been developed, taking advantage of the advantage of evaporating and removing impurities such as P, Al, and Ca by electron beam melting. Conventionally, a water-cooled crucible has been used as a silicon refining vessel. However, since the heat efficiency is low, a technique has been developed to improve the efficiency and use a graphite vessel to raise the temperature of molten silicon, that is, to further improve the impurity removal rate.
【０００５】[0005]
【発明が解決しようとする課題】このような黒鉛容器を
用いれば水冷容器に比べ、不純物（Ｐ、Ａｌ、Ｃａ）の
除去速度が大幅に向上するという利点はあったが黒鉛容
器の再利用を考えた場合、黒鉛容器の中にシリコンが付
着して離れなくなり、分離できないという問題があっ
た。特に、容器内壁の湯面より上部に付着した蒸着物は
上記不純物が濃縮されているため、除去しないと、シリ
コン不純物濃度のばらつき等、付着物からの汚染が原因
となる問題も生じた。The use of such a graphite container has the advantage that the rate of removal of impurities (P, Al, Ca) can be greatly improved as compared with a water-cooled container, but the graphite container can be reused. When considered, there was a problem that silicon adhered to the graphite container and could not be separated, so that it could not be separated. In particular, since the impurities adhering to the upper portion of the inner surface of the container from the hot water surface are concentrated, if not removed, there is also a problem caused by contamination from the adhering substances such as a variation in silicon impurity concentration.
【０００６】本発明はこのような問題を解決するために
開発されたもので、シリコンの電子ビーム溶解によるシ
リコン精製に用いる黒鉛容器の繰返し利用、長寿命化を
図ることを目的とする。The present invention has been developed to solve such a problem, and has as its object to repeatedly use a graphite container used for refining silicon by electron beam melting of silicon and prolong its life.
【０００７】[0007]
【課題を解決するための手段】本発明は電子ビームを加
熱源として用い、真空中でシリコンの精製を行う黒鉛製
シリコン精製容器の内面に、離型剤として電子ビーム溶
解に必要な高温、高真空に耐え、かつシリコンへの汚染
のないＳｉＣ又はＣの粉末を塗布あるいは蒸着すること
を特徴とするシリコン精製方法である。According to the present invention, an electron beam is used as a heating source, and a high temperature, high temperature necessary for melting an electron beam as a mold release agent is provided on the inner surface of a graphite silicon purification vessel for purifying silicon in a vacuum. A silicon refining method characterized by applying or depositing SiC or C powder that withstands vacuum and does not contaminate silicon.
【０００８】前記離型剤はシリコンの精製目標不純物濃
度よりも低い不純物濃度を有する材料とすると好まし
い。Preferably, the release agent is a material having an impurity concentration lower than the target impurity concentration of silicon.
【０００９】[0009]
【発明の実施の形態】図１はシリコンの電子ビーム溶解
によるシリコン精製に用いる黒鉛容器の断面図である。
本発明では黒鉛容器内面に離型剤を塗布し、シリコンの
剥離を容易にし、黒鉛容器の破損を防止し、容器の再利
用を可能とする。離型剤としてはＳｉＣ又はＣを用い
る。これらの離型剤は高温高真空で安定しており、かつ
シリコン中の炭素の溶解量が１００ｐｐｍ程度であり、
酸化除去しやすい。FIG. 1 is a sectional view of a graphite container used for purifying silicon by electron beam melting of silicon.
In the present invention, a release agent is applied to the inner surface of a graphite container to facilitate the peeling of silicon, prevent breakage of the graphite container, and enable reuse of the container. SiC or C is used as a release agent. These release agents are stable at high temperature and high vacuum, and the dissolved amount of carbon in silicon is about 100 ppm.
Easy to remove by oxidation.
