JP3122283B2 - Liquid phase growth method and apparatus - Google Patents
Liquid phase growth method and apparatusInfo
- Publication number
- JP3122283B2 JP3122283B2 JP05140277A JP14027793A JP3122283B2 JP 3122283 B2 JP3122283 B2 JP 3122283B2 JP 05140277 A JP05140277 A JP 05140277A JP 14027793 A JP14027793 A JP 14027793A JP 3122283 B2 JP3122283 B2 JP 3122283B2
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- substrate
- liquid phase
- phase growth
- pipe
- 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.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は液相成長法およびその装
置に関し、特に連続成長が可能で量産性のある液相成長
法およびその装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid phase growth method and an apparatus therefor, and more particularly to a liquid phase growth method capable of continuous growth and mass production and an apparatus therefor.
【０００２】[0002]
【従来の技術】液相成長法は準平衡状態からの結晶成長
であるため化学量論組成に近い良質の結晶が得られ、Ｇ
ａＡｓ等の化合物半導体の分野においてはすでに確立し
た技術としてＬＥＤやレーザ・ダイオードなどが生産さ
れている。2. Description of the Related Art Since the liquid phase growth method is a crystal growth from a quasi-equilibrium state, good quality crystals close to the stoichiometric composition can be obtained.
In the field of compound semiconductors such as aAs, LEDs, laser diodes, and the like have been produced as established technologies.
【０００３】最近では厚膜を得る目的でＳｉの液相成長
も試みられ（例えば特開昭５８−８９８７４号公報）、
太陽電池への応用が検討されている。Recently, a liquid phase growth of Si has been attempted for the purpose of obtaining a thick film (for example, Japanese Patent Application Laid-Open No. 58-89874).
Application to solar cells is being studied.
【０００４】しかしながら、従来の液相成長法では、一
般に、溶媒を冷却して過飽和状態とし、過剰溶質を基板
上に析出させるため、ある程度温度が下がったところで
一旦温度を元に引き上げ、再度結晶成長を行うといった
サイクルになる。そのために量産性に問題があった。特
に比較的厚膜を必要とする太陽電池用Ｓｉでは、成長時
における温度の下げ幅が大きく、元の温度に戻すまでの
時間損失がかなりあった。However, in the conventional liquid phase growth method, generally, in order to precipitate the excess solute on the substrate by cooling the solvent to a supersaturated state, once the temperature is lowered to some extent, the temperature is raised once based on the temperature, and the crystal is grown again. Is performed. Therefore, there was a problem in mass productivity. In particular, in the case of Si for a solar cell that requires a relatively thick film, the temperature drop during growth is large, and there is considerable time loss until the temperature returns to the original temperature.
【０００５】この点を改良し量産性を上げる目的で溶媒
内にあるいは溶媒と基板間に温度差を設けて連続成長を
可能とした温度差法が提案されている。すなわち、図４
に示されるように、溶媒溜の高さの範囲内に温度差を設
けることで溶媒上面の原料板２０５から溶媒２０６の下
面の基板２０３に溶質が輸送されて成長が行われる。し
かしながら、この場合には、狭い範囲での精密な温度制
御が必要となり、成長装置が高価なものとなってしまう
問題があった。For the purpose of improving this point and increasing mass productivity, a temperature difference method has been proposed in which a temperature difference is provided in a solvent or between a solvent and a substrate to enable continuous growth. That is, FIG.
As shown in (2), by providing a temperature difference within the range of the height of the solvent reservoir, the solute is transported from the raw material plate 205 on the upper surface of the solvent to the substrate 203 on the lower surface of the solvent 206 and growth is performed. However, in this case, there is a problem that precise temperature control in a narrow range is required, and the growth apparatus becomes expensive.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上述の従来
技術における問題を解決すべく本発明者による鋭意研究
の結果完成に至ったものであり、簡便で量産性のある液
相成長法およびその装置を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been accomplished as a result of intensive studies by the present inventors in order to solve the above-mentioned problems in the prior art. It is intended to provide the device.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明の方法
は、溶媒溜において溶媒に溶質を供給し、溶質が供給さ
れた溶媒をパイプを介して循環させるとともに、該パイ
プの一部に設けられた開口において基体を、溶質が供給
された溶媒に接触させることにより基体上に結晶を形成
することを特徴とする液相成長法に要旨が存在する。That is, the method of the present invention is to supply a solute to a solvent in a solvent reservoir, circulate the solvent to which the solute is supplied through a pipe, and provide the solute in a part of the pipe. There is a gist of a liquid phase growth method characterized in that a crystal is formed on a substrate by bringing the substrate into contact with a solvent supplied with a solute at the opening.
【０００８】[0008]
【課題を解決するための手段】本発明の液相成長法は、
溶質からなる蓋を有する溶媒溜において溶質からなる蓋
を有する溶媒に溶質を供給し、溶質が供給された溶媒を
熱交換器を有するパイプを介して循環させるとともに、
該パイプの一部に設けられた開口において基体を溶質が
供給された溶媒に接触させることにより基体上に結晶を
形成することを特徴とする。The liquid phase growth method of the present invention comprises:
Solute lid in solvent reservoir with solute lid
Solute supply, the solute is supplied solvent with circulating through a pipe having a heat exchanger in a solvent having,
A crystal is formed on the substrate by bringing the substrate into contact with a solvent supplied with a solute at an opening provided in a part of the pipe.
