JPH0936403A - Production of basic body and solar cell employing it - Google Patents
Production of basic body and solar cell employing itInfo
- Publication number
- JPH0936403A JPH0936403A JP7180459A JP18045995A JPH0936403A JP H0936403 A JPH0936403 A JP H0936403A JP 7180459 A JP7180459 A JP 7180459A JP 18045995 A JP18045995 A JP 18045995A JP H0936403 A JPH0936403 A JP H0936403A
- Authority
- JP
- Japan
- Prior art keywords
- mold
- substrate
- solar cell
- furnace
- plate
- 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.)
- Granted
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、基体の製造方法および
太陽電池に係る。より詳細には、安価で、かつ、不純物
の少ない表面を有する基体の製造方法に関する。また、
上記基体の製造方法による基体を用いることによって、
光電変換特性が改善された太陽電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate manufacturing method and a solar cell. More specifically, the present invention relates to a method for manufacturing a substrate which is inexpensive and has a surface with few impurities. Also,
By using the substrate according to the above method for producing a substrate,
The present invention relates to a solar cell having improved photoelectric conversion characteristics.
【０００２】[0002]
【従来の技術】各種機器の駆動エネルギー源や商用電力
と系統連結させる電源として、太陽電池が広く研究され
ている。2. Description of the Related Art Solar cells have been widely studied as a driving energy source for various devices and a power source for systematic connection with commercial power.
【０００３】このような太陽電池は、コスト的要請から
金属のように低価格で入手できる基体上に、光電変換素
子が形成できることが望まれている。[0003] In such a solar cell, it is desired that a photoelectric conversion element can be formed on a substrate such as a metal that can be obtained at a low price because of cost requirements.
【０００４】一方、太陽電池を構成する光電変換素子と
しては、一般にＳｉからなる半導体が用いられる。光エ
ネルギーを電気エネルギーに変換する効率の点からは、
前記半導体としては、単結晶Ｓｉを用いるのが好まし
い。しかし、太陽電池の大面積化および低コスト化の点
から、アモルファスＳｉが有利である。また近年では、
アモルファスＳｉ並みの低コストと単結晶Ｓｉ並みの高
い光電変換効率とを同時に得る目的から多結晶Ｓｉの使
用が検討されている。On the other hand, a semiconductor made of Si is generally used as a photoelectric conversion element constituting a solar cell. In terms of efficiency of converting light energy into electric energy,
It is preferable to use single crystal Si as the semiconductor. However, amorphous Si is advantageous in terms of increasing the area and cost of the solar cell. In recent years,
The use of polycrystalline Si is being studied for the purpose of simultaneously obtaining a low cost comparable to that of amorphous Si and a high photoelectric conversion efficiency comparable to that of single crystal Si.
【０００５】しかしながら、従来の単結晶Ｓｉや多結晶
Ｓｉからなる太陽電池では、塊状の結晶をスライスし、
板状体に加工して用いるため、その厚さを０．３ｍｍ以
下にすることは困難であった。したがって、光量を吸収
するのに必要十分な厚さ以上となっているため、材料の
有効利用が不十分であった。すなわち、コストを下げる
ためには、さらなる薄型化を図る必要があった。However, in a conventional solar cell made of single crystal Si or polycrystalline Si, a lump crystal is sliced,
Since it is used after being processed into a plate-like body, it is difficult to reduce the thickness to 0.3 mm or less. Therefore, since the thickness is more than necessary and sufficient to absorb the amount of light, the effective use of the material was insufficient. That is, in order to reduce the cost, it was necessary to further reduce the thickness.
【０００６】最近では、上述した薄型化を解決する方法
として、溶融したＳｉの液滴を鋳型に流し込むスピン法
によりシリコンシートを形成する方法が提案されてい
る。しかし、この方法によっても、厚さは最小０．１ｍ
ｍ〜０．２ｍｍ程度であり、結晶Ｓｉとして光吸収に必
要十分な膜厚（２０〜５０μｍ）に比べて、まだ薄型化
が不十分である。また、このような薄型化によって、シ
リコンシート自体が基体としての強度を維持することが
困難となる。その結果、必然的にシリコンシートを支持
する別の安価な基体が要求される。[0006] Recently, as a method for solving the above-mentioned thinning, a method of forming a silicon sheet by a spin method of pouring molten Si droplets into a mold has been proposed. However, even with this method, the minimum thickness is 0.1 m.
The thickness is about m to 0.2 mm, and the thinning is still insufficient as compared with the film thickness (20 to 50 μm) necessary for absorbing light as crystalline Si. Further, such thinning makes it difficult for the silicon sheet itself to maintain its strength as a substrate. As a result, there is a need for another inexpensive substrate that necessarily supports the silicon sheet.
【０００７】このような別の安価な基体としては、例え
ば金属級Ｓｉ（T.Warabisako, T.Saitoh, E.Kuroda, H.
Itoh. N.Nakamura and T.Tokuyama, “Efficient Solar
Cells from Metallurgical-GradeSilicon", Proceedin
gs of the 11th Conferenceon Solid State Devices, T
okyo, 1979; Japanese Journal of Applied Physics,
19 (1980) Supplement 19-1, p.539）が挙げられる。T.
Warabisako 等は、前記金属級Ｓｉを用いて基体を形成
し、その上に光吸収に必要十分な膜厚のＳｉ層を形成し
て太陽電池とする試みを報告している。As such another inexpensive substrate, for example, metallic grade Si (T. Warabisako, T. Saitoh, E. Kuroda, H.
Itoh. N. Nakamura and T. Tokuyama, “Efficient Solar
Cells from Metallurgical-GradeSilicon ", Proceedin
gs of the 11th Conferenceon Solid State Devices, T
okyo, 1979; Japanese Journal of Applied Physics,
19 (1980) Supplement 19-1, p.539). T.
Warabisako et al. Reported an attempt to form a substrate by using the above-mentioned metal-grade Si, and form a Si layer having a film thickness necessary and sufficient for light absorption on the substrate to obtain a solar cell.