【００１０】離型剤の塗布は、バインダとして水及びＰ
ＶＡを用い、黒鉛容器の内側に刷毛塗り又はスプレー
し、その後スタンプし高密度とする。スタンプするの
は、シリコンが離型剤層に浸み込むのを防止するためで
ある。離型剤を塗布することによりシリコンと容器との
付着が防止され、容器とシリコンインゴット分離後の黒
鉛容器の再利用、ならびに、汚染の原因となる蒸着した
シリコンの分離が可能となる。従って黒鉛容器の繰返し
使用、長寿命化を達成することができる。The release agent is applied by using water and P as a binder.
Brush or spray the inside of the graphite container using VA and then stamp and densify. Stamping is performed to prevent silicon from seeping into the release agent layer. By applying the release agent, adhesion between the silicon and the container is prevented, and it becomes possible to reuse the graphite container after separating the container and the silicon ingot and to separate deposited silicon which causes contamination. Therefore, the graphite container can be used repeatedly and the life can be extended.
【００１１】[0011]
【実施例】純水に１％のＰＶＡを加えた溶液を、平均粒
径０．５μｍの炭素粒子に加え、水分３０％のスラリー
とした。このスラリーを内寸３００ｍｍ×１５０ｍｍ×
５ｍｍの黒鉛容器の内壁にスプレーにより塗布し、スタ
ンプ後、黒鉛容器とともにＡｒ雰囲気中、１５００℃で
３時間乾燥した。乾燥後の炭素粒子層の厚みは、約１ｍ
ｍであった。EXAMPLE A solution obtained by adding 1% of PVA to pure water was added to carbon particles having an average particle size of 0.5 μm to prepare a slurry having a water content of 30%. This slurry has an inner size of 300 mm x 150 mm x
It was applied to the inner wall of a 5 mm graphite container by spraying, and after stamping, dried together with the graphite container in an Ar atmosphere at 1500 ° C. for 3 hours. The thickness of the carbon particle layer after drying is about 1 m
m.
【００１２】上記容器中に２０００ｇの市販金属級シリ
コンを装入し、電子ビーム出力３０ｋＷで１時間シリコ
ンの溶解を行った後、シリコンインゴットと容器の分離
を試みた結果、問題なく分離可能であることが判った。
同様に平均粒径０．４μｍの炭化珪素粒子についても同
上の実験を行ったところ同様の結果が得られた。After charging 2000 g of commercially available metal-grade silicon into the above container and dissolving the silicon with an electron beam output of 30 kW for 1 hour, separation of the silicon ingot from the container was attempted. It turns out.
Similarly, the same experiment was performed on silicon carbide particles having an average particle diameter of 0.4 μm, and similar results were obtained.
【００１３】また分離後のシリコンインゴット中の炭素
濃度を燃焼法により測定したところ５５ｐｐｍであっ
た。また、黒鉛容器表面に緻密な厚み約１００μｍの炭
化珪素膜を化学蒸着法により被覆し、同様の溶解テスト
を行ったところ、これも同様の結果が得られた。The carbon concentration in the silicon ingot after separation was measured by a combustion method and found to be 55 ppm. The surface of the graphite container was coated with a dense silicon carbide film having a thickness of about 100 μm by a chemical vapor deposition method, and the same dissolution test was performed. The same result was obtained.
【００１４】[0014]
【発明の効果】本発明によれば、電子ビームによる黒鉛
容器内のシリコン装置において、従来１〜２回の使用に
より新品に交換していた黒鉛容器が、繰返し使用するこ
とが可能となった。According to the present invention, in a silicon device in a graphite container using an electron beam, a graphite container which has been replaced with a new one by using once or twice can be used repeatedly.
【図面の簡単な説明】[Brief description of the drawings]
【図１】黒鉛容器の断面図である。FIG. 1 is a sectional view of a graphite container.
１ 黒鉛容器 ２ 離型剤 ３ シリコン 1 Graphite container 2 Release agent 3 Silicon
Claims (2)
でシリコン精製を行う黒鉛製シリコン精製容器の内面に
離型剤としてＳｉＣ又はＣを塗布あるいは蒸着すること
を特徴とするシリコン精製方法。1. A method for refining silicon, comprising applying or vapor depositing SiC or C as a release agent on the inner surface of a silicon refining container made of graphite for refining silicon in a vacuum using an electron beam as a heating source.