【０００９】本発明の液相成長装置は、溶媒に溶質を溶
かし込んで基体上に結晶を析出させる液相成長装置にお
いて、前記溶媒に前記溶質を供給する溶媒溜と、前記溶
質が供給された溶媒を循環させるパイプとを備え、該パ
イプの両端が前記溶媒溜の側壁に繋がっており、該パイ
プは熱交換器を有しており、前記パイプの途中には基体
と接触させるための開口が設けられており、前記溶媒溜
が前記溶質からなる蓋を有しており、該蓋の一部によっ
て溶媒の流路が形成されていることを特徴とする。A liquid phase growth apparatus according to the present invention is a liquid phase growth apparatus for dissolving a solute in a solvent to precipitate crystals on a substrate, wherein a solvent reservoir for supplying the solute to the solvent and the solute are supplied. A pipe for circulating the solvent, wherein both ends of the pipe are connected to side walls of the solvent reservoir, the pipe has a heat exchanger, and an opening for contacting the base is provided in the middle of the pipe. The solvent reservoir is provided
Has a lid made of the solute, and a part of the lid
A flow path for the solvent is formed .
【００１０】（実験１）静止基板上への成長 図１に示すように、カーボン製の溶媒溜１０５と、この
溶媒溜１０５の片側側面から出て、途中成長基板１０７
を載置したスライダ１０８に開口部１０９で接して、再
び溶媒溜１０５のもう一方の側面にもどるカーボン製の
平型パイプ１０３とが電気炉１０１内に配置されてお
り、溶媒溜１０５はさらにヒータブロック１０２で囲ま
れ、独立に温度制御ができるようになっている。スライ
ダ１０８は長さ方向に移動できるようになっており、ス
ライダ１０８の移動により基板１０７上への成長を開始
／終了する。図２に示すように溶媒溜３０１の内部には
数枚のカーボン製の仕切板３０２が設置されており、溶
液溜の蓋となる原料板３０３と組合わさって同図（ｂ）
のように溶媒の流路を形成する。この流路を溶媒が通る
間に原料板３０３から溶媒中に溶質が溶け込んで飽和状
態となる。溶媒溜１０５から出た溶媒は平型パイプで形
成された熱交換器１０４を循環する間に溶液溜１０５よ
り低い温度に設定された電気炉内１０１の温度により過
飽和状態となり、スライダ１０８と接した開口部１０９
においてスライダ上の基板１０７に溶質を析出させる。(Experiment 1) Growth on Stationary Substrate As shown in FIG. 1, a solvent reservoir 105 made of carbon,
And a flat pipe 103 made of carbon, which is in contact with the slider 108 on which is mounted the opening 108 and returns to the other side of the solvent reservoir 105 again, is disposed in the electric furnace 101. It is surrounded by a block 102 so that the temperature can be controlled independently. The slider 108 can move in the length direction, and the growth on the substrate 107 is started / terminated by the movement of the slider 108. As shown in FIG. 2, several carbon partition plates 302 are provided inside the solvent reservoir 301, and are combined with a raw material plate 303 serving as a lid of the solution reservoir, as shown in FIG.
A channel for the solvent is formed as shown in FIG. While the solvent passes through this flow path, the solute dissolves into the solvent from the raw material plate 303 and becomes saturated. The solvent discharged from the solvent reservoir 105 is supersaturated by the temperature of the electric furnace 101 set to a lower temperature than the solution reservoir 105 while circulating through the heat exchanger 104 formed by a flat pipe, and comes into contact with the slider 108. Opening 109
The solute is deposited on the substrate 107 on the slider.
【００１１】水素雰囲気中で十分純化したＳｎを溶媒と
して溶媒溜１０５および平型パイプ１０３内に満たし、
多結晶Ｓｉの原料板１０４で溶液溜に蓋をし、電気炉内
温度を９５０℃一定にして（１００）単結晶Ｓｉ基板１
０７をスライダ１０８上に置いた。予めスライダの位置
を調節してＳｉ基板１０７が平型パイプの開口部１０９
において接しないようにしておき、ヒータブロック１０
２により溶媒溜１０５の温度がその周りの電気炉内の温
度よりも５℃高くなるように設定して溶媒をロータ１０
６を用いて循環させた。Filling the solvent reservoir 105 and the flat pipe 103 with Sn sufficiently purified in a hydrogen atmosphere as a solvent,
The solution reservoir is covered with a polycrystalline Si raw material plate 104, the temperature in the electric furnace is kept constant at 950 ° C., and the (100) single crystal Si substrate 1
07 was placed on the slider 108. The position of the slider is adjusted in advance, and the Si substrate 107 is moved to the opening 109 of the flat pipe.
At the heater block 10
2 so that the temperature of the solvent reservoir 105 is set to be 5 ° C. higher than the temperature in the surrounding electric furnace, and the solvent is supplied to the rotor 10.
And circulated.
【００１２】充分時間が経ったところで、スライダ１０
８を動かして開口部１０９においてＳｉ基板１０７をＳ
ｎ溶媒と接触させ、溶媒を循環させながらそのままの状
態で３０分置き、その後スライダ１０８を再び動かして
Ｓｉ基板１０７をＳｎ溶媒から離して成長を終了した。After a sufficient time has passed, the slider 10
8 to move the Si substrate 107 in the opening 109
The substrate was kept in contact with the n solvent for 30 minutes while circulating the solvent, and then the slider 108 was moved again to separate the Si substrate 107 from the Sn solvent and terminate the growth.