【０００８】しかしながら、T.Warabisako 等の方法で
は、金属級Ｓｉを引き上げ法によって塊状結晶とした
後、これをスライスして板状基板を作製している。ゆえ
に、従来の単結晶Ｓｉを基体として用いたプロセスと同
じであり、安価な材料である金属級Ｓｉのメリットが生
かされていないという問題があった。また、現状では、
十分な特性を得るためには前記引き上げを２回行う必要
があり、製造に多大な時間がかかるという問題もあっ
た。However, in the method of T. Warabisco, et al., A plate-like substrate is prepared by slicing metal-like Si into a lump crystal by a pulling method. Therefore, the process is the same as the conventional process using single crystal Si as a substrate, and there is a problem that the merit of metal-grade Si, which is an inexpensive material, is not utilized. Also, at present,
In order to obtain sufficient characteristics, it is necessary to perform the pulling up twice, and there is also a problem that it takes a lot of time to manufacture.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、安価
で、かつ、不純物の少ない表面を有する基体の製造方法
を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for manufacturing a substrate having a surface which is inexpensive and has a small amount of impurities.
【００１０】また、本発明の他の目的は、上記基体の製
造方法による基体を用いることによって、光電変換特性
が改善された太陽電池を提供することである。Another object of the present invention is to provide a solar cell having improved photoelectric conversion characteristics by using the substrate produced by the above method for producing a substrate.
【００１１】[0011]
【課題を解決するための手段】本発明の基体の製造方法
は、半導体層を支持する基体の製造方法において、搬送
される方向に対して垂直方向に板状の溝を有する鋳型
が、前記板状の溝の内部にＳｉからなる原料を注入され
る第１工程と、前記鋳型をＳｉの融点よりも高い温度に
保ち、前記Ｓｉからなる原料を融解させて前記板状の溝
を満たす第２工程と、前記鋳型が搬送される方向に負の
温度勾配の設けられた炉内を、前記鋳型が移動する第３
工程と、前記鋳型が前記炉内を移動する間に、融解され
た前記Ｓｉを固化させる第４工程と、からなることを特
徴とする。A method of manufacturing a substrate according to the present invention is a method of manufacturing a substrate for supporting a semiconductor layer, wherein the mold having a plate-shaped groove in a direction perpendicular to a conveying direction is the plate. A first step of injecting a raw material made of Si into the inside of the groove having a groove shape; and a second step of melting the raw material made of Si by filling the template groove at a temperature higher than the melting point of Si to fill the plate-shaped groove. And a step of moving the mold in a furnace provided with a negative temperature gradient in a direction in which the mold is conveyed.
And a fourth step of solidifying the melted Si while the mold moves in the furnace.
【００１２】また、前記鋳型の材質は、カーボン・グラ
ファイト、シリコン・カーバイト、又は窒化珪素の中か
ら選択され、前記Ｓｉからなる原料は、金属級Ｓｉであ
ることが好ましい。It is preferable that the material of the mold is selected from carbon graphite, silicon carbide, and silicon nitride, and the raw material of Si is metallic grade Si.
【００１３】さらに、前記板状の溝の内面には、少なく
ともＳｉ3Ｎ4を含む離型剤が被膜されていることが望ま
しい。前記基体は、光電変換素子用として好適に用いら
れる。Further, it is desirable that the inner surface of the plate-shaped groove is coated with a release agent containing at least Si 3 N 4 . The base is suitably used for a photoelectric conversion element.
【００１４】本発明の太陽電池は、光電変換素子をなす
前記半導体層が、請求項１乃至５のいずれか１項に記載
の基体上に形成されたことを特徴とする。The solar cell of the present invention is characterized in that the semiconductor layer forming a photoelectric conversion element is formed on the substrate according to any one of claims 1 to 5.
【００１５】[0015]
【作用】本発明に係る請求項１では、第１工程から第４
工程を設けたため、以下に示す点の改善が図られた基体
の製造方法が得られる。In the first aspect of the present invention, the first to fourth steps are provided.
Since the steps are provided, it is possible to obtain a method for manufacturing a base body in which the following points are improved.
【００１６】まず、搬送される方向に対して垂直方向に
板状の溝を有する鋳型が、前記板状の溝の内部にＳｉか
らなる原料を注入される第１工程を設けたため、前記板
状の溝の内部に、原料を均一に注入することができる。First, since the mold having the plate-shaped groove in the direction perpendicular to the carrying direction is provided with the first step of injecting the raw material made of Si into the plate-shaped groove, the plate-shaped groove is formed. The raw material can be uniformly injected into the groove.
【００１７】また、前記鋳型をＳｉの融点よりも高い温
度に保ち、前記Ｓｉからなる原料を融解させて前記板状
の溝を満たす第２工程を設けたため、注入された原料は
十分に融解状態となる。Further, since the second step is provided in which the template is kept at a temperature higher than the melting point of Si and the raw material made of Si is melted to fill the plate-like groove, the injected raw material is sufficiently melted. Becomes
【００１８】さらに、前記鋳型が搬送される方向に負の
温度勾配の設けられた炉内を、前記鋳型が移動する第３
工程を設けたため、溶融した金属級Ｓｉが固化される
際、前記負の温度勾配により、鋳型の搬送される方向を
向いた面からＳｉの固化が始まり、これと反対側の面が
最後に固化する。その結果、金属級Ｓｉに含まれる不純
物は最後に固化する進行方向とは反対側の面付近に偏析
する。したがって、鋳型の搬送される方向を向いた面が
不純物の比較的少ない基板面として得られる。Further, the third mold is moved in a furnace provided with a negative temperature gradient in the direction in which the mold is conveyed.
Since a step is provided, when the molten metal-grade Si is solidified, the negative temperature gradient causes the solidification of Si to start from the surface of the mold facing the conveying direction, and the surface opposite to this solidifies last. To do. As a result, the impurities contained in the metallurgical Si are segregated in the vicinity of the surface on the side opposite to the traveling direction in which it is finally solidified. Therefore, the surface of the mold facing the carrying direction is obtained as the surface of the substrate containing relatively few impurities.
【００１９】またさらに、前記鋳型が前記炉内を移動す
る間に、融解された前記Ｓｉを固化させる第４工程を設
けたため、後加工無しに、金属級Ｓｉからなる板状の基
板が得られる。したがって、従来行われていた引き上げ
法のように基板形状をスライスするための工程が省略で
き、時間的・コスト的に改善する。Furthermore, since the fourth step of solidifying the melted Si is provided while the mold moves in the furnace, a plate-like substrate made of metal-grade Si can be obtained without post-processing. . Therefore, the step for slicing the substrate shape, which is required in the conventional pulling method, can be omitted, and the time and cost can be improved.
