JPS62113794A - Production of band silicon - Google Patents
Production of band siliconInfo
- Publication number
- JPS62113794A JPS62113794A JP25409985A JP25409985A JPS62113794A JP S62113794 A JPS62113794 A JP S62113794A JP 25409985 A JP25409985 A JP 25409985A JP 25409985 A JP25409985 A JP 25409985A JP S62113794 A JPS62113794 A JP S62113794A
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- Japan
- Prior art keywords
- crystal
- silicon
- crucible
- silicon melt
- band
- 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.)
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- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
Description
【発明の詳細な説明】 ［発明の技術分野］ 本発明は帯状シリコン結晶の製造方法に関する。[Detailed description of the invention] [Technical field of invention] The present invention relates to a method for manufacturing band-shaped silicon crystals.
［発明の技術的背ｌＩ］
太陽光発電コストの低下のため、太陽電池用シリコン基
板の価格低下が望まれており、帯状シリコン結晶は、イ
ンゴット状結晶を切断・加工する際に生じるような材料
損失がなく、加工費も極くわずかであることから有望視
されている。帯状シリコン結晶を安価に製造するための
ひとつの重要点は、結晶成長を長時間連続させることで
ある。[Technical Background of the Invention] In order to reduce the cost of solar power generation, it is desired to reduce the price of silicon substrates for solar cells. It is viewed as promising because there is no loss and processing costs are minimal. One important point for manufacturing band-shaped silicon crystals at low cost is to continue crystal growth for a long period of time.
帯状シリコン結晶を製造するためのひとつの方法として
以下に述べる手法がある。（Ｔ、Ｆ。One of the methods for manufacturing band-shaped silicon crystals is the method described below. (T.F.
Ｃ１５ｚｅｋ ｅｔ ａｔ、 Ｐｒｏｃｅｅｄｉｎｇ
ｓ ｏｆ ｔｈｅＳｙｌａｐｏｓｉａ ｏｎ Ｅ
Ｉｅｃｔｒｏｎｉｃ ａｎｄ ０ｐｔｉｃａｌＰｒｏ
ｐｅｒｔｉｅｓｏｆ Ｐｏ１ｙｃｒｙｓｔａｌｌｉｎ
ｅ ｏｒＩｍｐｕｒｅ Ｓｅｍ１ｃｏｎｄｕｃｔｏｒ
ｓ ａｎｄ Ｎｏｖｅｌ Ｓ ｉｌｉｃｏｎＧｒｏｗ
ｔｈ Ｍｅｔｈｏｄｓ、 １９８０． Ｅｌｅｃｔｒ
ｏｃｈｅｌｌｌ。C15zek et at, Proceedings
s of theSylaposia on E
Electronic and OpticalPro
parties of polycrystallin
e or Impure Sem1conductor
s and Novel SiliconGrow
th Methods, 1980. Electr
ochell.
Ｓｏｃ、’、 Ｐｅｎｎ１ｎａｔｏｎ 、 ＮＪ ：ｖ
ｏｌ 、 ８０−５ ：ｐｐ２１３−２２２およびＴ、
Ｆ、 Ｃ１５ｚｅｋ ｅｔ ａｌ。Soc,', Penn1naton, NJ:v
ol, 80-5: pp213-222 and T,
F, C15zek et al.
Ｊ、 Ｅｌｅｃｔｒｏｃｈｅｍ、 Ｓｏｃ、 、 １２
９ （１９８２）２８３８など）この方法の原理を第２
図に示す。J, Electrochem, Soc, , 12
9 (1982) 2838, etc.) The principle of this method is
As shown in the figure.
底部に２個の小孔２ａ、２ｂのあるるつぼ１にシリコン
融液３を収容し、一方、２本の結晶端支持材４ａ 、４
ｂをそれぞれるつぼ１の下部から上方に配置し、その後
、前記２本の支持材４ａ、４ｂの間のシリコン融液３と
２本の支持材４ａ 、 ４ｂとに種結晶５を接触させ、
この種結晶５を引上げるというものである。これにより
、２本の支持材４ａ 、４ｂおよび種結晶５の間に表面
張力によって張られたシリコン融液（すなわち、メニス
カス）６が連続的に結晶化することにより、帯状シリコ
ン結晶７が得られる。通常るつぼ１等の高温部は不活性
ガスを満たした外囲器（図示せず）に収納されている。A silicon melt 3 is contained in a crucible 1 having two small holes 2a and 2b at the bottom, while two crystal edge supports 4a and 4 are placed in the crucible 1.
b are respectively arranged from the bottom to the top of the crucible 1, and then the seed crystal 5 is brought into contact with the silicon melt 3 between the two supporting materials 4a and 4b and the two supporting materials 4a and 4b,
This seed crystal 5 is pulled up. As a result, the silicon melt (i.e., meniscus) 6 stretched by surface tension between the two supporting materials 4a, 4b and the seed crystal 5 is continuously crystallized, and a band-shaped silicon crystal 7 is obtained. . Usually, a high temperature part such as the crucible 1 is housed in an envelope (not shown) filled with an inert gas.