【００１３】成長の終了したＳｉ基板の表面を光学顕微
鏡および走査型電子顕微鏡で観察したところ非常に平滑
であり、また成長したＳｉ層の膜厚を段差計および走査
型電子顕微鏡により測定したところ、約２５μｍであっ
た。また反射電子回折法およびラマン分光法により、得
られたＳｉ層は下地Ｓｉ基板の方位を受け継いだ（１０
０）単結晶Ｓｉであることが確認された。When the surface of the grown Si substrate was observed with an optical microscope and a scanning electron microscope, the surface was extremely smooth. The thickness of the grown Si layer was measured with a step gauge and a scanning electron microscope. It was about 25 μm. The Si layer obtained by reflection electron diffraction and Raman spectroscopy inherited the orientation of the underlying Si substrate (10
0) It was confirmed to be single crystal Si.
【００１４】（実験２）移動基板上への連続成長 実験１の結果を基に移動基板上への連続成長を行った。
図４に示すようにスライダ４０８の上に細長く切り出し
た（１００）Ｓｉ基板４０７を置き、実験１と同じ条件
でＳｎを循環させ成長を行った。予めスライダの位置を
調節してＳｉ基板４０７が平型パイプの開口部４０９に
おいて接しないようにしておき、ヒータブロック４０２
により溶媒溜４０５の温度がその周りの電気炉内の温度
よりも５℃高くなるように設定して溶媒をロータ４０６
を用いて循環させた。(Experiment 2) Continuous growth on a moving substrate Based on the results of Experiment 1, continuous growth was performed on a moving substrate.
As shown in FIG. 4, a (100) Si substrate 407 cut long and thin was placed on the slider 408, and Sn was circulated and grown under the same conditions as in Experiment 1. The position of the slider is adjusted in advance so that the Si substrate 407 does not touch the opening 409 of the flat pipe, and the heater block 402
The temperature of the solvent reservoir 405 is set to be 5 ° C. higher than the temperature of the surrounding electric furnace by the
And circulated.
【００１５】充分時間が経ったところで、スライダ４０
８を送り速度５ｍｍ／分で送りながら開口部４０９にお
いてＳｉ基板４０７をＳｎ溶媒と接触させて結晶成長を
行った。Ｓｉ基板４０７が全て開口部４０９を通過し終
わったところでスライダ４０８の送りを止め、成長を終
了した。After a sufficient time has passed, the slider 40
8 was fed at a feed rate of 5 mm / min, and the Si substrate 407 was brought into contact with the Sn solvent at the opening 409 to grow a crystal. When all the Si substrates 407 passed through the openings 409, the feed of the slider 408 was stopped, and the growth was terminated.
【００１６】成長の終了したＳｉ基板の表面を光学顕微
鏡および走査型電子顕微鏡で観察したところ基板全面に
わたって平滑であり、また成長したＳｉ層の膜厚を段差
計および走査型電子顕微鏡により測定したところ、約５
μｍであった。また反射電子回折法およびラマン分光法
により、得られたＳｉ層は下地Ｓｉ基板の方位を受け継
いだ（１００）単結晶Ｓｉであることが確認された。When the surface of the grown Si substrate was observed with an optical microscope and a scanning electron microscope, it was found that the entire surface of the substrate was smooth, and the thickness of the grown Si layer was measured with a step gauge and a scanning electron microscope. , About 5
μm. Further, it was confirmed by reflection electron diffraction and Raman spectroscopy that the obtained Si layer was (100) single-crystal Si inherited from the orientation of the underlying Si substrate.
【００１７】このように溶媒溜と成長を行う場所を別々
にして独立に温度制御を行い、その間をパイプにより溶
媒を循環させることで連続で液相成長ができることが示
された。As described above, it has been shown that the liquid phase can be continuously grown by separately controlling the temperature in the solvent reservoir and the place where the growth is performed, and circulating the solvent through the pipe between them.
【００１８】以上述ベた実験結果に基づいて完成に至っ
た本発明は前述した様に、連続成長を行う液相成長法に
係わるものである。本発明の特徴は溶媒溜と成長基板の
場所を別にして独立に温度制御を行い、その間をパイプ
により溶媒を循環させるもので従来の連続液相成長法に
みられるような温度勾配を保つための精密温度制御を必
要としない点である。The present invention, which has been completed based on the experimental results described above, relates to the liquid phase growth method for performing continuous growth as described above. The feature of the present invention is that the temperature is independently controlled separately from the location of the solvent reservoir and the growth substrate, and the solvent is circulated through a pipe between them to maintain the temperature gradient as seen in the conventional continuous liquid phase growth method. This is a point that does not require precise temperature control.
【００１９】本発明に使用される溶媒を収納するための
溶媒溜のおよびスライダの材質としては主に高純度カー
ボンが使用される。High-purity carbon is mainly used as the material of the solvent reservoir for storing the solvent used in the present invention and the slider.
【００２０】本発明に用いられる溶媒、溶質としては従
来の液相成長法に用いられているものであればどのよう
な組み合わせでもよく、例えば、溶質にＳｉを使用する
場合には溶媒としては、例えばＳｎ，Ｇａ，Ｉｎ，Ｓ
ｂ，Ｂｉ等が用いられる。ここで溶媒としてＳｎを用い
ると、得られるＳｉ結晶は電気的に中性であり、成長後
にあるいは成長中に適宜所望の不純物を添加することで
所望のドーピング濃度で伝導型を決定することができ
る。The solvent and solute used in the present invention may be any combination as long as they are used in the conventional liquid phase growth method. For example, when Si is used for the solute, the solvent may be: For example, Sn, Ga, In, S
b, Bi, etc. are used. Here, when Sn is used as a solvent, the obtained Si crystal is electrically neutral, and the conductivity type can be determined at a desired doping concentration by adding a desired impurity as needed after or during growth. .