【００２０】本発明に係る請求項２では、前記鋳型の材
質が、カーボン・グラファイト、シリコン・カーバイ
ト、又は窒化珪素の中から選択されるため、繰り返し使
用に耐える鋳型が形成できる。その結果、低コスト化が
図られ、安価な基体の製造方法が得られる。According to the second aspect of the present invention, since the material of the mold is selected from carbon graphite, silicon carbide or silicon nitride, it is possible to form a mold that can be used repeatedly. As a result, cost reduction can be achieved and an inexpensive method for manufacturing a substrate can be obtained.
【００２１】本発明に係る請求項３では、前記Ｓｉから
なる原料が、金属級Ｓｉであるため、高純度Ｓｉ等で比
べた場合、材料費が非常に安く抑えられる。その結果、
通常のウエハと同等の強度を有する安価な基体の製造方
法が得られる。In the third aspect of the present invention, since the raw material made of Si is metallic grade Si, the material cost can be kept very low when compared with high purity Si or the like. as a result,
It is possible to obtain an inexpensive substrate manufacturing method having a strength equivalent to that of a normal wafer.
【００２２】本発明に係る請求項４では、前記板状の溝
の内面には、少なくともＳｉ3Ｎ4を含む離型剤が被膜さ
れているため、固化後の金属級Ｓｉからなる板状基体の
鋳型からの取り外しが容易となる。その結果、一度に多
数枚の板状基体の処理が可能になる。According to a fourth aspect of the present invention, since the inner surface of the plate-like groove is coated with a release agent containing at least Si 3 N 4 , the plate-like substrate made of metal-grade Si after solidification. Can be easily removed from the mold. As a result, a large number of plate-shaped substrates can be processed at one time.
【００２３】本発明に係る請求項５では、前記基体が、
光電変換素子用であるため、従来の単結晶Ｓｉ基体や多
結晶Ｓｉ基体に比べ材料の有効利用が可能となる。その
結果、製造コストの低い太陽電池を供給できる基体の製
造方法が得られる。According to a fifth aspect of the present invention, the substrate is
Since it is for a photoelectric conversion element, the material can be effectively used as compared with the conventional single crystal Si substrate or polycrystalline Si substrate. As a result, it is possible to obtain a method for manufacturing a base body that can supply a solar cell with low manufacturing cost.
【００２４】本発明に係る請求項６では、光電変換素子
をなす前記半導体層が、請求項１乃至５のいずれか１項
に記載の基体上に形成されたため、Ｓｉ等からなる半導
体層成長時に、前記基体から前記半導体層ヘの不純物移
動を低減できる。その結果、従来その対策として行われ
ていたゲッタリング処理を省略することができるため、
低コスト化が図れる。According to a sixth aspect of the present invention, since the semiconductor layer forming the photoelectric conversion element is formed on the substrate according to any one of the first to fifth aspects, a semiconductor layer made of Si or the like is grown. The migration of impurities from the base to the semiconductor layer can be reduced. As a result, the gettering process that was conventionally performed as a countermeasure can be omitted.
Cost reduction can be achieved.
【００２５】[0025]
（基体）本発明に係る基体に使用される金属級Ｓｉとし
ては、低純度、具体的には不純物元素を１ｐｐｍ乃至２
％含むものが安価で容易に用いられる。粉末状にしてか
ら、溶融される前に、必要に応じて予め塩酸等の酸によ
る処理を行い、不純物の量を軽減しておくことも可能で
ある。(Substrate) The metal-grade Si used for the substrate according to the present invention has a low purity, specifically, 1 ppm to 2 of an impurity element.
% Content is cheap and easy to use. It is also possible to reduce the amount of impurities by performing a treatment with an acid such as hydrochloric acid in advance, if necessary, after the powder is formed and before being melted.
【００２６】（鋳型）本発明に係る鋳型としては、縦方
向に板状に溝を設けたものであって、溝の数は一つの鋳
型に対して一つでも複数でもよく、またこのような溝を
持った鋳型を複数個連結した構造のものでも構わない。
鋳型の材質としては、加工の容易性や価格の点からカー
ボン・グラファイトが用いられる。しかし、溶融／固化
したＳｉを離型させる材料が塗布でき、かつ、融点がＳ
ｉのそれよりも高いものであれば何でも良く、シリコン
・カーバイトや窒化珪素等も使用可能である。(Mold) The mold according to the present invention has a plate-like groove provided in the longitudinal direction, and the number of grooves may be one or plural per one mold. It may have a structure in which a plurality of molds having grooves are connected.
As the material of the mold, carbon graphite is used in terms of easiness of processing and price. However, a material for releasing molten / solidified Si can be applied, and the melting point is S
Any material higher than that of i can be used, and silicon carbide, silicon nitride or the like can be used.
【００２７】（離型剤）本発明に係る鋳型内に塗布され
る離型剤としては、溶融したＳｉに対して反応を起こさ
ず接触角の大きいものが選ばれる。具体的にはＳｉ3Ｎ4
を主成分としたものが用いられ、必要に応じてＳｉＯ2
等が添加される。離型剤の鋳型内への被膜の仕方として
は、粉末状のＳｉ3Ｎ4を分散させた有機溶液あるいはシ
ラノール溶液を鋳型内にスプレーし、４００℃以上の熱
処理をして被膜を形成する。(Release Agent) As the release agent applied in the mold according to the present invention, a release agent having a large contact angle without causing a reaction with molten Si is selected. Specifically, Si 3 N 4
Is used as the main component, and if necessary, SiO 2
Etc. are added. As a method of coating the mold release agent in the mold, an organic solution or silanol solution in which powdery Si 3 N 4 is dispersed is sprayed into the mold, and heat treatment is performed at 400 ° C. or higher to form the film.