本方法に用いる結晶端支持材４ａ、４ｂおよび支持材４
ａ 、４ｂのるつぼ１への配置の手法は次のように行わ
れていた。すなわち、
■ 支持材４ａ、４ｂとしてグラファイト棒、石英棒、
サファイア棒など、シリコン融液に浸しても支持材の直
線性が失われ難いものを用い、第３図に示すように、支
持材４ａ、４ｂを種結晶５に予め接続させておき、この
第３図に示した種結晶５−支持材４ａ 、４ｂの一体物
をシリコン融液３を収容したるつぼ１に上方から挿入し
、種結晶５がシリコン融液３に接触した後引上げる。こ
の際、るつぼが十分深ければ底部に孔はなくともよい。Crystal edge supports 4a, 4b and support material 4 used in this method
The method for placing a and 4b in crucible 1 was as follows. That is, ■ graphite rods, quartz rods, as supporting materials 4a and 4b;
Using something that does not easily lose its linearity even when immersed in silicon melt, such as a sapphire rod, the supporting materials 4a and 4b are connected to the seed crystal 5 in advance as shown in FIG. The integrated seed crystal 5 and supporting materials 4a and 4b shown in FIG. 3 is inserted from above into the crucible 1 containing the silicon melt 3, and after the seed crystal 5 comes into contact with the silicon melt 3, it is pulled up. At this time, if the crucible is deep enough, there may be no hole at the bottom.
■ るつは１の底が浅い場合、第３図の種結晶５−支持
材４ａ 、４ｂの一体物をシリコン融液３上方から挿入
していき、るつぼ１の底部にあけた小孔２ａ、２ｂに支
持材４ａ、４ｂを通す。種の結晶５の部分がシリコン融
液３に接触した後、引上げを開始する。■ If the bottom of the crucible 1 is shallow, insert the integrated seed crystal 5-supporting materials 4a and 4b shown in FIG. Support members 4a and 4b are passed through 2b. After the seed crystal 5 comes into contact with the silicon melt 3, pulling is started.
■ 支持材４ａ 、４ｂとして、前記■に述べた如きシ
リコン融液中でも比較的直線性を保つ素材を用い、るつ
ぼ１内でシリコンが溶融している時点でるつぼ等を収納
した外囲器の外の下方から、支持材４ａ、４ｂをるつぼ
１の底にあけた小孔２ａ。■ As the supporting materials 4a and 4b, materials that maintain relatively linearity even in the silicon melt as described in (■) above are used, and when the silicon is melted in the crucible 1, the outside of the envelope containing the crucible etc. is used. A small hole 2a is formed in the bottom of the crucible 1 through the supports 4a and 4b from below.
２ｂに通るように挿入する。しかる後、シリコン融液３
の上方から種結晶５をおろして、シリコン融液３および
支持材４ａ、４ｂと接触させた後引上げる。Insert it so that it passes through 2b. After that, silicon melt 3
Seed crystal 5 is lowered from above, brought into contact with silicon melt 3 and supporting materials 4a and 4b, and then pulled up.
■ 支持材４ａ、４ｂとして、直径数十μｍの炭素Ｉ！
維、炭化硅素繊維などを（数百−数千水）束ねた織糸を
用い、結晶成長前の装置組込みの際（室温で）るつぼ１
底部の小孔２ａ、２ｂに上記支持材４ａ、４ｂを通して
おき、同時にシリコン原料をるつぼに入れる。しかる後
、温度を上昇させてシリコン原料を融解させた後、種結
晶５を上方からおろしてシリコン融液３および支持材４
ａ。■ Carbon I with a diameter of several tens of μm is used as the supporting materials 4a and 4b!
Using a weaving yarn made by bundling fibers, silicon carbide fibers, etc. (hundreds to thousands of water), the crucible 1 is used (at room temperature) when incorporated into the equipment before crystal growth.
The supporting materials 4a and 4b are passed through the small holes 2a and 2b at the bottom, and at the same time, the silicon raw material is put into the crucible. After that, the temperature is increased to melt the silicon raw material, and then the seed crystal 5 is lowered from above to form the silicon melt 3 and the support material 4.
a.
４ｂと接触させて結晶成長を開始する。4b to start crystal growth.