【００２１】本発明の方法において溶媒および基体がお
かれる雰囲気としてはＨ2あるいはＮ2が用いられ、圧力
については概ね１０-2Ｔｏｒｒ〜７６０Ｔｏｒｒが適当
であり、より好ましくは１０-1Ｔｏｒｒ〜７６０Ｔｏｒ
ｒの範囲である。In the method of the present invention, H 2 or N 2 is used as the atmosphere in which the solvent and the substrate are placed, and the pressure is preferably about 10 −2 Torr to 760 Torr, more preferably 10 −1 Torr to 760 Torr.
r.
【００２２】また本発明の方法における溶媒温度として
は、溶媒の種類によるがＳｎを用いる場合には８００℃
以上１１００℃以下に制御されるのが望ましい。The temperature of the solvent in the method of the present invention depends on the type of the solvent.
It is desirable that the temperature be controlled to 1100 ° C. or lower.
【００２３】なお、本発明はホモエピタキシャルのみな
らずヘテロエピタキシャルにも適用可能である。The present invention is applicable to not only homoepitaxial but also heteroepitaxial.
【００２４】なお、パイプ中における溶媒の速度は１〜
１００ｍｍ／ｍｉｎが好ましく、スライダの移動速度は
０〜３００ｍｍ／ｍｉｎが好ましい。また、溶媒溜にお
ける温度と基体温度との温度差ΔＴとしてはΔＴ＝３〜
５０℃が好ましい。ΔＴが小さすぎると基板表面から溶
質がメルトバックする恐れがあり、逆にΔＴが高すぎる
と成長速度の低下したり、あるいは基板に到達する前に
パイプ中の溶媒の中で結晶粒が析出したりする場合があ
る。The velocity of the solvent in the pipe is 1 to
100 mm / min is preferable, and the moving speed of the slider is preferably 0 to 300 mm / min. The temperature difference ΔT between the temperature in the solvent reservoir and the substrate temperature is ΔT = 3 to
50 ° C. is preferred. If the ΔT is too small, the solute may melt back from the substrate surface. Conversely, if the ΔT is too high, the growth rate may decrease, or crystal grains may precipitate in the solvent in the pipe before reaching the substrate. Or may be.
【００２５】[0025]
【実施例】以下、本発明の方法を実施して所望の結晶を
成長するところをより詳細に説明するが、本発明はこれ
らの実施例により何ら限定されるものではない。EXAMPLES Hereinafter, the method of growing a desired crystal by carrying out the method of the present invention will be described in more detail, but the present invention is not limited to these examples.
【００２６】（実施例１）図１に示す装置を用いてＳｉ
のエピタキシャル層を成長した。溶媒にＳｎ、溶質にＳ
ｉを用いて成長を行った。原料板１０４に多結晶Ｓｉ
を、またスライダ１０８上には基体として（１００）単
結晶Ｓｉウエハ１０７を置き、予めＳｉウエハがＳｎに
触れないようにしておき、電気炉内を９５０℃、ヒータ
ブロック１０２内を９６０℃一定に保った。充分時間が
経ったところでスライダ１０８を移動してＳｉウエハ１
０７を、Ｓｉが供給されたＳｎ溶媒に接触させ、このま
まの状態で３０分置いた。その後スライダ１０８を再度
移動してＳｉウエハ１０７をＳｎから離して成長を終了
した。(Embodiment 1) Using the apparatus shown in FIG.
Was grown. Sn for solvent and S for solute
Growth was performed using i. Polycrystalline Si for raw material plate 104
A (100) single crystal Si wafer 107 is placed on the slider 108 as a base so that the Si wafer does not touch Sn in advance, and the inside of the electric furnace is kept at 950 ° C. and the inside of the heater block 102 is kept at 960 ° C. Kept. When a sufficient time has passed, the slider 108 is moved and the Si wafer 1 is moved.
07 was brought into contact with the Sn solvent supplied with Si and left as it was for 30 minutes. Thereafter, the slider 108 was moved again to separate the Si wafer 107 from Sn, and the growth was terminated.
【００２７】成長したシリコン層の膜厚を段差計および
走査型電子顕微鏡により測定したところ、その膜厚は約
４０μｍであった。また反射電子回折法およびラマン分
光法により、得られたシリコン層は下地シリコン基板の
方位を受け継いだ（１００）単結晶シリコンであること
が確認された。When the film thickness of the grown silicon layer was measured by a step gauge and a scanning electron microscope, the film thickness was about 40 μm. Further, it was confirmed by reflection electron diffraction and Raman spectroscopy that the obtained silicon layer was (100) single crystal silicon inheriting the orientation of the underlying silicon substrate.
【００２８】（実施例２）実験２と同様にして多結晶Ｓ
ｉの連続成長を行った。キャスト法により形成した多結
晶Ｓｉを幅２０ｍｍ、長さ２００ｍｍ、厚さ０．６ｍｍ
に加工し、表面研磨した後に洗浄したものを基板とし
た。(Example 2) Polycrystalline S
i was continuously grown. Polycrystalline Si formed by casting method is 20mm wide, 200mm long, 0.6mm thick
The surface was polished, and the surface was polished and then washed to obtain a substrate.