【００２８】（炉）本発明に係る炉としては、電気炉が
制御性の上から好ましい。また、同一炉内にＳｉを融解
するためにＳｉの融点以上の温度一定に保たれた部位
と、Ｓｉの融点以上の温度から融点以下の温度に至るま
で負の温度勾配の設けられた部位とを有し、これらの部
位の間を鋳型が移動できる構造のものが望ましい。(Furnace) As the furnace according to the present invention, an electric furnace is preferable from the viewpoint of controllability. Further, in order to melt Si in the same furnace, a portion kept at a temperature equal to or higher than the melting point of Si and a portion provided with a negative temperature gradient from a temperature equal to or higher than the melting point of Si to a temperature equal to or lower than the melting point of Si. It is desirable that the structure has a structure such that the template can move between these sites.
【００２９】炉内に設けられる温度勾配、及び、鋳型が
温度勾配のある部位を移動するときの速度は、溶融させ
たＳｉの固化条件によって適宜決められる。しかし、固
化したシートの結晶性や不純物の偏析効果の点から、鋳
型が移動するときに受ける降温速度（＝温度勾配×移動
速度）は、およそ−３０℃／ｍｉｎ以下となるように設
定されるのが好ましい。The temperature gradient provided in the furnace and the speed at which the mold moves in the region having the temperature gradient are appropriately determined depending on the solidification conditions of the melted Si. However, from the viewpoint of the crystallinity of the solidified sheet and the segregation effect of impurities, the temperature decreasing rate (= temperature gradient × moving rate) received when the mold moves is set to be about −30 ° C./min or less. Is preferred.
【００３０】[0030]
【実施例】以下実施例により、本発明に係る基体の製造
方法および太陽電池について更に詳しく説明するが、本
発明はこれらの実施例により限定されるものではない。EXAMPLES The method for producing a substrate and the solar cell according to the present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.
【００３１】（実施例１）本例では、図１に示した基体
の製造工程に基づき、金属級Ｓｉの溶融／固化によるシ
ート基体の製造方法に関して説明する。図１の鋳型１０
１は、縦方向に板状の溝を設けたカーボン製のものを用
いた。また、溝の表面に固化したＳｉを容易に取り出す
目的で、その内面にはＳｉ3Ｎ4膜を塗布した。Example 1 In this example, a method of manufacturing a sheet substrate by melting / solidifying metal grade Si will be described based on the substrate manufacturing process shown in FIG. Mold 10 of FIG.
For No. 1, a carbon product having plate-shaped grooves in the longitudinal direction was used. Further, for the purpose of easily taking out the solidified Si on the surface of the groove, a Si 3 N 4 film was applied to the inner surface thereof.
【００３２】以下では、上記製造方法を工程に沿って説
明する。 （１）粉末状の金属級Ｓｉ１０３を、フィーダー１０２
を通して鋳型内の溝に投入し、カーボン製の蓋１０４で
溝の口を塞ぎ、図１に示すような電気炉内に置いた。 （２）Ｓｉの融点よりも高い一定温度に設定された電気
炉内に、ある一定時間保持することによって、粉末状金
属級Ｓｉを融液１０６にした。In the following, the manufacturing method will be described along with steps. (1) The powdery metal grade Si 103 is fed to the feeder 102.
It was charged into the groove in the mold through the through hole, the opening of the groove was closed with a carbon lid 104, and it was placed in an electric furnace as shown in FIG. (2) The powdery metallurgical grade Si was made into the melt 106 by holding for a certain period of time in an electric furnace set at a constant temperature higher than the melting point of Si.
【００３３】（３）同じ電気炉内に設けられた水平方向
に温度勾配のある部位の中をゆっくりと一定速度で鋳型
１０１を移動させた。このとき図１に示すように鋳型の
進行方向に対して温度勾配が負となるように設定した。 （４）鋳型が融点付近に相当する炉の部位を通過した
後、十分離れた所で温度を室温にまで落とした。 （５）固化した板状のシート基体を鋳型から取り出し
た。(3) The mold 101 was slowly moved at a constant speed in a portion having a temperature gradient in the horizontal direction provided in the same electric furnace. At this time, as shown in FIG. 1, the temperature gradient was set to be negative with respect to the moving direction of the mold. (4) After the mold passed through the part of the furnace near the melting point, the temperature was dropped to room temperature at a sufficiently distant place. (5) The solidified plate-shaped sheet substrate was taken out from the mold.
【００３４】以下では、上記工程（１）〜（５）によっ
て得られた、シート基体の表面付近の元素分析を行った
結果に関して説明する。The results of the elemental analysis near the surface of the sheet substrate obtained by the above steps (1) to (5) will be described below.
【００３５】表１は不純物分析の結果である。表１にお
いて、「金属級Ｓｉ」とは原料の分析結果であり、「進
行方向側」及び「反対側」とは形成したシート基体の場
合を示した。ここで、「進行方向側」とは、鋳型の進行
方向を向いた側の面を意味する。一方、「反対側」と
は、「進行方向側」の反対面である。Table 1 shows the results of the impurity analysis. In Table 1, “Metal grade Si” is the result of analysis of the raw material, and “advancing direction side” and “opposite side” indicate the case of the formed sheet substrate. Here, the "traveling direction side" means the surface on the side facing the traveling direction of the mold. On the other hand, the “opposite side” is the opposite side of the “traveling direction side”.
【００３６】表１から、溶融／固化という過程でかなり
の不純物の移動があったことが分かった。特に、「進行
方向側」は「反対側」に比べて、遥かに不純物の量が減
少していることが確認された。From Table 1, it was found that there was a considerable migration of impurities in the process of melting / solidification. In particular, it was confirmed that the amount of impurities on the “traveling direction side” was much smaller than that on the “opposite side”.
【００３７】[0037]
【表１】 [Table 1]
【００３８】表１の結果から、鋳型１０１が融点付近に
相当する炉の部位を通過する際、融液１０６は進行方向
を向いた側の面から固化が始まり、反対側の面は最後に
固化したため、金属級Ｓｉに含まれる不純物は進行方向
とは反対側の面付近に偏析することが分かった。またSe
ccoエッチングにより結晶粒界を顕在化させたところ、
得られたシートの結晶粒径は数ｍｍ〜数ｃｍまで拡大し
ており、通常のキャスティング法で得られるＳｉインゴ
ットの場合と同等であった。From the results shown in Table 1, when the mold 101 passes through the part of the furnace corresponding to the vicinity of the melting point, the melt 106 starts to solidify from the surface facing the advancing direction, and the opposite surface finally solidifies. Therefore, it was found that the impurities contained in the metal-grade Si segregated near the surface on the side opposite to the traveling direction. See Se
When the crystal grain boundaries were revealed by cco etching,
The crystal grain size of the obtained sheet was expanded to several mm to several cm, which was equivalent to that of the Si ingot obtained by the ordinary casting method.