濃度よりも低い不純物濃度を有する材料であることを特
徴とする請求項１記載のシリコン精製方法。2. The silicon refining method according to claim 1, wherein the release agent is a material having an impurity concentration lower than a target impurity concentration of silicon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8347803A JPH10182133A (en) | 1996-12-26 | 1996-12-26 | Refining of silicon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8347803A JPH10182133A (en) | 1996-12-26 | 1996-12-26 | Refining of silicon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10182133A true JPH10182133A (en) | 1998-07-07 |
Family
ID=18392696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8347803A Withdrawn JPH10182133A (en) | 1996-12-26 | 1996-12-26 | Refining of silicon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10182133A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005281085A (en) * | 2004-03-30 | 2005-10-13 | Nippon Steel Corp | Crucible made of graphite |
| JP2008175479A (en) * | 2007-01-19 | 2008-07-31 | Ulvac Japan Ltd | Silicon fusion vessel and fusion device using the same |
| JP2010043776A (en) * | 2008-08-11 | 2010-02-25 | Ulvac Japan Ltd | Water cooling crucible and electron beam melting furnace |
| JP2010517924A (en) * | 2007-02-14 | 2010-05-27 | コミサリア ア エナジー アトミック | Silicon purification equipment |
| WO2010089803A1 (en) * | 2009-02-06 | 2010-08-12 | アーベル・システムズ株式会社 | Process for producing solar battery from waste salt and sand in desert |
| WO2013015119A1 (en) * | 2011-07-25 | 2013-01-31 | 株式会社トクヤマ | Polysilicon receptacle |
| KR101364587B1 (en) * | 2012-05-24 | 2014-02-19 | 주식회사 티씨케이 | Crucible for sapphire single crystal growth device |
| EP2334849A4 (en) * | 2008-10-16 | 2015-06-17 | Korea Energy Research Inst | A graphite crucible for silicon electromagnetic induction heating and apparatus for silicon melting and refining using the graphite crucible |
-
1996
- 1996-12-26 JP JP8347803A patent/JPH10182133A/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005281085A (en) * | 2004-03-30 | 2005-10-13 | Nippon Steel Corp | Crucible made of graphite |
| JP2008175479A (en) * | 2007-01-19 | 2008-07-31 | Ulvac Japan Ltd | Silicon fusion vessel and fusion device using the same |
| JP2010517924A (en) * | 2007-02-14 | 2010-05-27 | コミサリア ア エナジー アトミック | Silicon purification equipment |
| JP2010043776A (en) * | 2008-08-11 | 2010-02-25 | Ulvac Japan Ltd | Water cooling crucible and electron beam melting furnace |
| EP2334849A4 (en) * | 2008-10-16 | 2015-06-17 | Korea Energy Research Inst | A graphite crucible for silicon electromagnetic induction heating and apparatus for silicon melting and refining using the graphite crucible |
| WO2010089803A1 (en) * | 2009-02-06 | 2010-08-12 | アーベル・システムズ株式会社 | Process for producing solar battery from waste salt and sand in desert |
| WO2010089812A1 (en) * | 2009-02-06 | 2010-08-12 | アーベル・システムズ株式会社 | Process for producing solar battery from waste salt and sand in desert |
| WO2013015119A1 (en) * | 2011-07-25 | 2013-01-31 | 株式会社トクヤマ | Polysilicon receptacle |
| JP2013023426A (en) * | 2011-07-25 | 2013-02-04 | Tokuyama Corp | Polysilicon receiving container |
| KR101364587B1 (en) * | 2012-05-24 | 2014-02-19 | 주식회사 티씨케이 | Crucible for sapphire single crystal growth device |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20040302 |