【００２９】図３に示すように、スライダ４０８の上に
多結晶Ｓｉ基板４０７を置き、実施例１と同じ条件でＳ
ｎ溶媒を循環させ成長を行った。平型パイプに設けられ
た開口部の長さを５０ｍｍ、Ｓｎ溶媒の循環速度を２５
ｍｍ／分とし、予めスライダの位置を調節してＳｉ基板
４０７が平型パイプの開口部４０９においてＳｎ溶媒と
接しないようにしておき、電気炉内を９５０℃、ヒータ
ブロック内を９６０℃一定に保った。As shown in FIG. 3, a polycrystalline Si substrate 407 is placed on a slider 408, and S
Growth was performed by circulating n solvents. The length of the opening provided in the flat pipe is 50 mm, and the circulation speed of the Sn solvent is 25.
mm / min, the position of the slider is adjusted in advance so that the Si substrate 407 does not come in contact with the Sn solvent at the opening 409 of the flat pipe, and the inside of the electric furnace is kept at 950 ° C. and the inside of the heater block is kept at 960 ° C. Kept.
【００３０】充分時間が経ったところで、スライダ４０
８を送り速度１０ｍｍ／分で送りながら開口部４０９に
おいて多結晶Ｓｉ基板４０７をＳｎ溶媒と接触させて結
晶成長を行った。多結晶Ｓｉ基板４０７が全て開口部４
０９を通過し終わったところでスライダ４０８の送りを
止め、成長を終了した。After a sufficient time has passed, the slider 40
8 was fed at a feed rate of 10 mm / min, and the polycrystalline Si substrate 407 was brought into contact with the Sn solvent at the opening 409 to grow crystals. All the openings 4 of the polycrystalline Si substrate 407
At the end of the passage through 09, the movement of the slider 408 was stopped, and the growth was terminated.
【００３１】成長したＳｉ層の膜厚を段差計および走査
型電子顕微鏡により測定したところ、ほぼ全面にわたっ
て一様で約７μｍであった。また成長したＳｉ層の方位
についてＥＣＰ（Ｅｌｅｃｔｒｏｎ Ｃｈａｎｎｅｌｉ
ｎｇ Ｐａｔｔｅｒｎ）法により調ベたところ、下地の
多結晶Ｓｉ基板の各々のグレインの結晶方位を受け継い
でいることが分かった。When the film thickness of the grown Si layer was measured by a step gauge and a scanning electron microscope, it was uniform and approximately 7 μm over almost the entire surface. Also, regarding the orientation of the grown Si layer, ECP (Electron Channelelli) was used.
ng (Pattern) method, it was found that the crystal orientation of each grain of the underlying polycrystalline Si substrate was inherited.
【００３２】（実施例３）実施例２と同様にして多結晶
Ｓｉの連続成長を行った。キャスト法により形成した多
結晶Ｓｉを幅２０ｍｍ、長さ２００ｍｍ、厚さ０．６ｍ
ｍに加工し、表面研磨した後に洗浄したものを基板とし
た。Example 3 Polycrystalline Si was continuously grown in the same manner as in Example 2. Polycrystalline Si formed by casting method is 20mm wide, 200mm long, 0.6m thick
m, the surface was polished, and then washed to obtain a substrate.
【００３３】図３に示すように、スライダ４０８の上に
多結晶Ｓｉ基板４０７を置き、Ｓｎを循環させ成長を行
った。平型パイプに設けられた開口部の長さを１００ｍ
ｍ、Ｓｎ溶媒の循環速度を４０ｍｍ／分とし、予めスラ
イダの位置を調節してＳｉ基板４０７が平型パイプの開
口部４０９においてＳｎ溶媒と接しないようにしてお
き、電気炉内を９５０℃、ヒータブロック内を９７０℃
一定に保った。As shown in FIG. 3, a polycrystalline Si substrate 407 was placed on a slider 408, and Sn was circulated for growth. The length of the opening provided in the flat pipe is 100m
The circulation speed of the m and Sn solvents was set to 40 mm / min, and the position of the slider was adjusted in advance so that the Si substrate 407 did not come into contact with the Sn solvent at the opening 409 of the flat pipe. 970 ° C inside the heater block
Kept constant.
【００３４】充分時間が経ったところで、スライダ４０
８を送り速度２０ｍｍ／分で送りながら開口部４０９に
おいて多結晶Ｓｉ基板４０７をＳｎ溶媒と接触させて結
晶成長を行った。多結晶Ｓｉ基板４０７が全て開口部４
０９を通過し終わったところでスライダ４０８の送りを
止め、成長を終了した。After a sufficient time has passed, the slider 40
8 was fed at a feed rate of 20 mm / min, and the polycrystalline Si substrate 407 was brought into contact with the Sn solvent at the opening 409 to grow a crystal. All the openings 4 of the polycrystalline Si substrate 407
At the end of the passage through 09, the movement of the slider 408 was stopped, and the growth was terminated.
【００３５】成長したＳｉ層の膜厚を段差計および走査
型電子顕微鏡により測定したところ、ほぼ全面にわたっ
て一様で約１８μｍであった。また成長したＳｉ層の方
位についてＥＣＰ（Ｅｌｅｃｔｒｏｎ Ｃｈａｎｎｅｌ
ｉｎｇ Ｐａｔｔｅｒｎ）法により調ベたところ、下地
の多結晶Ｓｉ基板の各々のグレインの結晶方位を受け継
いでいることが分かった。When the film thickness of the grown Si layer was measured with a step gauge and a scanning electron microscope, it was uniform and approximately 18 μm over almost the entire surface. Also, regarding the orientation of the grown Si layer, ECP (Electron Channel) was used.
(ing Pattern) method, it was found that the crystal orientation of each grain of the underlying polycrystalline Si substrate was inherited.
【００３６】このように多結晶基板上に結晶Ｓｉ層が基
板を送りながら連続で成長できることが示された。As described above, it has been shown that a crystalline Si layer can be continuously grown on a polycrystalline substrate while feeding the substrate.