【００３９】（実施例２）本例では、実施例１で得られ
たシート基体上に、ＣＶＤ法によりＳｉ層を結晶成長さ
せた場合を説明する。 （１）シート基体の不純物が偏析した側の面をＨＦ／Ｈ
ＮＯ3系のエッチャントにより数十μｍエッチバックし
た。 （２）原料ガスにＳｉＨ2Ｃｌ2を用いて、成長温度を１
０５０℃とし、約０．８μｍ／ｍｉｎの成長速度で、不
純物が少なかった側の面上にＳｉ層を３０μｍ形成し
た。 （３）成長終了後Ｓｉ層表面を光学顕微鏡及び走査型電
子顕微鏡で観察した。(Example 2) In this example, a case will be described in which a Si layer is crystal-grown on the sheet substrate obtained in Example 1 by the CVD method. (1) HF / H on the surface of the sheet substrate on the side where the impurities are segregated
Etched back by several tens of μm with a NO 3 based etchant. (2) SiH 2 Cl 2 is used as the source gas and the growth temperature is set to 1
The temperature was set to 050 ° C. and the growth rate was about 0.8 μm / min. (3) After the growth, the surface of the Si layer was observed with an optical microscope and a scanning electron microscope.
【００４０】その結果、得られたＳｉ層表面はシート基
体の表面と同等であり、比較的平坦なＳｉ層が形成され
た。また、結晶粒径も下地であるシートの大きさを受け
継いでいた。さらに、得られたＳｉ層表面のエッチピッ
ト密度は、約１×１０4個／ｃｍ2であった。As a result, the surface of the obtained Si layer was equivalent to the surface of the sheet substrate, and a relatively flat Si layer was formed. Further, the crystal grain size also inherits the size of the base sheet. Furthermore, the etch pit density on the surface of the obtained Si layer was about 1 × 10 4 pieces / cm 2 .
【００４１】（実施例３）本例では、実施例２で作製し
たＳｉ層を活性層として、その上に薄膜太陽電池を形成
した場合を説明する。(Example 3) In this example, the case where the thin film solar cell is formed on the Si layer produced in Example 2 as an active layer will be described.
【００４２】以下では、薄膜太陽電池の形成工程に沿っ
て説明する。 （１）Ｓｉ層の表面に、イオン打ち込み法により、Ｐを
８０ｋｅＶ、１×１０15／ｃｍ2の条件で打ち込んだ。
その後、アニール（温度８００℃、時間３０分）して、
ｎ+層を形成した。 （２）上記ｎ+層の上に、集電電極（Ｃｒ（０．０２μ
ｍ）／Ａｇ（１μｍ）／Ｃｒ（０．００４μｍ））／透
明電極（ＩＴＯ（０．０８５μｍ））を、真空蒸着によ
り形成した。 （３）シート基体の裏面に、Ａ１を蒸着し、裏面電極と
した。The process of forming a thin film solar cell will be described below. (1) P was implanted into the surface of the Si layer by an ion implantation method under the conditions of 80 keV and 1 × 10 15 / cm 2 .
After that, anneal (temperature 800 ℃, time 30 minutes),
An n + layer was formed. (2) On the n + layer, a collector electrode (Cr (0.02μ
m) / Ag (1 μm) / Cr (0.004 μm)) / transparent electrode (ITO (0.085 μm)) was formed by vacuum evaporation. (3) A1 was vapor-deposited on the back surface of the sheet substrate to form a back surface electrode.
【００４３】上記工程（１）〜（３）によって作製した
薄膜結晶太陽電池に対して、ＡＭ１．５（１００ｍＷ／
ｃｍ2）光照射下でのＩ−Ｖ特性を測定した。その結
果、セル面積２ｃｍ2の場合、開放電圧０．５７Ｖ、短
絡光電流２９ｍＡ／ｃｍ2、曲線因子０．７４となり、
変換効率１２．２％を得た。AM1.5 (100 mW / 100 mW / for the thin film crystal solar cell produced by the above steps (1) to (3)
cm 2 ) I-V characteristics under light irradiation were measured. As a result, when the cell area was 2 cm 2 , the open circuit voltage was 0.57 V, the short circuit photocurrent was 29 mA / cm 2 , and the fill factor was 0.74.
A conversion efficiency of 12.2% was obtained.
【００４４】本例の結果から、金属級Ｓｉを溶融／固化
したシート基体を用い、その上にＳｉ層を積層すること
で、良好な特性を有する薄膜結晶太陽電池が形成できる
ことが分かった。From the results of this example, it was found that a thin film crystal solar cell having good characteristics can be formed by using a sheet substrate obtained by melting / solidifying metallurgical Si and laminating a Si layer thereon.
【００４５】（実施例４）本例では、金属級Ｓｉの溶融
／固化によるシート基体の製造方法において、次に示す
２つの点が実施例１と異なる。 （イ）粉末状の金属級Ｓｉとして、１２０℃に加熱した
塩酸／過酸化水混合溶液に粉末状の金属級Ｓｉを通して
不純物を浸出させた後、水洗／乾燥したものを用いた。(Embodiment 4) This embodiment differs from Embodiment 1 in the following two points in the method of manufacturing a sheet substrate by melting / solidifying metal grade Si. (A) As the powdery metal-grade Si, one obtained by leaching impurities through a powdery metal-grade Si into a hydrochloric acid / peroxide water mixed solution heated at 120 ° C., followed by washing / drying was used.
【００４６】（ロ）上記（イ）で作製した粉末状の金属
級Ｓｉを、フィーダーを用いてカーボン・グラファイト
製の鋳型内の溝に充填した。但し、鋳型の溝の内面に
は、予めＳｉ3Ｎ4粉末を分散させたシラノール溶液を鋳
型内に塗布し、４００℃の熱処理をして離型用被膜を形
成した。他の点は、実施例１と同様とした。(B) The powdery metallurgical grade Si produced in (a) above was filled in the grooves in the carbon graphite mold using a feeder. However, on the inner surface of the groove of the mold, a silanol solution in which Si 3 N 4 powder was previously dispersed was applied to the inside of the mold and heat-treated at 400 ° C. to form a mold release film. Other points were the same as in Example 1.