［背景技術の問題点］
前述した■、■、■の従来方法では、それぞれ以下のよ
うな問題があった。すなわち、■の方法では、長尺の帯
状シリコン結晶を得ようとすればるつぼの深さを相当深
くしなければならず、実用的でない。また、種結晶と支
持材を一体化した部品を結晶成長ごとに製作しなければ
ならず、甚だ手数がかかる方法である。[Problems with Background Art] The conventional methods (1), (2), and (3) described above each have the following problems. That is, in method (2), if a long band-shaped silicon crystal is to be obtained, the depth of the crucible must be increased considerably, which is not practical. Furthermore, a part that integrates the seed crystal and the supporting material must be manufactured for each crystal growth, which is a very time-consuming method.
°■の方法では、■のようにるつぼを深くする必要はな
いが、長い帯状シリンコ結晶を得るには支持材を長くし
、これをシリコン融液上方からるつぼ底部の小孔に通さ
ねばならず、この操作はかなり困難である。というのは
、支持材がシリコン融−液に浸っても比較的直線性を保
つとはいっても、多少の変形が生じるからであり、これ
をシリコン融液に隠れて見えないるつぼ底部の２個の小
孔に同時に通すことは困難である。In method °■, it is not necessary to make the crucible deep as in method ■, but in order to obtain long band-shaped silinco crystals, the supporting material must be lengthened and passed through the small hole at the bottom of the crucible from above the silicon melt. , this operation is quite difficult. This is because although the supporting material maintains its relative straightness even when immersed in the silicon melt, some deformation occurs, and this is caused by the two invisible parts at the bottom of the crucible that are hidden in the silicon melt. It is difficult to pass through the small holes at the same time.
■の方法では、るつぼを深くせずとも長い帯状シリコン
結晶を得ることができ、また、支持材を配置するにも■
のような困難さはない。しかしながら、■、■について
も言えることであるが、グラファイト棒、石英棒、サフ
ァイア棒などのようなシリコン液中でも直線性を保つ材
料は高価であり、支持材だけを結晶からはずして再使用
することもほとんど不可能であるため、得られるシリコ
ン結晶基板も高価になってしまう。また、結晶成長の連
続性の目的には長い支持材が必要であるが、上述の材料
による長い素材は入手し難い。光通信用などのグラスフ
ァイバは長尺物が入手できるが、それほど安価ではなく
、小さく巻いておくことができず（直径２５０μｍのフ
ァイバでは巻取り直径は３０−４００必要）、装置が大
型化する。With method ①, long band-shaped silicon crystals can be obtained without making the crucible deep, and it is also possible to arrange the supporting material ②
It's not as difficult as . However, as can be said about ■ and ■, materials that maintain linearity even in silicone liquid, such as graphite rods, quartz rods, and sapphire rods, are expensive, and it is difficult to reuse only the supporting material by removing it from the crystal. Since this is almost impossible, the resulting silicon crystal substrate also becomes expensive. Further, long supporting materials are necessary for the purpose of continuous crystal growth, but long materials made of the above-mentioned materials are difficult to obtain. Glass fibers for optical communications are available in long lengths, but they are not very cheap and cannot be wound into small pieces (a fiber with a diameter of 250 μm requires a winding diameter of 30-400 μm), which increases the size of the equipment. .
これに対し、■に述べた炭素繊維などの織糸は、長さ数
順のものでも容易に入手でき、価格も前記のグラファイ
ト棒、石英棒などとは比較にならないほど安く、支持材
として適した材料と言える。On the other hand, weaving threads such as carbon fiber mentioned in (■) are easily available even in numerical order of length, and the price is much lower than that of the graphite rods, quartz rods, etc. mentioned above, making them suitable as supporting materials. It can be said that it is a good material.
しかしながら、炭素４ＩＮなどの織糸は結晶成長の過程
で切れてしまうことがある。これは、シリコン融液中に
ある程度の時間浸しておくと、シリコンと炭素が反応し
て織糸が細くなることがひとつの原因である。■に述べ
たような、織糸を予めるつぼに組込んでおく方法によれ
ば、上述のように結晶成長の過程で織糸が切れた場合や
、なんらかの理由により、結晶成長を種付けからやり直
そうとする場合、そのままではもはや成長を行うことが
できず、結晶製造装置の温度を下げ、再び組込みから始
める以外に方法がなかった。すなわち、炭素繊維などの
織糸はシリコン融液中では外力がなければ直線性を保て
ず、外囲器外部からるつぼの小孔を通してシリコン融液
上に出すという■に述べた手法を執ることはできない。However, weaving threads such as carbon 4IN may break during the crystal growth process. One reason for this is that when immersed in silicon melt for a certain amount of time, silicon and carbon react and the threads become thinner. According to the method described in (2), in which the weaving threads are assembled in a pot in advance, if the weaving threads break during the crystal growth process as described above, or for some other reason, the crystal growth must be restarted from seeding. In this case, it was no longer possible to grow the crystal as it was, and the only way was to lower the temperature of the crystal manufacturing equipment and start again by assembling the crystal. In other words, weaving threads such as carbon fibers cannot maintain their linearity in silicon melt without external force, so the method described in item (2) is taken, in which they are brought out from the outside of the envelope through the small holes of the crucible onto the silicon melt. I can't.
これまで述べたように、結晶端支持材を用いて帯状シリ
コン結晶を製造するに際しては、長尺の結晶を連続して
しかも安価に得る方法がなかった。As described above, when manufacturing band-shaped silicon crystals using crystal edge support materials, there has been no method to obtain long crystals continuously and at low cost.
［発明の目的］
本発明は前述の従来方法のさまざまな問題点に鑑みてな
されたもので、結晶端支持材を用いて製造する帯状シリ
コン結晶を、長時間連続して、しかも安価に製造する帯
状シリコン結晶の製造方法を提供することを目的とする
。[Object of the Invention] The present invention has been made in view of the various problems of the conventional methods described above, and it is an object of the present invention to continuously manufacture band-shaped silicon crystals using crystal edge supporting materials over a long period of time and at low cost. An object of the present invention is to provide a method for manufacturing band-shaped silicon crystals.
［発明の概要コ 上記目的を達成する本発明の概要は以下の通りである。[Summary of the invention] The outline of the present invention for achieving the above object is as follows.
すなわち、結晶端支持材として、それぞれの先端の一部
が棒状すなわち張力を加えずとも直線的であり、他の部
分が糸状即ち柔軟で張力を加えることにより直線状とな
る如き支持材を用い、結晶製造を開始するにあたり、前
記るつぼ内でシリコンを溶融させた状態下において、前
記支持材先端を、前記るつぼ等の高温部を収納しておく
外囲器の外部から、前記るつぼの小孔および前記シリコ
ン融液に貫通させることで前記支持材を所定位置に配置
させた後、結晶製造を行うことを特徴とするものである
。That is, as a crystal edge support material, a part of each tip is rod-like, that is, straight even without applying tension, and the other part is thread-like, that is, flexible, and becomes straight when tension is applied. To start crystal production, with the silicon melted in the crucible, the tip of the support material is inserted into the small hole of the crucible and The method is characterized in that crystal production is performed after the supporting material is placed at a predetermined position by penetrating the silicon melt.
また、前記支持材としては、糸状の支持材の先端一部分
をバインダなどにより固めるが、或いは、所望の長さの
棒状支持材と糸状支持材を予め接続させて成ることを特
徴とする。Further, the supporting material is characterized in that a portion of the tip of a thread-like supporting material is hardened with a binder or the like, or a rod-like supporting material of a desired length and a thread-like supporting material are connected in advance.
［発明の実施例］
本発明を実施するにあたって用いた帯状シリコン結晶の
製造装置を第２図を参照して説明する。[Embodiments of the Invention] An apparatus for producing band-shaped silicon crystals used in carrying out the present invention will be described with reference to FIG. 2.
シリコン融液３を収容するるっぽ１として、グラファイ
ト製で底部に径約１．５履の小孔２ ａ、 ２ ｂを１
００ｍ＋間隔で２カ所あけたものを使用し、グラファイ
ト製の抵抗加熱ヒータ（図示せず）で加熱できるように
した。るつぼ１．ヒータ等の高温部は外囲器（図示せず
）に収納し、アルゴンガスで外囲圏内部を満たした。一
方、るつぼ１の底部にあけた２個の小孔２ａ、２ｂとそ
の下方の外囲器とは、支持材４ａ、４ｂをそれぞれ導く
ための２本の案内路（図示せず）にて連結した。すなわ
ち、内径２ｍｍ程度の円筒状グラファイトを前記案内路
としてるつぼ１と外囲器の間に設置することで、支持材
４ａ、４ｂ用のそれぞれの通路ができることとなる。こ
の通路長は約２０ｃｒｔｔであった。A small hole 2a, 2b made of graphite and having a diameter of about 1.5 mm is provided at the bottom of the hole 1 to accommodate the silicon melt 3.
Two locations were used, spaced apart by 00 m, and could be heated with a graphite resistance heater (not shown). Crucible 1. High-temperature parts such as heaters were housed in an envelope (not shown), and the inside of the envelope was filled with argon gas. On the other hand, the two small holes 2a and 2b drilled in the bottom of the crucible 1 and the envelope below are connected by two guide paths (not shown) for guiding the supporting materials 4a and 4b, respectively. did. That is, by installing a cylindrical graphite having an inner diameter of about 2 mm as the guide path between the crucible 1 and the envelope, passages for the supporting materials 4a and 4b are created. The path length was approximately 20 crtt.
前記るつぼ１内にシリコン原料を入れ、前記ヒータにて
所定温度まで加熱しシリコンを融解させた。この状態下
において、直径１１ｎ！Ｒのグラファイト棒、石英棒な
どの外力を加えずとも直線性を保つ材料を前記案内路を
通して外囲器外部から前記るつぼ１内のシリコン融液３
の液面上に出すことができた。ところが、帯状シリコン
結晶を連続して長尺に、しかも安価に製造するに適した
素材である炭素織糸を同様に案内路を通して外囲器外部
から挿入しても、シリコン融液面上に出るどころか、る
つぼ底部の小孔の部分で行止まり、その後いくら織糸を
挿入しても案内路内に織糸が詰まる状態になるだけであ
った。A silicon raw material was placed in the crucible 1 and heated to a predetermined temperature using the heater to melt the silicon. Under this condition, the diameter is 11n! A material that maintains linearity without applying an external force, such as a graphite rod or a quartz rod, is passed through the guide path from the outside of the envelope to the silicon melt 3 in the crucible 1.
could be brought out above the liquid level. However, even if a carbon woven thread, which is a material suitable for producing continuous long silicon crystal strips at low cost, is inserted from the outside of the envelope through the guide path, it does not come out on the surface of the silicon melt. On the contrary, the thread would come to a dead end at the small hole in the bottom of the crucible, and no matter how much thread was inserted thereafter, the thread would only become clogged in the guide path.
そこで、本発明に係る帯状シリコン結晶の製造方法では
、以下のような手法を実施した。第１図は本発明の一実
施例であり、結晶端支持材４ａ。Therefore, in the method for manufacturing a band-shaped silicon crystal according to the present invention, the following method was implemented. FIG. 1 shows an embodiment of the present invention, showing a crystal edge support member 4a.
４ｂとする炭素織糸を３ｍずつ２本用意し、それぞれ直
径３Ｉ−Ｉ＋のドラム８ａ 、８ｂに巻付け、それぞれ
の織糸先端の約２０Ｃ１１４程度の部分９ａ 、 ９ｂ
に炭素セメントを塗布し、前記部分９ａ、９ｂに張力を
加えながら乾燥させた。乾燥させた後はこの部分９ａ
、９ｂは外力を加えずとも直線性を保っている棒状とな
った。前記るつぼ１内でシリコンを融解させた状態にお
いて、第１図の先端部を固めた支持材４ａ 、４ｂの棒
状部分９ａ 、９ｂを外囲器外部から案内路に挿入する
ことで、支持材４ａ 、４ｂをシリコン融液面上に出す
ことに成功した。前記ドラム８ａ 、８ｂをそれぞれ外
囲器下方に取付け、引続き種結晶５を上方からシリコン
融液３および支持材４ａ、４ｂに接触させ引上げること
により、長さ３ＴｒＬ１幅１０口の帯状シリコン結晶を
製造することができた。Prepare two carbon woven yarns of 3 m each, each having a diameter of 3I-I+, and wrap them around drums 8a and 8b, each having a diameter of 3I-I+, and place approximately 20C114 portions 9a and 9b at the tip of each yarn.
Carbon cement was applied to the parts 9a and 9b and dried while applying tension to the parts 9a and 9b. After drying, this part 9a
, 9b has a rod shape that maintains linearity even without applying external force. In the state where the silicon is melted in the crucible 1, the rod-shaped parts 9a and 9b of the supports 4a and 4b whose tips shown in FIG. , 4b was successfully brought out onto the surface of the silicon melt. The drums 8a and 8b are attached to the lower part of the envelope, and the seed crystal 5 is brought into contact with the silicon melt 3 and the supports 4a and 4b from above and pulled up to form a band-shaped silicon crystal with a length of 3 TrL and a width of 10 openings. was able to manufacture it.
また、結晶成長途中になんらかの原因により織糸自体が
切れてしまい、成長が中断するという現象が生じること
があった。支持材４ａ、４ｂを室温状態でるつぼに配置
しておくという従来の手法では、このような状況になる
ともはや結晶成長ができないのであるが、本発明の方法
では、切れてしまった織糸のかわりに先端を固めた新し
い織糸を再び挿入し直すことにより成長を再開すること
ができた。種結晶としては、成長が中断した結晶をその
まま用いた。この間の時間損失は数分であった。結晶成
長が中断した後の再開の手段は上述に限らず、切れた織
糸を案内路から抜出し、その先端を固めて再び使用して
もよい。この手段は上述より多少時間がかかる。或いは
、それまでに成長した結晶を取出し、新しい支持材と種
結晶とで成長を始めからやり直すこともできる。Further, there have been cases where the weaving threads themselves break due to some reason during crystal growth, causing a phenomenon in which the growth is interrupted. In the conventional method of placing the supporting materials 4a and 4b in a crucible at room temperature, crystal growth is no longer possible in such a situation, but in the method of the present invention, the broken weaving threads are replaced by Growth could be restarted by reinserting a new thread with a hardened tip. As a seed crystal, a crystal whose growth had been interrupted was used as it was. The time loss during this time was several minutes. The means for resuming crystal growth after it has been interrupted is not limited to the above-mentioned method, and the cut thread may be pulled out from the guide path, its tip may be hardened, and used again. This procedure is somewhat more time consuming than the one described above. Alternatively, the previously grown crystal can be removed and growth can be restarted from the beginning using a new support material and seed crystal.
上記の実施例においては、結晶端支持材としての織糸の
先端部分を固めるのに炭素セメントの使用について述べ
たが、これに限らず、エポキシ系樹脂、フォトリソグラ
フィ用のレジスト材、化学接着材、化学のり等を用いて
も同様の効果が得られた。In the above example, the use of carbon cement to solidify the tip of the weaving thread as a crystal edge support material is described, but the use is not limited to this. A similar effect was obtained using chemical glue, etc.
さて、結晶端支持材の先端部分を固めてシリコン融液中
を通すため、得られる帯状シリコン結晶中に太陽電池素
子とした場合に悪影響を及ぼす不純物が混入することが
心配された。得られた結晶中のＦｅ 、Ｃｕ 、Ｔｉ
、Ｖ等の金属不純物について分析した結果、いずれも数
ｐｐｂもしくはそれ以下で、太陽電池の素子特性上問題
はなかった。この理由は、支持材を案内路に挿入した際
、案内路のるつぼ付近の部分が高温であるため、バイン
ダ中の不純物が溶剤などとともに抜けてしまうこと、お
よび、バインダで固めた部分が短く、融液中に浸ってい
る時間がごく短いため、バインダ中の不純物がシリコン
融液にあまり溶けないこと、更にはシリコン融液中に不
純物が溶けても結晶成長の際の偏析により、結晶中には
取込まれないことが考えられる。Now, since the tip of the crystal end support material is solidified and passed through the silicon melt, there was concern that impurities that would have a negative impact on the resulting band-shaped silicon crystal would be mixed in when used as a solar cell element. Fe, Cu, Ti in the obtained crystal
As a result of analysis of metal impurities such as , V, etc., they were found to be several ppb or less, and there were no problems in terms of the device characteristics of the solar cell. The reason for this is that when the support material is inserted into the guide path, the part of the guide path near the crucible is high temperature, so impurities in the binder escape together with the solvent, and the part solidified with the binder is short. Since the time spent immersed in the silicon melt is very short, impurities in the binder do not dissolve very well in the silicon melt.Furthermore, even if impurities dissolve in the silicon melt, they do not dissolve into the crystal due to segregation during crystal growth. may not be incorporated.
［発明の他の実施例コ
前述の実施例においては、支持材として炭素織糸の先端
部をバインダ等で固めたものを用いる方法について述べ
たが、他の実施例として次のような方法もある。すなわ
ち、支持材の先端を固めるかわりに、例えば長さ約２０
ｃｍ、直径１ｓ＋のグラファイト棒の下端に炭素織糸
を炭素セメントなどで接続し、グラファイト棒の上端を
前述のように案内路を通して外囲器外からるつぼへ導く
のである。この手法によっても前述と同様の効果が得ら
れた。[Other Embodiments of the Invention In the above-mentioned embodiments, a method was described in which the tip of the carbon woven yarn was hardened with a binder etc. as a support material, but as another embodiment, the following method may also be used. be. That is, instead of hardening the tip of the support, e.g.
A carbon woven thread is connected to the lower end of a graphite rod with a diameter of 1 s+ cm, using carbon cement, and the upper end of the graphite rod is guided from outside the envelope to the crucible through the guide path as described above. This method also produced the same effect as described above.
また、以下のような手法もとれる。すなわち、上記のグ
ラファイト棒の上端に炭素織糸を接続し、炭素織糸を下
方へ垂らす。グラファイト棒と炭素織糸を共に案内路へ
通して外囲器外からるつぼへ挿入し、種付けを行う。グ
ラファイト棒と炭素織糸の接続を弱くしておき、種付け
により種結晶と支持材である織糸とを接触させた後に、
グラファイト棒と炭素織糸とがはずれるようにしておけ
ば、グラファイト棒を何度も使用することができる。In addition, the following methods can also be used. That is, a carbon woven thread is connected to the upper end of the graphite rod, and the carbon woven thread is hung downward. Both the graphite rod and the carbon woven yarn are passed through the guide path and inserted into the crucible from outside the envelope to perform seeding. After weakening the connection between the graphite rod and the carbon thread and bringing the seed crystal into contact with the support material, the thread,
If the graphite rod and the carbon woven yarn are separated, the graphite rod can be used many times.
その他、本発明の変形例として、目的に応じて支持材の
先端部のみではなく、ある途中の部分を固めたり、また
は、例えば先端から１ｒｒＬは織糸、そこから１０ＣＩ
Ｒはグラファイト棒や石英棒、そこから後はまた織糸と
いうように、各種材質の支持材をつぎ足したものにより
結晶成長を行うこともできる。In addition, as a modification of the present invention, depending on the purpose, not only the tip of the support material but also a certain intermediate portion may be stiffened, or, for example, 1rrL from the tip may be a weaving thread, and 10CI from there.
Crystal growth can also be performed using a support material made of various materials, such as a graphite rod or a quartz rod for R, and a weaving thread after that.
尚、本発明に係る帯状シリコン結晶の製造方法は、これ
までに述べた実施例に限られるものではなく、支持材の
材質、バインダの材質など様々な変形が可能であり、本
発明の趣旨の範囲で実施することができる。Note that the method for manufacturing a band-shaped silicon crystal according to the present invention is not limited to the embodiments described so far, and various modifications such as the material of the supporting material and the material of the binder are possible, and the method of manufacturing the band-shaped silicon crystal according to the present invention is not limited to the embodiments described above. It can be carried out within a range.
［発明の効果コ
上述のように、本発明に係る帯状シリコン結晶の製造方
法によれば、２本の結晶端支持材同志の間で結晶を成長
させる手法において、支持材として安価で長尺のものが
容易に入手できる炭素１１１織糸や炭化硅素繊維織糸を
用いて、シリンコ原料が融解している状態でも外部から
所定の位置に支持材を配置することができる。このため
、従来の如くグラファイト棒、石英棒などを支持材とし
て使用するより長尺の帯状シリコン結晶が容易に得られ
るうえ、支持材自体が切れるなど結晶成長が中断しても
極く短い時間内に成長を再開できるという効果がある。[Effects of the Invention] As described above, according to the method for manufacturing a band-shaped silicon crystal according to the present invention, in the method of growing a crystal between two crystal end supports, an inexpensive and long length support material can be used. By using readily available carbon-111 woven yarn or silicon carbide fiber woven yarn, the supporting material can be placed at a predetermined position from the outside even when the silicone raw material is molten. For this reason, longer band-shaped silicon crystals can be obtained more easily than conventional methods that use graphite rods, quartz rods, etc. as supporting materials, and even if crystal growth is interrupted due to cutting of the supporting material itself, it can be achieved within an extremely short period of time. This has the effect of allowing growth to resume.
従って、結晶成長の時間的な歩留りが向上し、一方、支
持材も安価であるため、帯状シリコン結晶の製造コスト
の低下に功を奏する等の効果がある。Therefore, the temporal yield of crystal growth is improved, and since the supporting material is also inexpensive, it is effective in reducing the manufacturing cost of band-shaped silicon crystals.
第１図は本発明に係る帯状シリコン結晶製造に用いる支
持材の一例を示す説明図、第２図は帯状シリコン結晶製
造原理の説明図、第３図は従来技術である種結晶−支持
材一体物の構成図である。
１・・・るつぼ、２ａ、２ｂ・・・小孔、３・・・シリ
コン融液、４ａ、４ｂ・・・結晶端支持材、５・・・種
結晶、６・・・メニスカス、７・・・帯状シリコン結晶
、Ｂａ。
８１）・・・ドラム、９ａ 、９ｂ・・・棒状部分。
出願人代理人 弁理士 鈴江武彦
第１図
第２図 第３図Fig. 1 is an explanatory diagram showing an example of a support material used in the production of band-shaped silicon crystals according to the present invention, Fig. 2 is an explanatory diagram of the principle of producing band-shaped silicon crystals, and Fig. 3 is a conventional technique in which seed crystal and support material are integrated. It is a configuration diagram of an object. DESCRIPTION OF SYMBOLS 1... Crucible, 2a, 2b... Small hole, 3... Silicon melt, 4a, 4b... Crystal edge support material, 5... Seed crystal, 6... Meniscus, 7...・Striped silicon crystal, Ba. 81)...Drum, 9a, 9b...rod-shaped portion. Applicant's agent Patent attorney Takehiko Suzue Figure 1 Figure 2 Figure 3
Claims (3)
部より、少なくとも２本の結晶端支持材を、前記小孔そ
れぞれを通じて前記るつぼの上方に配置し、また、前記
るつぼにシリコン融液を収容し、その後、前記結晶端支
持材同志間の前記シリコン融液と前記結晶端支持材とに
種結晶を接触させ、この種結晶を引上げることにより、
前記結晶端支持材の間に表面張力により張られたシリコ
ン融液を連続的に結晶化させて帯状シリコン結晶を製造
する方法において、前記結晶端支持材として、それぞれ
の一部が棒状すなわち張力を加えずとも直線的であり、
他の部分が糸状即ち柔軟で張力を加えることにより直線
状となる如き結晶端支持材を用い、結晶製造を開始する
にあたり、前記るつぼ内でシリコンを溶融させた状態下
において、前記結晶端支持材を、るつぼ等の高温部を収
納しておく外囲器の外部から、前記るつぼの小孔および
前記シリコン融液に貫通させることで前記結晶端支持材
を所定位置に配置させた後、結晶製造を行うことを特徴
とする帯状シリコン結晶の製造方法。(1) At least two crystal edge supports are placed above the crucible through each of the small holes from the bottom of the crucible having at least two small holes in the bottom, and silicon melt is poured into the crucible. Then, by bringing a seed crystal into contact with the silicon melt between the crystal edge supporting materials and the crystal edge supporting material, and pulling up the seed crystal,
In the method of manufacturing a band-shaped silicon crystal by continuously crystallizing a silicon melt stretched between the crystal edge supports by surface tension, each part of the crystal edge supports is rod-shaped, that is, a part of the silicon melt is stretched by surface tension. It is linear even without adding,
When starting crystal production using a crystal edge support material whose other parts are thread-like, that is, flexible, and which becomes straight when tension is applied, the crystal edge support material is melted in the crucible. is passed through the small holes of the crucible and the silicon melt from the outside of the envelope that houses a high-temperature part such as a crucible, so that the crystal end support material is placed in a predetermined position, and then crystal production is performed. A method for manufacturing a band-shaped silicon crystal, characterized by performing the following steps.
の一部分をバインダ等により固められて成るものを用い
ていることを特徴とする特許請求の範囲第１項記載の帯
状シリコン結晶の製造方法。(2) A method for manufacturing a band-shaped silicon crystal according to claim 1, characterized in that the crystal end support material is formed by solidifying a portion of the tip of each thread-like material with a binder or the like. .
の素材を接続して成るものを用いることを特徴とする特
許請求の範囲第１項記載の帯状シリコン結晶の製造方法
。(3) The method for producing a band-shaped silicon crystal according to claim 1, characterized in that the crystal edge support material is made by connecting a thread-like material to a rod-like material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25409985A JPS62113794A (en) | 1985-11-13 | 1985-11-13 | Production of band silicon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25409985A JPS62113794A (en) | 1985-11-13 | 1985-11-13 | Production of band silicon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62113794A true JPS62113794A (en) | 1987-05-25 |
| JPH0375514B2 JPH0375514B2 (en) | 1991-12-02 |
Family
ID=17260207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25409985A Granted JPS62113794A (en) | 1985-11-13 | 1985-11-13 | Production of band silicon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62113794A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009029761A1 (en) * | 2007-08-31 | 2009-03-05 | Evergreen Solar, Inc. | Ribbon crystal string with extruded refractory material |
| US8304057B2 (en) | 2007-08-31 | 2012-11-06 | Max Era, Inc. | Ribbon crystal end string with multiple individual strings |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58194798A (en) * | 1982-05-07 | 1983-11-12 | Toshiba Corp | Apparatus for growth of flat plate silicon crystal |
-
1985
- 1985-11-13 JP JP25409985A patent/JPS62113794A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58194798A (en) * | 1982-05-07 | 1983-11-12 | Toshiba Corp | Apparatus for growth of flat plate silicon crystal |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009029761A1 (en) * | 2007-08-31 | 2009-03-05 | Evergreen Solar, Inc. | Ribbon crystal string with extruded refractory material |
| US7651768B2 (en) | 2007-08-31 | 2010-01-26 | Evergreen Solar, Inc. | Reduced wetting string for ribbon crystal |
| CN101784701A (en) * | 2007-08-31 | 2010-07-21 | 长青太阳能股份有限公司 | Ribbon crystal string with extruded refractory material |
| US8304057B2 (en) | 2007-08-31 | 2012-11-06 | Max Era, Inc. | Ribbon crystal end string with multiple individual strings |
| US8309209B2 (en) | 2007-08-31 | 2012-11-13 | Max Era, Inc. | Ribbon crystal string for increasing wafer yield |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0375514B2 (en) | 1991-12-02 |
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