【００３７】なお、上述の実施例２、実施例３ではスラ
イダ上に載置された基板を用いた場合を示したが、例え
ば表面にＳｉ層を付着したウエブ状基板をＳｎ溶媒に接
触させてＲｏｌｌ−ｔｏ−Ｒｏｌｌで基板を一方向に送
りながら連続成膜をすることも可能である。In the above-described second and third embodiments, the case where the substrate mounted on the slider is used has been described. For example, a web-like substrate having a Si layer adhered to the surface is brought into contact with a Sn solvent. It is also possible to form a continuous film while feeding the substrate in one direction by roll-to-roll.
【００３８】（実施例４）ｎ+ｐ型薄膜結晶太陽電池を
本発明の連続液相成長法を用いて作製した。まず実施例
１と同様にして５００μｍ厚のｐ型多結晶Ｓｉウエハ
（ρ＝０．０１Ω・ｃｍ）上に図１に示す装置を用いて
多結晶Ｓｉ層を成長した。Example 4 An n + p-type thin film crystal solar cell was manufactured by using the continuous liquid phase growth method of the present invention. First, a polycrystalline Si layer was grown on a 500 μm-thick p-type polycrystalline Si wafer (ρ = 0.01 Ω · cm) using the apparatus shown in FIG.
【００３９】原料板としてｐ型多結晶Ｓｉ（ρ＝２Ω・
ｃｍ）を用い、予め多結晶ＳｉウエハがＳｎ溶媒に触れ
ないようにしておき、電気炉内を９５０℃、ヒータブロ
ック内を９６０℃一定に保った。充分時間が経ったとこ
ろでスライダを移動して多結晶ＳｉウエハをＳｎ溶媒に
接触させ、このままの状態で４０分置いた。その後スラ
イダを再度移動して基板をＳｎから離して成長を終了し
た。As a raw material plate, p-type polycrystalline Si (ρ = 2Ω ·
cm), the polycrystalline Si wafer was kept in contact with the Sn solvent in advance, and the inside of the electric furnace was kept at 950 ° C. and the inside of the heater block was kept at 960 ° C. After a sufficient time had passed, the slider was moved to bring the polycrystalline Si wafer into contact with the Sn solvent, and was left for 40 minutes in this state. Thereafter, the slider was moved again to separate the substrate from Sn, and the growth was terminated.
【００４０】成長したＳｉ層の膜厚を段差計および走査
型電子顕微鏡により測定したところ、約５０μｍであっ
た。次に成長したＳｉ層の表面にＰＯＣｌ3を拡散源と
して９００℃の温度でＰの熱拡散を行ってｎ+層を形成
し、０．５μｍ程度の接合深さを得た。形成されたｎ+
層表面のデッド層をウェット酸化後、エッチングにより
除去し、約０．２μｍの適度な表面濃度をもった接合深
さを得た。When the film thickness of the grown Si layer was measured by a step gauge and a scanning electron microscope, it was about 50 μm. Next, P was thermally diffused at a temperature of 900 ° C. using POCl 3 as a diffusion source on the surface of the grown Si layer to form an n + layer, and a junction depth of about 0.5 μm was obtained. N + formed
After wet oxidation of the dead layer on the layer surface, the layer was removed by etching to obtain a junction depth having an appropriate surface concentration of about 0.2 μm.
【００４１】最後にＥＢ（Ｅｌｅｃｔｒｏｎ Ｂｅａ
ｍ）蒸着により集電電極（Ｔｉ／Ｐｄ／Ａｇ（４０ｎｍ
／２０ｎｍ／１μｍ））／ＩＴＯ透明導電膜（８２０ｎ
ｍ）をｎ+層上に、また裏面電極（Ａｌ（１μｍ））を
基板裏面にそれぞれ形成した。Finally, EB (Electron Beam)
m) A current collecting electrode (Ti / Pd / Ag (40 nm
/ 20nm / 1μm)) / ITO transparent conductive film (820n
m) was formed on the n + layer, and a back electrode (Al (1 μm)) was formed on the back of the substrate.
【００４２】このようにして得られた薄膜多結晶Ｓｉ太
陽電池についてＡＭ１．５（１００ｍＷ／ｃｍ2）光照
射下でのＩ−Ｖ特性について測定したところ、セル面積
４ｃｍ2で開放電圧０．５７Ｖ、短絡光電流３３．５ｍ
Ａ／ｃｍ2、曲線因子０．７２となり、エネルギー変換
効率１３．７％を得た。When the IV characteristics of the thin-film polycrystalline Si solar cell thus obtained were measured under irradiation of AM1.5 (100 mW / cm 2 ) light, the open-circuit voltage was 0.57 V at a cell area of 4 cm 2. , Short-circuit photocurrent 33.5m
A / cm 2 , fill factor was 0.72, and an energy conversion efficiency of 13.7% was obtained.
【００４３】以上述べたように、本発明によれば、溶媒
溜と成長基板とを独立に温度制御し、その間をパイプに
より溶媒を循環させることで、従来のように精密制御を
必要とせずに連続して結晶成長が行えることが示され
た。As described above, according to the present invention, the temperature of the solvent reservoir and the growth substrate are independently controlled, and the solvent is circulated through the pipe between them, thereby eliminating the need for precise control as in the prior art. It was shown that crystal growth can be performed continuously.
【００４４】[0044]
【発明の効果】以上述ベてきたように、本発明によれば
液相法において簡便な構成で連続して結晶成長をするこ
とが可能となった。本発明は結晶の厚みを必要とするデ
バイス、特に太陽電池の量産方法として最適である。As described above, according to the present invention, it is possible to continuously grow crystals with a simple structure in a liquid phase method. The present invention is most suitable as a method for mass-producing devices requiring crystal thickness, particularly solar cells.