【００４７】以下では、上記製造方法を工程に沿って説
明する。 （１）図１に示す構造の電気炉内に鋳型を投入し、Ｓｉ
の融点よりも高い一定温度（１５００℃）に保持した。 （２）一定時間（３０分〜１時間）経過したところで、
同じ炉内の別の部位に設定された負の温度勾配（１℃／
ｍｍ）の中を、１０ｍｍ／ｍｉｎの速度で移動させた。 （３）Ｓｉが完全に固化し終わってからもしばらく移動
を続け、融点よりも十分低い温度領域に鋳型が来たとこ
ろで電気炉のヒータを切り、鋳型の温度を室温まで下げ
た。In the following, the manufacturing method will be described along with steps. (1) The mold is put into an electric furnace having the structure shown in FIG.
It was kept at a constant temperature (1500 ° C) above the melting point of. (2) When a certain time (30 minutes to 1 hour) has passed,
Negative temperature gradient set at another site in the same furnace (1 ℃ /
mm) at a speed of 10 mm / min. (3) Even after Si was completely solidified, it continued to move for a while, and when the mold came to a temperature region sufficiently lower than the melting point, the heater of the electric furnace was turned off and the temperature of the mold was lowered to room temperature.
【００４８】以下では、上記工程（１）〜（３）によっ
て得られた、シート基体の表面付近の元素分析を行った
結果に関して説明する。The results of elemental analysis of the vicinity of the surface of the sheet substrate obtained by the above steps (1) to (3) will be described below.
【００４９】表２は不純物分析の結果である。表２にお
いて、「進行方向側」とは、鋳型の進行方向を向いた側
の面を意味する。一方、「反対側」とは、「進行方向
側」の反対面である。Table 2 shows the results of the impurity analysis. In Table 2, "the advancing direction side" means the surface on the side facing the advancing direction of the mold. On the other hand, the “opposite side” is the opposite side of the “traveling direction side”.
【００５０】[0050]
【表２】 表２から、鋳型の進行方向を向いた側の面では、反対側
の面に比ベて遥かに不純物の量が減少していることが分
かった。[Table 2] From Table 2, it was found that the amount of impurities on the surface facing the advancing direction of the mold was much smaller than that on the opposite surface.
【００５１】また、Seccoエッチングにより結晶粒界を
顕在化させたところ、得られたシート基体の結晶粒径は
数ｍｍ〜数ｃｍまで拡大しており、通常のキャステイン
グ法で得られるＳｉインゴットの場合と同等であった。When the crystal grain boundaries were revealed by Secco etching, the crystal grain size of the obtained sheet substrate was expanded to several mm to several cm. In the case of the Si ingot obtained by the ordinary casting method, Was equivalent to.
【００５２】（実施例５）本例では、金属級Ｓｉの溶融
／固化によるシート基体の製造方法において、次に示す
２つの点が実施例１と異なる。 （イ）図１に示すようなＳｉＣ製の鋳型を作製し、鋳型
内の溝の内面にはＳｉ3Ｎ4粉末を分散させたシラノール
溶液を塗布し、６００℃の熱処理をして離型用被膜を形
成した。Example 5 This example differs from Example 1 in the following two points in the method of manufacturing a sheet substrate by melting / solidifying metal grade Si. (A) A mold made of SiC as shown in FIG. 1 was prepared, and a silanol solution in which Si 3 N 4 powder was dispersed was applied to the inner surface of the groove in the mold, and heat treatment was performed at 600 ° C. for mold release. A film was formed.
【００５３】（ロ）１２０℃に加熱した塩酸／過酸化水
混合溶液に粉末状の金属級Ｓｉを通して不純物を浸出さ
せた後、水洗／乾燥してからフィーダーを用いて鋳型内
の溝に充填した。他の点は、実施例１と同様とした。(B) Impurities were leached through a powdery metallic grade Si into a hydrochloric acid / peroxide water mixed solution heated at 120 ° C., washed with water / dried, and then filled in a groove in a mold using a feeder. . Other points were the same as in Example 1.
【００５４】以下では、上記製造方法を工程に沿って説
明する。 （１）図１に示す構造の電気炉内に鋳型を投入し、１４
８０℃の一定温度に保持した。 （２）４０分程経過したところで、同じ炉内の別の部位
に設定された−０．５℃／ｍｍの温度勾配の中を、１５
ｍｍ／ｍｉｎの速度で移動させた。 （３）Ｓｉが完全に固化し終わってからもしばらく移動
を続け、融点よりも十分低い温度領域に鋳型が来たとこ
ろで電気炉のヒータを切り、鋳型の温度を室温まで下げ
た。The above manufacturing method will be described below step by step. (1) The mold is put into the electric furnace having the structure shown in FIG.
The temperature was kept constant at 80 ° C. (2) When about 40 minutes have passed, a temperature gradient of −0.5 ° C./mm set at another site in the same furnace was changed to 15
It was moved at a speed of mm / min. (3) Even after Si was completely solidified, it continued to move for a while, and when the mold came to a temperature region sufficiently lower than the melting point, the heater of the electric furnace was turned off and the temperature of the mold was lowered to room temperature.
【００５５】（４）固化した板状のシートを鋳型から取
り出し、シート基体の不純物が偏析した側の面をＨＦ／
ＨＮＯ3系のエッチャントにより数十μｍエッチバック
した。 （５）エッチバックした面をサンドブラストで荒らして
から、シート基体に対して１１００℃、３時間のゲッタ
リング処理を行った。(4) The solidified plate-shaped sheet was taken out of the mold, and the surface of the sheet substrate on which impurities were segregated was HF /
Etched back by several tens of μm by HNO 3 type etchant. (5) The etched back surface was roughened by sandblasting, and then the sheet substrate was subjected to gettering treatment at 1100 ° C. for 3 hours.
【００５６】表３は、上記工程（１）〜（５）によって
得られたシート基体において、鋳型の進行方向を向いた
側の面に対して元素分析を行った結果である。Table 3 shows the results of elemental analysis on the surface of the sheet substrate obtained by the above steps (1) to (5) facing the advancing direction of the mold.
【００５７】[0057]
【表３】 表３から、鋳型の進行方向を向いた側の面の不純物量
は、ゲッタ処理後の方が処理前に比べて低減しているこ
とが分かった。[Table 3] From Table 3, it was found that the amount of impurities on the surface on the side facing the advancing direction of the mold was smaller after the getter treatment than before the treatment.
【００５８】（実施例６）本例では、金属級Ｓｉの溶融
／固化によるシート基体の製造方法において、次に示す
２つの点が実施例１と異なる。その後、得られたシート
基体上に、ＣＶＤ法によりＳｉ層を堆積して太陽電池を
形成した。(Embodiment 6) This embodiment differs from Embodiment 1 in the following two points in the method of manufacturing a sheet substrate by melting / solidifying metal grade Si. Then, a Si layer was deposited on the obtained sheet substrate by a CVD method to form a solar cell.
【００５９】（イ）図１に示すようなＳｉ3Ｎ4製の鋳型
を作製して用いた。 （ロ）１２０℃に加熱した塩酸／過酸化水混合溶液に粉
末状の金属級Ｓｉを通して不純物を浸出させた後、水洗
／乾燥してからフィーダーを用いて鋳型内の溝に充填し
た。他の点は、実施例１と同様とした。(B) A mold made of Si 3 N 4 as shown in FIG. 1 was prepared and used. (B) Impurities were leached through a powdery metal-grade Si into a hydrochloric acid / peroxide water mixed solution heated to 120 ° C., washed with water / dried, and then filled in a groove in a mold using a feeder. Other points were the same as in Example 1.
【００６０】以下では、上述したシート基体の製造方法
と太陽電池の形成を、工程に沿って説明する。 （１）図１に示す構造の電気炉内に鋳型を投入し、１４
８０℃の一定温度に保持した。 （２）１時間経過したところで、同じ炉内の別の部位に
設定された−０．３℃／ｍｍの温度勾配の中を、３０ｍ
ｍ／ｍｉｎの速度で移動させた。 （３）Ｓｉが完全に固化し終わってからもしばらく移動
を続け、融点よりも十分低い温度領域に鋳型が来たとこ
ろで電気炉のヒータを切り、鋳型の温度を室温まで下げ
た。The method of manufacturing the above-mentioned sheet substrate and the formation of the solar cell will be described below along with the steps. (1) The mold is put into the electric furnace having the structure shown in FIG.
The temperature was kept constant at 80 ° C. (2) After 1 hour, a temperature gradient of −0.3 ° C./mm set at another site in the same furnace was changed to 30 m.
It was moved at a speed of m / min. (3) Even after Si was completely solidified, it continued to move for a while, and when the mold came to a temperature region sufficiently lower than the melting point, the heater of the electric furnace was turned off and the temperature of the mold was lowered to room temperature.
【００６１】（４）固化した板状のシートを鋳型から取
り出し、シート基体の不純物が偏析した側の面を、ＨＦ
／ＨＮＯ3系のエッチャントにより数十μｍエッチバッ
クした。 （５）エッチバックした面をサンドブラストで荒らして
から、シート基体に対して１１００℃、３時間のゲッタ
リング処理を行った。 （６）不純物量が低減された側の面（鋳型の進行方向を
向いた側の面）上に、ＳｉＨ2Ｃｌ2を用い、成長温度ｌ
０５０℃、成長速度約０．８μｍ／ｍｉｎにて、Ｓｉ層
を４０μｍ形成した。(4) The solidified plate-shaped sheet was taken out of the mold, and the surface of the sheet substrate on which impurities were segregated was HF.
/ HNO 3 type etchant was used to etch back several tens of μm. (5) The etched back surface was roughened by sandblasting, and then the sheet substrate was subjected to gettering treatment at 1100 ° C. for 3 hours. (6) SiH 2 Cl 2 is used on the surface on the side where the amount of impurities is reduced (the surface facing the advancing direction of the mold), and the growth temperature 1
A Si layer of 40 μm was formed at 050 ° C. and a growth rate of about 0.8 μm / min.
【００６２】（７）Ｓｉ層の表面に、ＰＯＣｌ3を拡散
源として９００℃の温度でＰの熱拡散を行い、ｎ+層を
形成した。その接合深さは、０．５μｍ程度であった。 （８）形成されたｎ+層表面のデッド層をエッチングに
より除去した。その結果、約０．２μｍの適度な表面濃
度をもった接合深さを形成した。 （９）ｎ+層の上に、ＩＴＯからなる透明導電膜（約
０．１μｍ）を、電子ビーム蒸着法によって形成した。(7) On the surface of the Si layer, P was thermally diffused at a temperature of 900 ° C. using POCl 3 as a diffusion source to form an n + layer. The junction depth was about 0.5 μm. (8) The dead layer on the surface of the formed n + layer was removed by etching. As a result, a junction depth having an appropriate surface concentration of about 0.2 μm was formed. (9) A transparent conductive film (about 0.1 μm) made of ITO was formed on the n + layer by an electron beam evaporation method.
【００６３】（１０）透明導電膜の上に、集電電極（Ｃ
ｒ（０．０２μｍ）／Ａｇ（１μｍ）／Ｃｒ（０．００
４μｍ））を真空蒸着により形成した。 （１１）シート基体の裏面に、Ａｌを蒸着して裏面電極
を形成した。(10) A collector electrode (C
r (0.02 μm) / Ag (1 μm) / Cr (0.00
4 μm)) was formed by vacuum evaporation. (11) On the back surface of the sheet substrate, Al was deposited to form a back surface electrode.
【００６４】上記工程（１）〜（１１）によって作製し
た薄膜結晶太陽電池に対して、ＡＭ１．５（１００ｍＷ
／ｃｍ2）光照射下でのＩ−Ｖ特性を測定した。その結
果、セル面積２ｃｍ2の場合、開放電圧０．５６Ｖ、短
絡光電流３１ｍＡ／ｃｍ2、曲線因子０．７５となり、
変換効率１３．０％を得た。AM1.5 (100 mW) was applied to the thin film crystal solar cell manufactured by the above steps (1) to (11).
/ Cm 2 ) I-V characteristics under light irradiation were measured. As a result, when the cell area is 2 cm 2 , the open circuit voltage is 0.56 V, the short-circuit photocurrent is 31 mA / cm 2 , and the fill factor is 0.75.
A conversion efficiency of 13.0% was obtained.
【００６５】本例の結果から、金属級Ｓｉを溶融／固化
したシート基体を用い、その上にＳｉ層を積層すること
で、良好な特性を有する薄膜結晶太陽電池が形成できる
ことが分かった。From the results of this example, it was found that a thin film crystal solar cell having good characteristics can be formed by using a sheet substrate obtained by melting / solidifying metallurgical Si and laminating a Si layer thereon.
【００６６】[0066]
【発明の効果】以上説明したように、本発明によれば、
インゴットからスライスする工程を省略可能な基体の製
造方法がえられる。As described above, according to the present invention,
A method for manufacturing a substrate can be obtained in which the step of slicing from an ingot can be omitted.
【００６７】また、前記基体の製造方法により形成され
た基体を用いることで、量産性が高く、安価で、かつ良
質の太陽電池がえられる。Further, by using the substrate formed by the above-mentioned substrate manufacturing method, it is possible to obtain a solar cell of high mass productivity, low cost, and good quality.
【図１】図１は、本発明に係る基体の製造工程を説明し
た概略図である。FIG. 1 is a schematic view illustrating a manufacturing process of a substrate according to the present invention.
１０１ 鋳型、 １０２ フィーダー、 １０３ 金属級Ｓｉ、 １０４ 蓋、 １０５ ヒータ、 １０６ 融液Ｓｉ、 １０７ 固化Ｓｉ、 １０８ 不純物偏析領域、 １０９ 炉管。 101 mold, 102 feeder, 103 metal grade Si, 104 lid, 105 heater, 106 melt Si, 107 solidified Si, 108 impurity segregation region, 109 furnace tube.
Claims (6)
いて、搬送される方向に対して垂直方向に板状の溝を有
する鋳型が、前記板状の溝の内部にＳｉからなる原料を
注入される第１工程と、前記鋳型をＳｉの融点よりも高
い温度に保ち、前記Ｓｉからなる原料を融解させて前記
板状の溝を満たす第２工程と、前記鋳型が搬送される方
向に負の温度勾配の設けられた炉内を、前記鋳型が移動
する第３工程と、前記鋳型が前記炉内を移動する間に、
融解された前記Ｓｉを固化させる第４工程と、からなる
ことを特徴とする基体の製造方法。1. A method of manufacturing a substrate for supporting a semiconductor layer, wherein a mold having a plate-shaped groove in a direction perpendicular to a conveying direction is filled with a raw material made of Si into the plate-shaped groove. A first step of maintaining the mold at a temperature higher than the melting point of Si, melting the raw material of Si to fill the plate-like groove, and a negative direction in which the mold is conveyed. In a furnace provided with a temperature gradient, a third step of moving the mold, and while the mold moves in the furnace,
A fourth step of solidifying the melted Si, the method for producing a substrate.
イト、シリコン・カーバイト、又は窒化珪素の中から選
択されることを特徴とする請求項１に記載の基体の製造
方法。2. The method of manufacturing a substrate according to claim 1, wherein the material of the mold is selected from carbon graphite, silicon carbide, and silicon nitride.
あることを特徴とする請求項１又は２に記載の基体の製
造方法。3. The method for producing a substrate according to claim 1, wherein the raw material made of Si is metallurgical grade Si.
ｉ3Ｎ4を含む離型剤が被膜されていることを特徴とする
請求項１乃至３のいずれか１項に記載の基体の製造方
法。4. The inner surface of the plate-shaped groove has at least S.
The method for producing a substrate according to any one of claims 1 to 3, wherein a release agent containing i 3 N 4 is coated.
を特徴とする請求項１乃至４のいずれか１項に記載の基
体の製造方法。5. The method for producing a substrate according to claim 1, wherein the substrate is for a photoelectric conversion element.
求項１乃至５のいずれか１項に記載の基体上に形成され
たことを特徴とする太陽電池。6. A solar cell, wherein the semiconductor layer forming a photoelectric conversion element is formed on the substrate according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18045995A JP3596828B2 (en) | 1995-07-17 | 1995-07-17 | Substrate manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18045995A JP3596828B2 (en) | 1995-07-17 | 1995-07-17 | Substrate manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0936403A true JPH0936403A (en) | 1997-02-07 |
| JP3596828B2 JP3596828B2 (en) | 2004-12-02 |
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ID=16083601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18045995A Expired - Fee Related JP3596828B2 (en) | 1995-07-17 | 1995-07-17 | Substrate manufacturing method |
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| Country | Link |
|---|---|
| JP (1) | JP3596828B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387780B1 (en) | 1996-09-19 | 2002-05-14 | Canon Kabushiki Kaisha | Fabrication process of solar cell |
| US6602767B2 (en) | 2000-01-27 | 2003-08-05 | Canon Kabushiki Kaisha | Method for transferring porous layer, method for making semiconductor devices, and method for making solar battery |
| EP2132769A1 (en) * | 2007-03-21 | 2009-12-16 | Mossey Creek Technology, Llc | Method of making a solar grade silicon wafer |
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|---|---|---|---|---|
| US6387780B1 (en) | 1996-09-19 | 2002-05-14 | Canon Kabushiki Kaisha | Fabrication process of solar cell |
| US6869863B2 (en) | 1996-09-19 | 2005-03-22 | Canon Kabushiki Kaisha | Fabrication process of solar cell |
| US6602767B2 (en) | 2000-01-27 | 2003-08-05 | Canon Kabushiki Kaisha | Method for transferring porous layer, method for making semiconductor devices, and method for making solar battery |
| EP2132769A1 (en) * | 2007-03-21 | 2009-12-16 | Mossey Creek Technology, Llc | Method of making a solar grade silicon wafer |
| EP2132769A4 (en) * | 2007-03-21 | 2011-06-29 | Mossey Creek Technology Llc | Method of making a solar grade silicon wafer |
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| Publication number | Publication date |
|---|---|
| JP3596828B2 (en) | 2004-12-02 |
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