【図１】本発明の方法を実施するために用いられた連続
液相成長装置の概略図である。FIG. 1 is a schematic diagram of a continuous liquid phase growth apparatus used to carry out the method of the present invention.
【図２】本発明の方法を実施するために用いられた溶媒
溜の概略図である。FIG. 2 is a schematic diagram of a solvent reservoir used to carry out the method of the present invention.
【図３】本発明の方法を実施するために用いられた連続
液相成長装置の概略図である。FIG. 3 is a schematic diagram of a continuous liquid phase growth apparatus used to carry out the method of the present invention.
【図４】従来の連続液相成長装置の概略図である。FIG. 4 is a schematic view of a conventional continuous liquid phase growth apparatus.
１０１，４０１ 電気炉、 １１１，４１１ 熱交換器、 １０２，４０２ ヒータブロック、 ２０１ ボート、 １０３，４０３ 循環パイプ、 １０４，２０５，３０３，４０４ 原料板、 １０５，３０１，４０５ 溶媒溜、 １０６，４０６ ロータ、 １０７，２０３，４０７ 基板、 １０８，２０２，２０４，４０８ スライダ、 １１０，２０６，４１０ 溶媒。 101,401 electric furnace, 111,411 heat exchanger, 102,402 heater block, 201 boat, 103,403 circulation pipe, 104,205,303,404 raw material plate, 105,301,405 solvent reservoir, 106,406 rotor 107, 203, 407 substrate, 108, 202, 204, 408 slider, 110, 206, 410 solvent.
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/208,21/368 C30B 19/00 - 19/12 Continuation of the front page (58) Field surveyed (Int.Cl. 7 , DB name) H01L 21 / 208,21 / 368 C30B 19/00-19/12
Claims (17)
蓋の一部を溶媒に溶解させることによって溶媒に溶質を
供給し、溶質が供給された溶媒を熱交換器を有するパイ
プを介して循環させるとともに、該パイプの一部に設け
られた開口において基体を溶質が供給された溶媒に接触
させることにより基体上に結晶を形成することを特徴と
する液相成長法。1. A solvent reservoir having a lid made of a solute .
A solute is supplied to the solvent by dissolving a part of the lid in the solvent, the solvent supplied with the solute is circulated through a pipe having a heat exchanger, and a substrate is provided at an opening provided in a part of the pipe. A liquid phase growth method comprising forming a crystal on a substrate by contacting a solvent with a solvent supplied with a solute.
それに接する基体の温度よりも高くすることを特徴とす
る請求項１記載の液相成長法。2. The liquid phase growth method according to claim 1, wherein the temperature of the solvent reservoir is higher than the temperature of the circulation pipe and the substrate in contact with the circulation pipe.
循環用のロータにより溶質が供給された溶媒を循環させ
ることを特徴とする請求項１または２に記載の液相成長
法。3. The liquid phase growth method according to claim 1, wherein the solvent supplied with the solute is circulated by a solvent circulation rotor provided in a part of the inside of the pipe.
イダを移動しながら前記循環パイプの開口部において前
記溶媒と前記基体とを接触させることにより成長を行う
ことを特徴とする請求項１ないし３のいずれか１項に記
載の液相成長法。4. The method according to claim 1, wherein the substrate is arranged on a slider, and the growth is performed by bringing the solvent into contact with the substrate at an opening of the circulation pipe while moving the slider. 4. The liquid phase growth method according to any one of the above items 3.
該連続基体を移動させながら前記循環パイプの開口部に
おいて前記溶媒と前記連続基体とを接触させることによ
り成長を行うことを特徴とする請求項１記載の液相成長
法。5. The substrate is a web-like continuous substrate,
Liquid phase growth method according to claim 1, characterized in that the growth by contacting said solvent with said continuous base at the opening of the circulation pipe reluctant such moving said continuous body.
それに接する基体の温度とをそれぞれ一定に保つことを
特徴とする請求項１ないし５のいずれか１項に記載の液
相成長法。6. The liquid phase growth method according to claim 1, wherein the temperature of the solvent reservoir and the temperature of the circulation pipe and the substrate in contact therewith are kept constant.
請求項１ないし６のいずれか１項に記載の液相成長法。7. The liquid phase growth method according to claim 1, wherein the solvent is Sn.
請求項１ないし７のいずれか１項に記載の液相成長法。8. The liquid phase growth method according to claim 1, wherein the solute is Si.
を析出させる液相成長装置において、 前記溶媒に前記溶質を供給する溶媒溜と、前記溶質が供
給された溶媒を循環させるパイプとを備え、該パイプの
両端が前記溶媒溜の側壁に繋がっており、該パイプは熱
交換器を有しており、前記パイプの途中には基体と接触
させるための開口が設けられており、前記溶媒溜が前記
溶質からなる蓋を有しており、該蓋の一部によって溶媒
の流路が形成されていることを特徴とする液相成長装
置。9. A liquid phase growth apparatus for dissolving a solute in a solvent to precipitate crystals on a substrate, comprising: a solvent reservoir for supplying the solute to the solvent; and a pipe for circulating the solvent to which the solute is supplied. provided, both ends of the pipe are connected to the side wall of said solvent reservoir, the pipe has a heat exchanger, in the middle of the pipe is provided with an opening for contact with the substrate, the solvent The reservoir is
It has a lid made of solute, and a part of the lid
A liquid phase growth apparatus, wherein a flow path is formed .
びそれに接する基体の温度とを独立して温度制御するた
めの手段を設けたことを特徴とする請求項９記載の液相
成長装置。10. The liquid phase growth apparatus according to claim 9, further comprising means for independently controlling the temperature of the solvent reservoir and the temperature of the circulation pipe and the substrate in contact with the circulation pipe.
に配置するとともに溶媒溜周辺に溶媒溜を独立して加熱
するための手段を設けたことを特徴とする請求項１０記
載の液相成長装置。11. The liquid phase growth according to claim 10, wherein said solvent reservoir and said pipe are arranged in an electric furnace and means for independently heating said solvent reservoir are provided around said solvent reservoir. apparatus.
ータが設けられていることを特徴とする請求項９ないし
１１のいずれか１項に記載の液相成長装置。12. The liquid phase growth apparatus according to claim 9, wherein a rotor for circulating a solvent is provided in a part of the pipe.
がら前記パイプの開口部において前記溶媒と前記基体と
が接するように配置されたスライダが設けられているこ
とを特徴とする請求項９ないし１２のいずれか１項に記
載の液相成長装置。13. A slider according to claim 9, further comprising a slider disposed so as to contact said solvent and said base at an opening of said pipe while holding and moving said base. The liquid phase growth apparatus according to claim 1.
り、前記パイプの開口部において前記溶媒と接触し得る
ように前記連続基体を移動させるための手段を設けたこ
とを特徴とする請求項９ないし１２のいずれか１項に記
載の液相成長装置。14. The substrate according to claim 9, wherein said substrate is a web-shaped continuous substrate, and means is provided for moving said continuous substrate so as to contact said solvent at an opening of said pipe. 13. The liquid phase growth apparatus according to any one of claims 12 to 12.
びそれに接する基体の温度とをそれぞれ一定に保つため
の制御手段を設けたことを特徴とする請求項９ないし１
４のいずれか１項に記載の液相成長装置。15. A control means for keeping the temperature of the solvent reservoir and the temperature of the circulating pipe and the substrate in contact with the circulating pipe constant, respectively.
5. The liquid phase growth apparatus according to any one of 4.
る請求項９ないし１５のいずれか１項に記載の液相成長
装置。16. The liquid phase growth apparatus according to claim 9, wherein the solvent is Sn.
る請求項９ないし１６のいずれか１項に記載の液相成長
装置。17. The liquid phase growth apparatus according to claim 9, wherein the solute is Si.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05140277A JP3122283B2 (en) | 1993-06-11 | 1993-06-11 | Liquid phase growth method and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05140277A JP3122283B2 (en) | 1993-06-11 | 1993-06-11 | Liquid phase growth method and apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06349751A JPH06349751A (en) | 1994-12-22 |
| JP3122283B2 true JP3122283B2 (en) | 2001-01-09 |
Family
ID=15265039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05140277A Expired - Fee Related JP3122283B2 (en) | 1993-06-11 | 1993-06-11 | Liquid phase growth method and apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3122283B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5003642B2 (en) * | 2008-09-30 | 2012-08-15 | 豊田合成株式会社 | Group III nitride semiconductor crystal manufacturing equipment |
-
1993
- 1993-06-11 JP JP05140277A patent/JP3122283B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06349751A (en) | 1994-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2693032B2 (en) | Method for forming semiconductor layer and method for manufacturing solar cell using the same | |
| JP3839750B2 (en) | Photovoltaic device manufacturing equipment | |
| US6869863B2 (en) | Fabrication process of solar cell | |
| US20010051387A1 (en) | Method of growing silicon crystal in liquid phase and method of producing solar cell | |
| JPS5945634B2 (en) | Method for manufacturing vertical p-n junctions when pulling silicon disks from silicon melt | |
| US6391108B2 (en) | Liquid phase growth method of silicon crystal, method of producing solar cell, and liquid phase growth apparatus | |
| US20080142763A1 (en) | Directional crystallization of silicon sheets using rapid thermal processing | |
| JP3122283B2 (en) | Liquid phase growth method and apparatus | |
| US7118625B2 (en) | Liquid phase growth method for silicon crystal, manufacturing method for solar cell and liquid phase growth apparatus for silicon crystal | |
| US6824609B2 (en) | Liquid phase growth method and liquid phase growth apparatus | |
| JP2915434B2 (en) | Method and apparatus for forming semiconductor layer and method for manufacturing solar cell using this method | |
| JP3212725B2 (en) | Liquid phase growth method and liquid phase growth apparatus | |
| JP2006216761A (en) | Consecutive liquid-phase film forming method and device | |
| JP2003092285A (en) | Manufacturing method for semiconductor substrate | |
| Belouet | Growth of polysilicon sheets by the RAD process | |
| JPH11292693A (en) | Liquid phase growth of silicon crystal, production of solar cell and liquid phase growth device | |
| JP3069208B2 (en) | Method for manufacturing thin-film polycrystalline Si solar cell | |
| JPH09110591A (en) | Production of plate-like silicon crystal and solar battery | |
| CN114945712A (en) | Thin plate-like single crystal manufacturing apparatus and thin plate-like single crystal manufacturing method | |
| JP2000264618A (en) | Production of silicon plate polycrystal | |
| JPH0912394A (en) | Production of planar crystal | |
| JP2000178095A (en) | Crystal growth process | |
| JPH09315891A (en) | Production of plate silicon crystal and solar cell manufactured with the plate crystal | |
| JP2004161583A (en) | Method for manufacturing thin sheet, and solar battery | |
| JPH08333193A (en) | Production of semiconductor crystal and apparatus therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |