JP2001093842A - Plasma cvd apparatus, and method of manufacturing silicon-based thin-film photoelectric converter - Google Patents
Plasma cvd apparatus, and method of manufacturing silicon-based thin-film photoelectric converterInfo
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- JP2001093842A JP2001093842A JP27279999A JP27279999A JP2001093842A JP 2001093842 A JP2001093842 A JP 2001093842A JP 27279999 A JP27279999 A JP 27279999A JP 27279999 A JP27279999 A JP 27279999A JP 2001093842 A JP2001093842 A JP 2001093842A
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- electrode
- gas
- photoelectric conversion
- substrate
- silicon
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- 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]
【発明の属する技術分野】本発明は、プラズマＣＶＤ装
置およびこのプラズマＣＶＤ装置を用いて非晶質または
結晶質シリコン系薄膜光電変換層を成膜する工程を含む
シリコン系薄膜光電変換装置の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma CVD apparatus and a method for manufacturing a silicon-based thin film photoelectric conversion apparatus including a step of forming an amorphous or crystalline silicon-based thin film photoelectric conversion layer using the plasma CVD apparatus. About.
【０００２】なお、本明細書において、「結晶質」と
「微結晶」の用語は、部分的に非晶質状態を含むものを
も意昧するものとする。[0002] In the present specification, the terms "crystalline" and "microcrystal" are intended to include those partially including an amorphous state.
【０００３】[0003]
【従来の技術】薄膜光電変換装置の代表的なものとして
非晶質シリコン系太陽電池が知られている。この太陽電
池に用いられる非晶質光電変換材料は、通常２００℃前
後の低い成膜温度の下でプラズマＣＶＤ法によって形成
できるため、基板としてガラス、ステンレス、有機フィ
ルム等の安価なものを使用できる。その結果、非晶質光
電変換材料は、低コストの光電変換装置を製造するのた
めの有力材料として期待されている。また、非晶質シリ
コンは可視光領域での吸収係数が大きいため、５００ｎ
ｍ以下の薄い膜厚の非晶質シリコンからなる光電変換層
を有する太陽電池において１５ｍＡ／ｃｍ2以上の短絡
電流が実現されている。2. Description of the Related Art An amorphous silicon solar cell is known as a typical thin film photoelectric conversion device. Since the amorphous photoelectric conversion material used for this solar cell can be formed by a plasma CVD method under a low film formation temperature of about 200 ° C., inexpensive materials such as glass, stainless steel, and organic films can be used as the substrate. . As a result, an amorphous photoelectric conversion material is expected as a leading material for manufacturing a low-cost photoelectric conversion device. Further, since amorphous silicon has a large absorption coefficient in the visible light region, 500 n
A short-circuit current of 15 mA / cm 2 or more has been realized in a solar cell having a photoelectric conversion layer made of amorphous silicon having a thin film thickness of not more than m.
【０００４】しかしながら、非晶質シリコン系材料は長
期間の光照射を受けると、Stebler-Wronsky効果により
光電変換特性が低下するなどの問題を抱えており、さら
にその有効感度波長領域が８００ｎｍ程度に制限されて
いる。したがって、非晶質シリコン系材料を用いた光電
変換装置においては、その信頼性や高性能化には限界が
見られ、基板選択の自由度や低コストプロセスを利用し
得るという本来の利点が十分には生かされていない。However, amorphous silicon-based materials suffer from problems such as deterioration of photoelectric conversion characteristics due to the Stebler-Wronsky effect when exposed to light for a long period of time, and the effective sensitivity wavelength region is reduced to about 800 nm. Limited. Therefore, in a photoelectric conversion device using an amorphous silicon-based material, its reliability and high performance are limited, and the inherent advantages of the freedom of substrate selection and the use of a low-cost process are sufficient. Has not been utilized.
【０００５】このようなことから、近年、例えば多結晶
シリコンや微結晶シリコンのような結晶質シリコンを含
む薄膜を利用した光電変換装置の開発が精力的に行なわ
れている。これらの開発は、安価な基板上に低温プロセ
スで良質の結晶質シリコン薄膜を形成することによって
光電変換装置の低コスト化と高性能化を両立させるとい
う試みであり、太陽電池だけでなく光センサ等の様々な
光電変換装置への応用が期待されている。[0005] For these reasons, in recent years, photoelectric conversion devices using thin films containing crystalline silicon such as polycrystalline silicon and microcrystalline silicon have been vigorously developed. These developments attempt to achieve both low-cost and high-performance photoelectric conversion devices by forming high-quality crystalline silicon thin films on low-cost processes on inexpensive substrates. It is expected to be applied to various photoelectric conversion devices.
【０００６】結晶質シリコン薄膜の形成方法としては、
例えばＣＶＤ法やスパッタリング法にて基板上に直接堆
積させるか、同様のプロセスで一旦非晶質膜を堆積させ
た後に熱アニールやレーザアニールを行なうことによっ
て結晶化を図るなどの方法が知られている。いずれの方
法においても前述した安価な基板を用いるためには成膜
時の温度を５５０℃以下にする必要がある。As a method of forming a crystalline silicon thin film,
For example, a method of depositing directly on a substrate by a CVD method or a sputtering method, or a method of achieving crystallization by performing thermal annealing or laser annealing after once depositing an amorphous film by a similar process is known. I have. In any method, in order to use the inexpensive substrate described above, the temperature at the time of film formation needs to be 550 ° C. or less.
【０００７】前記各成膜プロセスの中でも、プラズマＣ
ＶＤ法によって直接結晶質シリコン薄膜を堆積させる手
法は、プロセスの低温化や薄膜の大面積化が最も容易で
あり、しかも比較的簡便なプロセスで高品質な結晶質薄
膜が得られるものと期待されている。In each of the above-mentioned film forming processes, plasma C
The method of directly depositing a crystalline silicon thin film by the VD method is expected to be able to obtain a high-quality crystalline thin film by a relatively simple process because it is easiest to lower the temperature of the process and increase the area of the thin film. ing.
【０００８】ところで、プラズマＣＶＤ法に用いられる
装置としては従来より図７および図８に示す構造のもの
が知られている。図７中の矩形状の反応容器１は、対向
する両側壁に排気部材である排気管２，２がそれぞれ連
結されている。前記排気管２，２は、それら他端が図示
しない真空ポンプ等に連結されている。基板を出し入れ
するための図示しないバルブは、前記反応容器１の対向
する側壁に設けられている。矩形状の第１電極３は、前
記反応容器１内に支持軸４により支持されて配置されて
いる。前記第１電極３上部には、載置されるべき基板を
加熱するための図示しないヒータが内蔵されている。前
記第１電極３は、例えばグランドに接続されている。矩
形中空状の第２電極５は、前記反応容器１内に前記第１
電極３の上面と対向するように配置され、上面に前記反
応容器１を貫通してその内部に延出されたガス供給管６
が連結されている。この第２電極５は、図８に示すよう
に前記第１電極３と対向する前面にガス吹き出し板７を
有する。このガス吹き出し板７には、記第１電極３と対
向する底面側に開口した複数の拡口穴８とこれら穴８の
背面の前記ガス吹き出し板７部分に開口して連通された
その穴８より径の小さいガス導入穴９とからなるガス吹
き出し穴１０が設けられている。例えば高周波電源（図
示せず）は、前記第２電極５に接続されている。By the way, as an apparatus used for the plasma CVD method, an apparatus having a structure shown in FIGS. 7 and 8 has been conventionally known. In the rectangular reaction vessel 1 in FIG. 7, exhaust pipes 2 and 2 as exhaust members are respectively connected to opposing side walls. The other ends of the exhaust pipes 2 and 2 are connected to a vacuum pump or the like (not shown). Valves (not shown) for taking in and out of the substrate are provided on opposite side walls of the reaction vessel 1. The rectangular first electrode 3 is disposed in the reaction vessel 1 while being supported by a support shaft 4. Above the first electrode 3, a heater (not shown) for heating a substrate to be mounted is incorporated. The first electrode 3 is connected to, for example, the ground. The rectangular hollow second electrode 5 is provided inside the reaction vessel 1 with the first electrode 5.
A gas supply pipe 6 is disposed so as to face the upper surface of the electrode 3 and penetrates through the reaction vessel 1 on the upper surface and extends therein.
Are connected. The second electrode 5 has a gas blowing plate 7 on the front surface facing the first electrode 3 as shown in FIG. The gas blowing plate 7 has a plurality of opening holes 8 opened on the bottom side facing the first electrode 3 and the holes 8 opened and communicated with the gas blowing plate 7 on the back of these holes 8. A gas blowing hole 10 including a gas introducing hole 9 having a smaller diameter is provided. For example, a high frequency power supply (not shown) is connected to the second electrode 5.
【０００９】このような構成のＣＶＤ装置において、図
示しないバルブを通して基板１１を反応容器１内の第１
電極３上に載置し、その第１電極３に内蔵した図示しな
いヒータの発熱により前記基板１１を所望温度に加熱す
る。反応ガス（例えばシラン系ガスと水素を含む反応ガ
ス）をガス供給管６を通して中空状の第２電極５内に導
入し、その底部に配置されたガス吹き出し板７の複数の
ガス吹き出し穴１０から反応ガスを第１電極３上の基板
１１に向けて吹き出す。同時に、図示しない真空ポンプ
のような排気装置を駆動して前記反応容器１内のガスを
排気管２，２を通して排気して前記反応容器１内を所定
の真空度に保持する。In the CVD apparatus having such a configuration, the substrate 11 is passed through the valve (not shown) and the first substrate 11 in the reaction vessel 1.
The substrate 11 is placed on the electrode 3, and the substrate 11 is heated to a desired temperature by heat generated by a heater (not shown) built in the first electrode 3. A reaction gas (for example, a reaction gas containing a silane-based gas and hydrogen) is introduced into the hollow second electrode 5 through a gas supply pipe 6, and from a plurality of gas ejection holes 10 of a gas ejection plate 7 disposed at the bottom thereof. The reaction gas is blown toward the substrate 11 on the first electrode 3. At the same time, an exhaust device such as a vacuum pump (not shown) is driven to exhaust the gas in the reaction vessel 1 through the exhaust pipes 2 and 2 to maintain the inside of the reaction vessel 1 at a predetermined degree of vacuum.
【００１０】反応容器１内の真空度が安定した状態で、
図示しない電源から前記第２電極５に例えば高周波電力
を印加する。このような高周波電力の印加により前記ガ
ス吹き出し板７と前記基板１１の間にプラズマ１２が生
成される。プラズマ１２が生成されると、その中で反応
ガス（シラン系ガス）が分解されてシリコンが前記所望
温度（例えば５５０℃以下）に加熱された前記基板１１
表面に堆積されてシリコン薄膜が成膜される。In a state where the degree of vacuum in the reaction vessel 1 is stable,
For example, high-frequency power is applied to the second electrode 5 from a power source (not shown). By applying such high frequency power, plasma 12 is generated between the gas blowout plate 7 and the substrate 11. When the plasma 12 is generated, a reaction gas (silane-based gas) is decomposed therein and silicon is heated to the desired temperature (for example, 550 ° C. or lower).
The silicon thin film is deposited on the surface.
【００１１】[0011]
【発明が解決しようとする課題】しかしながら、前述し
た従来のＣＶＤ装置において反応ガスをガス供給管６か
ら中空状の第２電極５内に供給し、この第２電極５底部
に配置されたガス吹き出し板７のガス吹き出し穴１０か
ら第１電極３上の基板１１に向けて吹き出して主に前記
ガス吹き出し板７と前記基板１１の間にプラズマ１２を
生成する際、前記ガス吹き出し穴１０間の平坦なガス吹
き出し板７部分の表面にパウダーのような反応ガスの生
成物が付着して成長する。成長したパウダーは、成膜中
に剥離、落下して前記基板１１表面の薄膜に付着する。
その結果、薄膜の膜質が劣化したり、そのパウダー付着
部での異常成膜により膜厚が不均一になったりする。However, in the above-mentioned conventional CVD apparatus, a reactive gas is supplied from the gas supply pipe 6 into the hollow second electrode 5, and a gas blowout arranged at the bottom of the second electrode 5 is supplied. When a plasma 12 is generated between the gas blowout plate 7 and the substrate 11 by blowing out from the gas blowout hole 10 of the plate 7 toward the substrate 11 on the first electrode 3, the flatness between the gas blowout holes 10 is generated. A reaction gas product such as powder adheres to the surface of the gas blowing plate 7 and grows. The grown powder peels off during film formation, falls, and adheres to the thin film on the surface of the substrate 11.
As a result, the quality of the thin film is degraded, or the film thickness becomes non-uniform due to abnormal film formation at the powder attachment portion.
【００１２】このような成膜中の薄膜へのパウダーの落
下、付着を回避するためには前記第２電極のクリーニン
グを頻繁に行なう必要がある。In order to prevent the powder from falling and sticking to the thin film during film formation, it is necessary to frequently clean the second electrode.
【００１３】したがって、従来のＣＶＤ装置を非晶質ま
たは多結晶シリコンまたは部分的に非晶質相を含む微結
晶シリコンのような薄膜、例えば光電変換装置の製造に
おける非晶質または結晶質シリコン系光電変換層、の形
成に適用すると、クリーニング頻度が多くなるため、実
効的な稼動時間が短くなって光電変換装置のスループッ
トの向上が困難となり、低コスト化の妨げとなる。Therefore, a conventional CVD apparatus can be used to form a thin film such as amorphous or polycrystalline silicon or microcrystalline silicon partially containing an amorphous phase, for example, an amorphous or crystalline silicon-based material in the production of a photoelectric conversion device. When applied to the formation of the photoelectric conversion layer, the frequency of cleaning increases, so that the effective operation time is shortened, and it is difficult to improve the throughput of the photoelectric conversion device, which hinders cost reduction.
【００１４】本発明は、成膜中の中空状電極のガス吹き
出し板へのパウダーのような反応ガスの生成物の付着を
抑制することが可能なプラズマＣＶＤ装置を提供するこ
とを目的とする。It is an object of the present invention to provide a plasma CVD apparatus capable of suppressing adhesion of a reaction gas product such as powder to a gas blowing plate of a hollow electrode during film formation.
【００１５】本発明は、シリコン系光電変換層を有する
光電変換ユニットを積層する際、前記プラズマＣＶＤ装
置を用いて高品位のシリコン系光電変換層を成膜して製
造工程のスループットの向上および性能改善を達成した
シリコン系薄膜光電変換装置の製造方法を提供すること
を目的とする。According to the present invention, when stacking a photoelectric conversion unit having a silicon-based photoelectric conversion layer, a high-quality silicon-based photoelectric conversion layer is formed using the plasma CVD apparatus to improve the throughput of the manufacturing process and improve the performance. An object of the present invention is to provide a method of manufacturing a silicon-based thin-film photoelectric conversion device that achieves improvement.
【００１６】[0016]
【課題を解決するための手段】本発明に係わるプラズマ
ＣＶＤ装置は、排気部材を有する反応容器と、前記反応
容器内に配置され、被処理基板を保持する第１電極と、
前記反応容器内に前記第１電極に対向して配置された中
空状の第２電極と、前記第２電極内に反応ガスを供給す
るためのガス供給手段と、前記第２電極に電力を印加す
るための電源とを具備し、前記中空状の第２電極は、前
記第１電極と対向する面に多数の異形のガス吹き出し穴
が開口されたガス吹き出し板を有することを特徴とする
ものである。According to the present invention, there is provided a plasma CVD apparatus comprising: a reaction vessel having an exhaust member; a first electrode disposed in the reaction vessel and holding a substrate to be processed;
A hollow second electrode disposed in the reaction vessel so as to face the first electrode, gas supply means for supplying a reaction gas into the second electrode, and applying power to the second electrode And a power supply for performing the operation, wherein the hollow second electrode has a gas blowing plate having a number of irregular gas blowing holes formed on a surface facing the first electrode. is there.
【００１７】本発明に係わる別のプラズマＣＶＤ装置
は、排気部材を有する反応容器と、前記反応容器内に配
置され、被処理基板を保持する第１電極と、前記反応容
器内に前記第１電極に対向して配置された中空状の第２
電極と、前記第２電極内に反応ガスを供給するためのガ
ス供給手段と、前記第２電極に電力を印加するための電
源とを具備し、前記中空状の第２電極は、前記第１電極
と対向する面に複数のガス吹き出し穴が開口され、かつ
これらガス吹き出し穴間にこの穴と異なる寸法の複数の
凹部が設けられたガス吹き出し板を有することを特徴と
するものである。Another plasma CVD apparatus according to the present invention comprises a reaction vessel having an exhaust member, a first electrode disposed in the reaction vessel and holding a substrate to be processed, and a first electrode in the reaction vessel. The hollow second
An electrode, a gas supply unit for supplying a reaction gas into the second electrode, and a power supply for applying power to the second electrode, wherein the hollow second electrode includes the first electrode. A gas blowout plate is provided with a plurality of gas blowout holes opened on a surface facing the electrode, and a plurality of concave portions having dimensions different from those of the gas blowout holes provided between the gas blowout holes.
【００１８】本発明に係わるシリコン系薄膜光電変換装
置の製造方法は、基板上に形成された少なくとも１つの
光電変換ユニットを含み、この光電変換ユニットはプラ
ズマＣＶＤ法によって順次積層された一導電型半導体層
と、シリコン系薄膜光電変換層と、逆導電型半導体層と
を含むシリコン系薄膜光電変換装置を製造するに際し、
前記ユニットのうちのいずれかの層は、前述したプラズ
マＣＶＤ装置の反応容器内の第１電極に前記基板を保持
するとともに、電源から中空状の第２電極に電力を供給
し、かつシラン系ガスと水素ガスを含む反応ガスを前記
中空状の第２電極におけるガス吹き出し板のガス吹き出
し穴を通して前記第１電極の基板に向けて吹き出し、前
記基板と前記第２電極間にプラズマを発生させることに
より成膜されることを特徴とするものである。A method of manufacturing a silicon-based thin-film photoelectric conversion device according to the present invention includes at least one photoelectric conversion unit formed on a substrate, wherein the photoelectric conversion unit is a one-conductivity type semiconductor sequentially stacked by a plasma CVD method. In manufacturing a silicon-based thin film photoelectric conversion device including a layer, a silicon-based thin film photoelectric conversion layer, and a semiconductor layer of the opposite conductivity type,
One of the layers of the unit holds the substrate on the first electrode in the reaction vessel of the plasma CVD apparatus described above, supplies power from a power source to the hollow second electrode, and includes a silane-based gas. And a reaction gas containing hydrogen gas is blown toward the substrate of the first electrode through a gas blowout hole of a gas blowout plate in the hollow second electrode to generate plasma between the substrate and the second electrode. It is characterized by being formed into a film.
【００１９】[0019]
【発明の実施の形態】以下、本発明に係わるプラズマＣ
ＶＤ装置を図１〜図３を参照して詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a plasma C according to the present invention will be described.
The VD device will be described in detail with reference to FIGS.
【００２０】図１は、本発明に係わるプラズマＣＶＤ装
置を示す概略図、図２は図１のプラズマＣＶＤ装置の要
部断面図、図３は図２のIII−III矢視図である。FIG. 1 is a schematic view showing a plasma CVD apparatus according to the present invention, FIG. 2 is a sectional view of a main part of the plasma CVD apparatus of FIG. 1, and FIG. 3 is a view taken along the line III-III of FIG.
【００２１】矩形状の反応容器２１は、対向する両側壁
に排気部材である排気管２２，２２がそれぞれ連結され
ている。前記排気管２２，２２は、それら他端が図示し
ない真空ポンプ等に連結されている。基板を出し入れす
るための図示しないバルブは、前記反応容器２１の対向
する側壁に設けられている。The rectangular reaction vessel 21 has exhaust pipes 22 and 22 as exhaust members connected to opposite side walls, respectively. The other ends of the exhaust pipes 22 are connected to a vacuum pump or the like (not shown). A valve (not shown) for taking in and out the substrate is provided on the opposite side wall of the reaction vessel 21.
【００２２】矩形状の第１電極２３は、前記反応容器２
１内に支持軸２４により支持されて配置されている。前
記第１電極２３上部には、載置されるべき基板を加熱す
るための図示しないヒータが内蔵されている。前記第１
電極２３は、例えばグランドに接続されている。The rectangular first electrode 23 is connected to the reaction vessel 2.
1 and supported by a support shaft 24. Above the first electrode 23, a heater (not shown) for heating a substrate to be mounted is incorporated. The first
The electrode 23 is connected to, for example, the ground.
【００２３】矩形中空状の第２電極２５は、前記反応容
器２１内に前記第１電極２３の上面と対向するように配
置されている。図示しない高周波電源は、前記第２電極
２５に接続されている。ガス供給管２６は、前記反応容
器２１を貫通してその内部に延出され、その先端が前記
矩形中空状の第２電極２５の上面に連結されている。前
記第２電極２５は、図２および図３に示すように前記第
１電極３と対向する前面にガス吹き出し板２７が配置さ
れた構造を有する。ガスの分散性を向上するために前記
ガス吹き出し板２７の裏面に更に図示しないガス分散板
を数枚設けている。The rectangular hollow second electrode 25 is disposed in the reaction vessel 21 so as to face the upper surface of the first electrode 23. A high-frequency power supply (not shown) is connected to the second electrode 25. The gas supply pipe 26 penetrates through the reaction vessel 21 and extends into the inside thereof, and the tip thereof is connected to the upper surface of the rectangular hollow second electrode 25. The second electrode 25 has a structure in which a gas blowing plate 27 is disposed on the front surface facing the first electrode 3 as shown in FIGS. In order to improve gas dispersibility, several gas dispersion plates (not shown) are further provided on the back surface of the gas blowing plate 27.
【００２４】前記ガス吹き出し板２７には、前記第１電
極２３と対向する面側に開口された複数の円柱状拡口穴
２８とこれら穴２８の背面の前記ガス吹き出し板２７部
分に開口して連通されたその穴２８より径の小さいガス
導入穴２９とからなる第１ガス吹き出し穴３０が設けら
れている。前記拡口穴２８より直径の小さい複数の円柱
状の第２ガス吹き出し穴３１は、前記第１ガス吹き出し
穴３０の間に前記ガス吹き出し板２７部分に開口されて
いる。The gas blow-out plate 27 has a plurality of cylindrical openings 28 opened on the surface side facing the first electrode 23 and the gas blow-out plate 27 at the back of these holes 28. There is provided a first gas blowout hole 30 including a gas introduction hole 29 having a smaller diameter than the hole 28 communicated therewith. A plurality of cylindrical second gas outlets 31 having a smaller diameter than the opening 28 are open to the gas outlet plate 27 between the first gas outlets 30.
【００２５】前記第１ガス吹き出し穴３０の拡口穴２８
は、１〜２０ｍｍ、好ましくは２〜１０ｍｍ、さらに好
ましくは４〜５ｍｍの直径を有することが望ましい。The widening hole 28 of the first gas blowing hole 30
Has a diameter of 1 to 20 mm, preferably 2 to 10 mm, more preferably 4 to 5 mm.
【００２６】前記第２ガス吹き出し穴３１は、０．１〜
５ｍｍ、好ましくは０．３〜２ｍｍの直径を有すること
が望ましい。The second gas blowing hole 31 has a diameter of 0.1 to
It is desirable to have a diameter of 5 mm, preferably 0.3-2 mm.
【００２７】次に、前述した図１〜図３に示す構成のプ
ラズマＣＶＤ装置の作用を説明する。Next, the operation of the plasma CVD apparatus having the structure shown in FIGS. 1 to 3 will be described.
【００２８】まず、図示しないバルブを通して基板３２
を反応容器２１内の第１電極２３上に載置し、その第１
電極２３に内蔵した図示しないヒータの発熱により前記
基板３２を所望温度に加熱する。反応ガス（例えばシラ
ン系ガスと水素を含む反応ガス）をガス供給管２６を通
して中空状の第２電極２５内に導入し、その底部に配置
されたガス吹き出し板２７の互いに異形の複数の第１ガ
ス吹き出し穴３０および複数の第２ガス吹き出し穴３１
から前記第１電極２３上の基板３２に向けて吹き出す。
同時に、図示しない真空ポンプのような排気装置を駆動
して前記反応容器２１内のガスを排気管２２，２２を通
して排気して前記反応容器２１内を所定の真空度に保持
する。First, the substrate 32 is passed through a valve (not shown).
Is placed on the first electrode 23 in the reaction vessel 21 and the first
The substrate 32 is heated to a desired temperature by the heat generated by a heater (not shown) built in the electrode 23. A reaction gas (for example, a reaction gas containing a silane-based gas and hydrogen) is introduced into the hollow second electrode 25 through a gas supply pipe 26, and a plurality of deformed first gas discharge plates 27 arranged on the bottom of the second electrode 25 are disposed. Gas blowout hole 30 and a plurality of second gas blowout holes 31
Is blown out toward the substrate 32 on the first electrode 23.
At the same time, an exhaust device such as a vacuum pump (not shown) is driven to exhaust the gas in the reaction vessel 21 through the exhaust pipes 22 to maintain the inside of the reaction vessel 21 at a predetermined degree of vacuum.
【００２９】反応容器２１内の真空度が安定した状態
で、図示しない電源から前記第２電極２５に例えば高周
波電力を印加する。このような高周波電力の印加により
前記ガス吹き出し板２７と前記基板３２の間にプラズマ
３３が生成される。プラズマ３３が生成されると、その
中で反応ガス（シラン系ガス）が分解されてシリコンが
前記所望温度（例えば５５０℃以下）に加熱された前記
基板３２表面に堆積されてシリコン薄膜が成膜される。While the degree of vacuum in the reaction vessel 21 is stable, for example, high-frequency power is applied to the second electrode 25 from a power source (not shown). By applying such high frequency power, a plasma 33 is generated between the gas blowing plate 27 and the substrate 32. When the plasma 33 is generated, a reaction gas (silane-based gas) is decomposed therein, and silicon is deposited on the surface of the substrate 32 heated to the desired temperature (for example, 550 ° C. or lower) to form a silicon thin film. Is done.
【００３０】前述した成膜時において、前記中空状の第
２電極２５の前記第１電極２３と対向するガス吹き出し
板２７に径の大きな拡口穴２８を有する複数の第１ガス
吹き出し穴３０を開口するとともに、これら第１ガス吹
き出し穴３０間に位置する前記ガス吹き出し板２７部分
に前記拡口穴２８の径より小さい第２ガス吹き出し穴３
１を開口することによって、前記ガス吹き出し板２７の
平坦な面積を実効的に減少させることができる。このた
め、反応ガスを前記ガス吹き出し板２７に開口された第
１、第２のガス吹き出し穴３０，３１から第１電極２３
上の基板３２に向けて吹き出して主に前記ガス吹き出し
板２７と前記基板３２の間にプラズマ３３を生成する
際、前記ガス吹き出し板２７の平坦な面積を実効的に減
少させることにより、そのガス吹き出し板２７の平坦部
にパウダーのような反応ガスの生成物が付着して成長す
るのを抑制することができる。その結果、成膜中に第２
電極２５のガス吹き出し板２７から前記パウダーが剥
離、落下して前記基板３２表面の薄膜に付着するのを抑
制できる。At the time of the above-described film formation, a plurality of first gas blowing holes 30 having a large-diameter widening hole 28 are formed in the gas blowing plate 27 of the hollow second electrode 25 facing the first electrode 23. The second gas blowout holes 3 smaller than the diameter of the widening holes 28 are formed in the gas blowout plate 27 located between the first gas blowout holes 30 while being opened.
By opening the opening 1, the flat area of the gas blowing plate 27 can be effectively reduced. For this reason, the reaction gas is supplied to the first electrode 23 from the first and second gas blowing holes 30 and 31 opened in the gas blowing plate 27.
When the plasma is generated between the gas blowing plate 27 and the substrate 32 mainly by blowing toward the upper substrate 32, the gas is reduced by effectively reducing the flat area of the gas blowing plate 27. It is possible to suppress a reaction gas product such as powder from adhering to the flat portion of the blowing plate 27 and growing the powder. As a result, the second
The powder can be prevented from peeling and falling from the gas blowing plate 27 of the electrode 25 and adhering to the thin film on the surface of the substrate 32.
【００３１】したがって、パウダーの付着に起因する薄
膜の膜質劣化、そのパウダー付着部での異常成膜により
膜厚の不均一化を防止できる。Therefore, it is possible to prevent the quality of the thin film from deteriorating due to the adhesion of the powder, and to prevent the film thickness from becoming non-uniform due to abnormal film formation at the portion where the powder is attached.
【００３２】また、前記第２電極２５のガス吹き出し板
２７へのパウダー付着を抑制できることによって、クリ
ーニングの頻度を減少でき、実効的な稼動時間を長くで
きるため、生産性を向上できる。Further, since the powder adhesion of the second electrode 25 to the gas blowing plate 27 can be suppressed, the frequency of cleaning can be reduced and the effective operation time can be extended, so that the productivity can be improved.
【００３３】さらに、前記中空状の第２電極２５の前記
第１電極２３との対向するガス吹き出し板２７に複数の
第１、第２のガス吹き出し穴３０，３１を開口すること
によって、従来のＣＶＤ装置に比べてガスの吹き出し箇
所を増加できるため、前記ガス吹き出し板２７と前記基
板３２のガス分布を均一化できる。その結果、前記ガス
吹き出し板２７と前記基板３２の間にプラズマ３３を生
成することによって、均一な薄膜を前記基板３２表面に
成膜できる。Further, a plurality of first and second gas blowout holes 30 and 31 are formed in the gas blowout plate 27 of the hollow second electrode 25 facing the first electrode 23, so that a conventional gas blowout hole is formed. Since the number of gas blowing locations can be increased as compared with the CVD apparatus, the gas distribution on the gas blowing plate 27 and the substrate 32 can be made uniform. As a result, a uniform thin film can be formed on the surface of the substrate 32 by generating the plasma 33 between the gas blowing plate 27 and the substrate 32.
【００３４】次に、本発明に係わるプラズマＣＶＤ装置
の他の形態を図４を参照して説明する。なお、前述した
図１〜図３と同様な部材は同符号を付して説明を省略す
る。Next, another embodiment of the plasma CVD apparatus according to the present invention will be described with reference to FIG. The same members as those in FIGS. 1 to 3 described above are denoted by the same reference numerals, and description thereof is omitted.
【００３５】このプラズマＣＶＤ装置は、中空状の第２
電極２５のガス吹き出し板２７における第１電極２３と
対向する面側から開口された複数の円柱状拡口穴３４と
これら穴３４の背面の前記ガス吹き出し板２７部分に開
口して連通したその穴３４より径の小さいガス導入穴３
５とからなるガス吹き出し穴３６を設け、さらに前記ガ
ス吹き出し穴３６の間の前記ガス吹き出し板２７の前記
第１電極２３と対向する面から開口された前記拡口穴３
４より径の小さい複数の円柱状凹部（未貫通穴）３７を
設けた構造を有する。This plasma CVD apparatus has a hollow second
A plurality of cylindrical opening holes 34 opened from the surface of the gas blowout plate 27 of the electrode 25 facing the first electrode 23, and the holes opened to communicate with the gas blowout plate 27 at the back of these holes 34. Gas inlet hole 3 smaller in diameter than 34
5. The gas outlet holes 36 formed from the surface of the gas outlet plate 27 facing the first electrode 23 between the gas outlet holes 36 are provided.
It has a structure in which a plurality of cylindrical concave portions (not-through holes) 37 having a diameter smaller than 4 are provided.
【００３６】前記ガス吹き出し穴３６の拡口穴３４は、
１〜２０ｍｍ、好ましくは２〜１０ｍｍ、さらに好まし
くは４〜５ｍｍの直径を有することが望ましい。The widening hole 34 of the gas blowing hole 36 is
It is desirable to have a diameter of 1 to 20 mm, preferably 2 to 10 mm, more preferably 4 to 5 mm.
【００３７】前記円柱状凹部３７は、０．１〜５ｍｍ、
好ましくは０．３〜２ｍｍの直径を有することが望まし
い。The cylindrical recess 37 has a size of 0.1 to 5 mm,
Preferably, it has a diameter of 0.3 to 2 mm.
【００３８】このような図４に示す構成によれば、成膜
時において前記中空状の第２電極２５の前記第１電極２
３と対向するガス吹き出し板２７に従来のＣＶＤ装置と
同様な径の大きな拡口穴３４を有する複数のガス吹き出
し穴３６を開口するとともに、これらガス吹き出し穴３
６間に位置する前記ガス吹き出し板２７部分に前記拡口
穴３４の径より小さい円柱状凹部３７を開口することに
よって、前記ガス吹き出し板２７の平坦な面積を実効的
に減少させることができる。このため、反応ガスを前記
ガス吹き出し板２７に開口されたガス吹き出し穴３６か
ら第１電極２３上の基板３２に向けて吹き出して主に前
記ガス吹き出し板２７と前記基板３２の間にプラズマ３
３を生成する際、小さい円柱状穴３７の内部のプラズマ
をエッチングモードにすることにより現状の放電条件を
殆ど変更することなく，前記ガス吹き出し板２７の平坦
な面積を実効的に減少させることにより、そのガス吹き
出し板２７の平坦部にパウダーのような反応ガスの生成
物が付着して成長するのを抑制することができる。その
結果、成膜中に第２電極２５のガス吹き出し板２７から
前記パウダーが剥離、落下して前記基板３２表面の薄膜
に付着するのを抑制できるため、パウダーの付着に起因
する薄膜の膜質劣化、そのパウダー付着部での異常成膜
により膜厚の不均一化を防止できる。According to the structure shown in FIG. 4, the first electrode 2 of the hollow second electrode 25 is formed at the time of film formation.
A plurality of gas blowing holes 36 having a large opening 34 having the same diameter as the conventional CVD apparatus are opened in the gas blowing plate 27 facing the gas blowing plate 3.
By opening a cylindrical concave portion 37 smaller than the diameter of the widening hole 34 in the portion of the gas blowing plate 27 located between the six, the flat area of the gas blowing plate 27 can be effectively reduced. For this reason, the reaction gas is blown out from the gas blowing holes 36 opened in the gas blowing plate 27 toward the substrate 32 on the first electrode 23, and the plasma 3 mainly flows between the gas blowing plate 27 and the substrate 32.
When the gas discharge plate 27 is generated, the plasma inside the small cylindrical hole 37 is set to an etching mode, thereby effectively reducing the flat area of the gas blowing plate 27 without substantially changing the current discharge conditions. In addition, it is possible to suppress the reaction gas product such as powder from adhering to the flat portion of the gas blowing plate 27 and growing the powder. As a result, it is possible to prevent the powder from peeling and falling from the gas blowing plate 27 of the second electrode 25 during film formation, and to prevent the powder from adhering to the thin film on the surface of the substrate 32. In addition, it is possible to prevent the film thickness from becoming non-uniform due to abnormal film formation at the powder adhering portion.
【００３９】また、前記第２電極２５のガス吹き出し板
２７へのパウダー付着を抑制できることによって、クリ
ーニングの頻度を減少でき、実効的な稼動時間を長くで
きるため、生産性を向上できる。Further, since the powder adhesion of the second electrode 25 to the gas blowing plate 27 can be suppressed, the frequency of cleaning can be reduced and the effective operation time can be extended, so that the productivity can be improved.
【００４０】次に、本発明に係わるプラズマＣＶＤ装置
のさらに他の形態を図５を参照して説明する。なお、前
述した図１〜図３と同様な部材は同符号を付して説明を
省略する。Next, still another embodiment of the plasma CVD apparatus according to the present invention will be described with reference to FIG. The same members as those in FIGS. 1 to 3 described above are denoted by the same reference numerals, and description thereof is omitted.
【００４１】このプラズマＣＶＤ装置は、中空状の第２
電極２５のガス吹き出し板２７にガス吹き出し穴３８を
貫通して設け、さらに前記ガス吹き出し穴３８の間の前
記ガス吹き出し板２７の前記ガス吹き出し穴３８より径
の大きな複数の円柱状凹部（未貫通穴）３９を設けた構
造を有する。This plasma CVD apparatus has a hollow second
A gas blowout hole 38 is provided through the gas blowout plate 27 of the electrode 25, and a plurality of cylindrical recesses (not penetrated) larger in diameter than the gas blowout hole 38 of the gas blowout plate 27 between the gas blowout holes 38. (Hole) 39 is provided.
【００４２】このような図５に示す構成によれば、成膜
時において前記中空状の第２電極２５の前記第１電極２
３と対向するガス吹き出し板２７に複数のガス吹き出し
穴３８を開口するとともに、これらガス吹き出し穴３８
間に位置する前記ガス吹き出し板２７部分に前記ガス吹
き出し穴３８の径より大きい円柱状凹部３９を開口する
ことによって、前記ガス吹き出し板２７の平坦な面積を
実効的に減少させることができる。このため、反応ガス
を前記ガス吹き出し板２７に開口されたガス吹き出し穴
３６から第１電極２３上の基板３２に向けて吹き出して
主に前記ガス吹き出し板２７と前記基板３２の間にプラ
ズマ３３を生成する際、大きい円柱状穴３９の内部のプ
ラズマをエッチングモードにすることによって、前記ガ
ス吹き出し板２７の平坦な面積を実効的に減少させるこ
とにより、そのガス吹き出し板２７の平坦部にパウダー
のような反応ガスの生成物が付着して成長するのを抑制
することができる。その結果、成膜中に第２電極２５の
ガス吹き出し板２７から前記パウダーが剥離、落下して
前記基板３２表面の薄膜に付着するのを抑制できるた
め、パウダーの付着に起因する薄膜の膜質劣化、そのパ
ウダー付着部での異常成膜により膜厚の不均一化を防止
できる。According to the structure shown in FIG. 5, the first electrode 2 of the hollow second electrode 25 is formed at the time of film formation.
A plurality of gas blowout holes 38 are opened in the gas blowout plate 27 facing
By opening a cylindrical recess 39 larger than the diameter of the gas blowing hole 38 in the portion of the gas blowing plate 27 located therebetween, the flat area of the gas blowing plate 27 can be effectively reduced. For this reason, the reaction gas is blown out from the gas blowout holes 36 opened in the gas blowout plate 27 toward the substrate 32 on the first electrode 23 to generate the plasma 33 mainly between the gas blowout plate 27 and the substrate 32. At the time of generation, the plasma inside the large cylindrical hole 39 is set to the etching mode, so that the flat area of the gas blowing plate 27 is effectively reduced. It is possible to suppress the product of such a reaction gas from adhering and growing. As a result, it is possible to prevent the powder from peeling and falling from the gas blowing plate 27 of the second electrode 25 during film formation, and to prevent the powder from adhering to the thin film on the surface of the substrate 32. In addition, it is possible to prevent the film thickness from becoming non-uniform due to abnormal film formation at the powder adhering portion.
【００４３】また、前記第２電極２５のガス吹き出し板
２７へのパウダー付着を抑制できることによって、クリ
ーニングの頻度を減少でき、実効的な稼動時間を長くで
きるため、生産性を向上できる。Further, since the powder adhesion of the second electrode 25 to the gas blowing plate 27 can be suppressed, the frequency of cleaning can be reduced and the effective operation time can be extended, so that the productivity can be improved.
【００４４】なお、本発明に係わるＣＶＤ装置において
前記ガス吹き出し板に設けるガス吹き出し穴および凹部
は円柱状に限らず、三角柱状、四角柱状、六角柱状等の
任意形状にしてもよい。Incidentally, in the CVD apparatus according to the present invention, the gas blowout holes and the concave portions provided in the gas blowout plate are not limited to the columnar shape, but may be of any shape such as a triangular prism, a quadrangular prism, a hexagonal prism or the like.
【００４５】次に、本発明に係わるシリコン系薄膜光電
変換装置の製造方法を図６を参照して説明する。Next, a method for manufacturing a silicon-based thin film photoelectric conversion device according to the present invention will be described with reference to FIG.
【００４６】図６は、本発明の１つの実施形態により製
造されるシリコン系薄膜光電変換装置を模式的に示す斜
視図である。FIG. 6 is a perspective view schematically showing a silicon-based thin-film photoelectric conversion device manufactured according to one embodiment of the present invention.
【００４７】（第１工程）まず、基板１０１上に裏面電
極１１０を形成する。(First Step) First, the back electrode 110 is formed on the substrate 101.
【００４８】前記基板１０１としては、例えばステンレ
ス等の金属、有機フィルム、または低融点の安価なガラ
ス等を用いることができる。As the substrate 101, for example, a metal such as stainless steel, an organic film, or an inexpensive glass having a low melting point can be used.
【００４９】前記裏面電極１１０は、例えばＴｉ，Ｃ
ｒ，Ａｌ，Ａｇ，Ａｕ，ＣｕおよびＰｔから選択された
少なくとも１以上の金属またはこれらの合金からなる層
を含む金属薄膜１０２およびＩＴＯ，ＳｎＯ2，および
ＺｎＯから選択された少なくとも１つ以上の酸化物から
なる層を合む透明導電性薄膜１０３をこの順序で積層す
ることにより形成される。ただし、金属薄膜１０２また
は透明導電性薄膜１０３のみで裏面電極１１０を構成し
てもよい。これらの薄膜１０２，１０３は、例えば蒸着
法やスパッタリング法によって形成される。The back electrode 110 is made of, for example, Ti, C
a metal thin film 102 including a layer made of at least one metal selected from r, Al, Ag, Au, Cu and Pt, or an alloy thereof; and at least one oxidation selected from ITO, SnO 2 , and ZnO It is formed by laminating the transparent conductive thin films 103 which combine layers made of an object in this order. However, the back electrode 110 may be constituted only by the metal thin film 102 or the transparent conductive thin film 103. These thin films 102 and 103 are formed by, for example, an evaporation method or a sputtering method.
【００５０】（第２工程）次いで、前記裏面電極１１０
上にプラズマＣＶＤ法によって一導電型半導体層１０
４、結晶質シリコン系薄膜光電変換層１０５および逆導
電型半導体層１０６を順次積層することにより光電変換
ユニット１１１を形成する。この光電変換ユニット１１
１は、１ユニットに限らず、複数のユニットを前記裏面
電極に形成してもよい。(Second Step) Next, the back electrode 110
One conductivity type semiconductor layer 10 is formed thereon by plasma CVD.
4. The photoelectric conversion unit 111 is formed by sequentially laminating the crystalline silicon-based thin film photoelectric conversion layer 105 and the opposite conductivity type semiconductor layer 106. This photoelectric conversion unit 11
1 is not limited to one unit, and a plurality of units may be formed on the back surface electrode.
【００５１】前記一導電型半導体層１０４、結晶質シリ
コン系薄膜光電変換層１０５および逆導電型半導体層１
０６について、以下に詳述する。The one-conductivity-type semiconductor layer 104, the crystalline silicon-based thin-film photoelectric conversion layer 105, and the opposite-conductivity-type semiconductor layer 1
06 will be described in detail below.
【００５２】１）一導電型半導体層１０４ この一導電型半導体層１０４は、例えば導電型決定不純
物原子であるリンが０．０１原子％以上ドープされたｎ
型シリコン層、またはボロンが０．０１原子％以上ドー
ブされたｐ型シリコン層などを用いることができる。た
だし、一導電型半導体層１０４に関するこれらの条件は
限定的なものではなく、不純物原子としては例えばｐ型
シリコン層においてはアルミニウム等でもよく、またシ
リコンカーバイドやシリコンゲルマニウムなどの合金材
料を用いてもよい。1) One-Conductivity-Type Semiconductor Layer 104 The one-conductivity-type semiconductor layer 104 is formed of, for example, n doped with 0.01% by atom or more of phosphorus, which is a conductivity-type determining impurity atom.
A silicon layer or a p-type silicon layer in which boron is doped by 0.01 atomic% or more can be used. However, these conditions for the one-conductivity-type semiconductor layer 104 are not limited. For example, the impurity atoms may be aluminum or the like in a p-type silicon layer, or may be an alloy material such as silicon carbide or silicon germanium. Good.
【００５３】一導電型シリコシ系薄膜１０４は、多結
晶、微結晶、または非晶質のいずれでもよく、その膜厚
は１〜１００ｎｍより好ましくは２〜３０ｎｍにするこ
とが望ましい。The one-conductivity-type silicon-based thin film 104 may be polycrystalline, microcrystalline, or amorphous, and its thickness is preferably 1 to 100 nm, more preferably 2 to 30 nm.
【００５４】２）結晶質シリコン系薄膜光電変換層１０
５ この結晶質シリコン系薄膜光電変換層１０５は、例えば
前述した図１〜図３に示すプラズマＣＶＤ装置を用い、
その反応容器２１内の第１電極２３に予め一導電型の半
導体層１０４が成膜された前記基板１０１（３２）を保
持するとともに、電源から中空状の第２電極２５に電力
を供給し、かつシラン系ガスと水素ガスを含む反応ガス
をガス供給管６を通して前記中空状の第２電極２５内に
供給し、この第２電極２５の底部に配置されたガス吹き
出し板２７に開口した互いに異形の複数の第１、第２の
ガス吹き出し穴３０，３１から前記第１電極２３上の基
板３２に向けて吹き込み、前記基板３２と前記第２電極
２５間にプラズマを発生させることにより成膜される。2) Crystalline silicon-based thin film photoelectric conversion layer 10
5 The crystalline silicon-based thin-film photoelectric conversion layer 105 is formed, for example, by using the plasma CVD apparatus shown in FIGS.
While holding the substrate 101 (32) on which the semiconductor layer 104 of one conductivity type is formed in advance on the first electrode 23 in the reaction vessel 21, power is supplied from a power source to the hollow second electrode 25, A reaction gas containing a silane-based gas and a hydrogen gas is supplied through the gas supply pipe 6 into the second hollow electrode 25, and the gas outlet plate 27 disposed at the bottom of the second electrode 25 has an irregular shape. Is blown from the plurality of first and second gas blowing holes 30 and 31 toward the substrate 32 on the first electrode 23, and plasma is generated between the substrate 32 and the second electrode 25 to form a film. You.
【００５５】前記成膜工程において、前記第１電極２３
に内蔵したヒータによる基板のシリコン堆積部の温度は
ガラス等の安価な基板の使用を可能にする５５０℃以下
とすることが好ましい。In the film forming step, the first electrode 23
It is preferable that the temperature of the silicon deposition portion of the substrate by the heater built in is set to 550 ° C. or lower which enables the use of an inexpensive substrate such as glass.
【００５６】前記成膜工程において、前記反応容器２１
内の圧力を５Ｔｏｒｒ以上の高い圧力にすることが好ま
しい。このような条件に設定することにより、前記基板
３２表面に成膜される結晶質シリコン薄膜へのイオンダ
メージを低減することが可能になる。その結果、成膜速
度を速めるために高周波パワーを高く（例えばプラズマ
放電電力密度が１００ｍＷ／ｃｍ2以上）したり、ガス
流量を増加させても、成膜中の薄膜表面へのイオンダメ
ージを低減して結晶質シリコン系薄膜光電変換層を高速
度で成膜することが可能になる。また、高圧力にするこ
とによって、結晶粒界や粒内の欠陥が水素でパッシベー
ションされ易くなるため、それらに起因する結晶質シリ
コン系薄膜への欠陥密度を減少させることが可能にな
る。より好ましい前記反応容器２１内の圧力は５〜２０
Ｔｏｒｒである。In the film forming step, the reaction vessel 21
It is preferable to set the internal pressure to a high pressure of 5 Torr or more. By setting such conditions, ion damage to the crystalline silicon thin film formed on the surface of the substrate 32 can be reduced. As a result, even if the high-frequency power is increased (for example, the plasma discharge power density is 100 mW / cm 2 or more) or the gas flow rate is increased in order to increase the deposition rate, ion damage to the thin film surface during deposition is reduced. As a result, a crystalline silicon-based thin film photoelectric conversion layer can be formed at a high speed. Further, by setting the pressure to a high pressure, the crystal grain boundaries and the defects in the grains are easily passivated by hydrogen, so that the defect density in the crystalline silicon-based thin film due to these can be reduced. More preferably, the pressure in the reaction vessel 21 is 5-20.
Torr.
【００５７】前記成膜工程において、前記第１電極２３
とこの電極２３に近接する前記第２電極２５のガス吹き
出し板２７との間の距離は１．５ｃｍ以下にすることが
好ましい。このように前記第１電極２３と前記第２電極
２５のガス吹き出し板２７間の距離を１．５ｃｍ以下と
短くすることにより、前記反応容器２１内の圧力を５Ｔ
ｏｒｒ以上にしても前述したように前記第１電極２３の
基板３２と第２電極２５の間にプラズマ３３を安定して
生成できる。In the film forming step, the first electrode 23
It is preferable that the distance between the second electrode 25 and the gas blowing plate 27 in the vicinity of the electrode 23 be 1.5 cm or less. As described above, by reducing the distance between the first electrode 23 and the gas blowing plate 27 of the second electrode 25 to 1.5 cm or less, the pressure in the reaction vessel 21 is reduced to 5T.
Even at orr or more, the plasma 33 can be stably generated between the substrate 32 of the first electrode 23 and the second electrode 25 as described above.
【００５８】前記シラン系ガスとしては、例えばモノシ
ラン、ジシラン等が好ましいが、これらに加えて四フッ
化ケイ素、四塩化ケイ素、ジクロルシラン等のハロゲン
化ケイ素ガスを用いてもよい。このようなシラン系ガス
に加えて希ガス等の不活性ガス、好ましくはヘリウム、
ネオン、アルゴン等を用いもよい。As the silane-based gas, for example, monosilane, disilane and the like are preferable. In addition, silicon halide gas such as silicon tetrafluoride, silicon tetrachloride and dichlorosilane may be used. In addition to such a silane-based gas, an inert gas such as a rare gas, preferably helium,
Neon, argon, or the like may be used.
【００５９】前記成膜工程において、前記反応容器２１
内に導入される全反応ガス（シラン系ガスと水素ガスを
含む）に含まれるシラン系ガスに対する水素ガスの流量
比は１００倍以上にすることが好ましい。このように全
反応ガスに含まれるシラン系ガスに対する水素ガスの流
量比を１００倍以上にすることによって、活性化された
水素のエッチング作用等によって、低品位で剥離し易い
結晶質シリコンが反応場である膜堆積部以外に領域に堆
積されのを防ぐことが可能になる。In the film forming step, the reaction vessel 21
The flow rate ratio of the hydrogen gas to the silane-based gas contained in all the reaction gases (including the silane-based gas and the hydrogen gas) introduced therein is preferably 100 times or more. By setting the flow rate ratio of the hydrogen gas to the silane-based gas contained in the total reaction gas to be 100 times or more, crystalline silicon that is low in quality and easily peeled off due to the activated hydrogen etching action or the like is formed in the reaction field. Therefore, it is possible to prevent deposition in a region other than the film deposition portion.
【００６０】前記成膜工程において、プラズマ放電電力
密度を１００ｍＷ／ｃｍ2以上にすることが好ましい。In the film forming step, the plasma discharge power density is preferably set to 100 mW / cm 2 or more.
【００６１】このような図１〜図３に示すプラズマＣＶ
Ｄ装置を用いて、シラン系ガスと水素ガスを含む反応ガ
スをガス供給管２６を通して中空状の第２電極２５に供
給し、その底部に配置されたガス吹き出し板２７の互い
に異形の複数の第１、第２のガス吹き出し穴３０，３１
から前記第１電極２３上の基板３２に向けて吹き出すと
共に、前記第２電極２５に例えば高周波電力を印加する
ことによって、前述したように前記ガス吹き出し板２７
の平坦な面積を実効的に減少させることができる。この
ため、反応ガスを前記ガス吹き出し板２７に開口された
第１、第２のガス吹き出し穴３０，３１から第１電極２
３上の基板３２に向けて吹き出すと共に、前記第２電極
２５に例えば高周波電力を印加して主に前記ガス吹き出
し板２７と前記基板３２の間にプラズマ３３を生成する
際、前記ガス吹き出し板２７の平坦な面積を実効的に減
少させることにより、そのガス吹き出し板２７の平坦部
にパウダーのような反応ガスの生成物が付着して成長す
るのを抑制することができる。その結果、成膜中に第２
電極２５のガス吹き出し板２７から前記パウダーが剥
離、落下して前記第１電極２３上に載置した基板３２
（１０１）の一導電型半導体の薄膜に付着するのを抑制
できる。したがって、パウダーの付着に起因する結晶質
シリコン系薄膜光電変換層の膜質劣化、そのパウダー付
着部での異常成膜による結晶質シリコン系薄膜光電変換
層の膜厚の不均一化を防止できる。The plasma CV shown in FIGS.
Using a D apparatus, a reaction gas containing a silane-based gas and a hydrogen gas is supplied to a hollow second electrode 25 through a gas supply pipe 26, and a plurality of irregularly shaped first gas discharge plates 27 arranged at the bottom of the second electrode 25 are provided. 1. Second gas outlet holes 30, 31
Is blown out toward the substrate 32 on the first electrode 23 and, for example, high-frequency power is applied to the second electrode 25, so that the gas
Can be effectively reduced. For this reason, the reaction gas is supplied from the first and second gas blowout holes 30 and 31 opened in the gas blowout plate 27 to the first electrode 2.
When the plasma is generated between the gas blow-out plate 27 and the substrate 32 by applying, for example, high-frequency power to the second electrode 25 while blowing out the gas toward the substrate 32 on the By effectively reducing the flat area of the gas blowout plate, it is possible to suppress the reaction gas product such as powder from adhering to and growing on the flat portion of the gas blowing plate 27. As a result, the second
The powder is peeled off from the gas blowing plate 27 of the electrode 25, dropped, and the substrate 32 placed on the first electrode 23.
(101) Adhesion to a thin film of one conductivity type semiconductor can be suppressed. Therefore, it is possible to prevent deterioration of the film quality of the crystalline silicon-based thin film photoelectric conversion layer due to the adhesion of the powder and nonuniformity of the film thickness of the crystalline silicon-based thin film photoelectric conversion layer due to abnormal film formation at the portion where the powder is attached.
【００６２】また、前記第２電極２５のガス吹き出し板
２７へのパウダー付着を抑制できることによって、クリ
ーニングの頻度を減少でき、実効的な稼動時間を長くで
きるため、シリコン系薄膜光電変換装置の生産性を向上
できる。Further, since the powder adhesion of the second electrode 25 to the gas blowing plate 27 can be suppressed, the frequency of cleaning can be reduced and the effective operation time can be lengthened, so that the productivity of the silicon-based thin film photoelectric conversion device can be improved. Can be improved.
【００６３】さらに、前記中空状の第２電極２５の前記
第１電極２３との対向するガス吹き出し板２７に複数の
第１、第２のガス吹き出し穴３０，３１を開口すること
によって、従来のＣＶＤ装置に比べてガスの吹き出し箇
所を増加できるため、前記ガス吹き出し板２７と前記基
板３２のガス分布を均一化できる。その結果、前記ガス
吹き出し板２７と前記基板３２の間にプラズマ３３を生
成することによって、基板３２（１０１）の一導電型半
導体の表面全体に均一な膜厚を有する高品位の結晶質シ
リコン系薄膜光電変換層を成膜することができる。Further, a plurality of first and second gas blowout holes 30 and 31 are formed in the gas blowout plate 27 of the hollow second electrode 25 facing the first electrode 23, so that a conventional gas blowout hole is formed. Since the number of gas blowing locations can be increased as compared with the CVD apparatus, the gas distribution on the gas blowing plate 27 and the substrate 32 can be made uniform. As a result, a plasma 33 is generated between the gas blow-out plate 27 and the substrate 32, thereby forming a high-quality crystalline silicon-based material having a uniform film thickness over the entire surface of the one conductivity type semiconductor of the substrate 32 (101). A thin film photoelectric conversion layer can be formed.
【００６４】なお、プラズマＣＶＤ装置は図１〜図３に
示す構造に限らず、前述した図４または図５に示すプラ
ズマＣＶＤ装置を用いても成膜中に第２電極２５のガス
吹き出し板２７から前記パウダーが剥離、落下して前記
第１電極２３上に載置した基板３２（１０１）の一導電
型半導体の薄膜に付着するのを抑制して、パウダーの付
着に起因する結晶質シリコン系薄膜光電変換層の膜質劣
化、そのパウダー付着部での異常成膜による結晶質シリ
コン系薄膜光電変換層の膜厚の不均一化を防止できる。The plasma CVD apparatus is not limited to the structure shown in FIGS. 1 to 3, and the gas blowout plate 27 of the second electrode 25 can be formed during the film formation by using the plasma CVD apparatus shown in FIG. 4 or FIG. Of the substrate 32 (101) placed on the first electrode 23 to prevent the powder from peeling and dropping from attaching to the thin film of the one-conductivity-type semiconductor. Deterioration of the film quality of the thin-film photoelectric conversion layer and non-uniformity of the film thickness of the crystalline silicon-based thin-film photoelectric conversion layer due to abnormal film formation at the powder attachment portion can be prevented.
【００６５】また、前述したように反応容器内の圧力を
５Ｔｏｒｒ以上の高い圧力にする条件の下で高周波パワ
ーを増大したり、反応ガスの流量を増加させて成膜速度
を向上するによって、膜成長初期における結晶核生成時
間を短くできるために相対的に核発生密度を減少でき、
大粒径で強く結晶配向した結晶粒を有する結晶質シリコ
ン系薄膜を形成することが可能になる。Further, as described above, under the condition that the pressure in the reaction vessel is set to a high pressure of 5 Torr or more, the high-frequency power is increased, or the flow rate of the reaction gas is increased to improve the film formation rate, thereby increasing the film formation rate. Since the crystal nucleation time in the initial stage of growth can be shortened, the nucleation density can be relatively reduced,
It is possible to form a crystalline silicon-based thin film having a crystal grain having a large grain size and strong crystal orientation.
【００６６】具体的には、結晶質シリコン系薄膜光電変
換層１０５はその中に含まれる結晶粒の多くが一導電型
半導体層（下地層）１０４から上方に柱状に延びて成長
される。これらの多くの結晶粒は膜面に平行に（１１
０）の優先結晶配向面を有し、そのＸ線回折で求めた
（２２０）回折ピークに対する（１１１）回折ピークの
強度比は２／５以下、より好ましくは１／１０以下であ
ることが望ましい。More specifically, the crystalline silicon-based thin-film photoelectric conversion layer 105 is grown such that many of the crystal grains contained therein extend upward from the one-conductivity-type semiconductor layer (base layer) 104 in a columnar manner. Many of these grains are parallel to the film plane (11
0), and the intensity ratio of the (111) diffraction peak to the (220) diffraction peak determined by X-ray diffraction is preferably 2/5 or less, more preferably 1/10 or less. .
【００６７】さらに、前記成膜工程において前記基板の
シリコン堆積部（一導電型半導体層）の温度を１００〜
４００℃に設定することにより、０．１原子％以上で２
０原子％以下の水素を含む多結晶シリコンまたは体積結
晶化分率８０％以上の微結晶シリコンからなる結晶質シ
リコン系薄膜光電変換層を形成することが可能になる。Further, in the film forming step, the temperature of the silicon deposition portion (one conductivity type semiconductor layer) of the substrate is set to 100 to 100.
By setting the temperature at 400 ° C., 2
This makes it possible to form a crystalline silicon-based thin-film photoelectric conversion layer made of polycrystalline silicon containing 0 atomic% or less of hydrogen or microcrystalline silicon having a volume crystallization fraction of 80% or more.
【００６８】なお、結晶質シリコン系薄膜光電変換層は
０．５〜１０μｍの厚さを有することが好ましい。The crystalline silicon-based thin-film photoelectric conversion layer preferably has a thickness of 0.5 to 10 μm.
【００６９】また、下地層である一導電型層１０４の表
面形状が実質的に平面である場合でも、光電変換層１０
５の形成後のその表面にはその膜厚よりも約１桁ほど小
さい間隔の微細な凹凸を有する表面テクスチャ構造が形
成される。Further, even when the surface shape of the one-conductivity-type layer 104 as the underlayer is substantially flat, the photoelectric conversion layer 10
After the formation of 5, a surface texture structure having fine irregularities at intervals of about one digit smaller than the film thickness is formed on the surface.
【００７０】３）逆導電型半導体層１０６ この逆導電型半導体層１０６としては、例えば導電型決
定不純物原子であるボロンが０．０１原子％以上ドープ
されたｐ型シリコン薄膜、またはリンが０．０１原子％
以上ドープされたｎ型シリコン薄膜などが用いられ得
る。ただし、逆導電型半導体層１０６についてのこれら
の条件は限定的なものではない。不純物原子としては、
例えばｐ型シリコンにおいてはアルミニウム等でもよ
く、またシリコンカーバイドやシリコンゲルマニウム等
の合金材料の膜を用いてもよい。この逆導電極シリコン
系薄膜１０６は、多結晶、微結晶または非晶質のいずれ
でもよく、その膜厚は３〜１００ｎｍの範囲内に設定さ
れ、より好ましくは５〜５０ｎｍの範囲内に設定され
る。3) Reverse conductivity type semiconductor layer 106 As the reverse conductivity type semiconductor layer 106, for example, a p-type silicon thin film doped with 0.01% by atom or more of boron, which is a conductivity type determining impurity atom, or 0.1% phosphorus. 01 atomic%
An n-type silicon thin film doped as described above may be used. However, these conditions for the opposite conductivity type semiconductor layer 106 are not limited. As impurity atoms,
For example, in the case of p-type silicon, aluminum or the like may be used, or a film of an alloy material such as silicon carbide or silicon germanium may be used. The reverse conductive silicon-based thin film 106 may be polycrystalline, microcrystalline, or amorphous, and has a thickness in the range of 3 to 100 nm, more preferably in the range of 5 to 50 nm. You.
【００７１】（第３工程）次いで、前記光電変換ユニッ
ト１１１上に透明導電性酸化膜１０７、櫛形状の金属電
極１０８を順次形成することにより図６に示す構造の光
電変換装置を製造する。(Third Step) Then, a transparent conductive oxide film 107 and a comb-shaped metal electrode 108 are sequentially formed on the photoelectric conversion unit 111 to manufacture a photoelectric conversion device having a structure shown in FIG.
【００７２】前記透明導電性酸化膜１０７は、例えばＩ
ＴＯ，ＳｎＯ2，ＺｎＯ等から選択された少なくとも１
以上の層から形成される。The transparent conductive oxide film 107 is made of, for example, I
At least one selected from TO, SnO 2 , ZnO, etc.
It is formed from the above layers.
【００７３】前記櫛形状の金属電極１０８（グリッド電
極）は、例えばＡｌ，Ａｇ，Ａｕ，Ｃｕ，Ｐｔ等から選
択された少なくとも１以上の金属またはこれらの合金の
層をパターニングすることにより形成される。これらの
金属もしくは合金の層は、例えばスパッタリング法また
は蒸着法によって成膜される。The comb-shaped metal electrode 108 (grid electrode) is formed by patterning a layer of at least one metal selected from, for example, Al, Ag, Au, Cu, Pt, or an alloy thereof. . These metal or alloy layers are formed by, for example, a sputtering method or an evaporation method.
【００７４】このような方法で製造された図６に示す光
電変換装置において、光１０９は前記透明導電性酸化膜
１０７に入射されて光電変換がなされ、前記裏面電極１
１０の例えば金属薄膜１０２および前記金属電極１０８
の端子間から出力される。In the photoelectric conversion device shown in FIG. 6 manufactured by such a method, the light 109 is incident on the transparent conductive oxide film 107 to perform photoelectric conversion, and
10 of the metal thin film 102 and the metal electrode 108
Are output between the terminals.
【００７５】なお、図６ではシリコン系薄膜光電変換装
置の１つを例示しているだけであって、本発明は図６に
示すシリコン結晶質光電変換層を含む少なくとも１つの
結晶系薄膜光電変換ユニットに加えて、周知の方法で形
成される非晶質光電変換層を含む少なくとももう１つの
非晶質系薄膜光電変換ユニットをも含むタンデム型光電
変換装置、または１つ以上の非晶質系薄膜光電変換ユニ
ットを有する光電変換装置にも適用することが可能であ
る。FIG. 6 illustrates only one of the silicon-based thin film photoelectric conversion devices, and the present invention provides at least one crystalline thin film photoelectric conversion device including the silicon crystalline photoelectric conversion layer shown in FIG. A tandem-type photoelectric conversion device including, in addition to the unit, at least another amorphous-based thin-film photoelectric conversion unit including an amorphous photoelectric conversion layer formed by a known method, or one or more amorphous-based photoelectric conversion devices The present invention can be applied to a photoelectric conversion device having a thin film photoelectric conversion unit.
【００７６】以上述べた本発明によれば、シリコン系薄
膜光電変換装置の一連の製造工程のうちで、スループッ
トを向上させる結晶質シリコン系光電変換層をプラズマ
ＣＶＤ装置により成膜する際、その第２電極のガス吹き
出し板へのパウダー付着を抑制してクリーニング頻度を
低減しつつ、前記ガス吹き出し板のパウダーが剥離、落
下して前記結晶質シリコン系光電変換層の下地層に付着
するのを抑制してその光電変換層の膜質劣化、異常成長
を防止できるため、シリコン系薄膜光電変換装置の高性
能化と低コスト化に大きく貢献することができる。According to the present invention described above, in a series of manufacturing processes of a silicon-based thin film photoelectric conversion device, when a crystalline silicon-based photoelectric conversion layer for improving throughput is formed by a plasma CVD device, The powder of the gas blowing plate is prevented from peeling and falling and adhering to the underlying layer of the crystalline silicon-based photoelectric conversion layer while suppressing the powder adhesion to the gas blowing plate of the two electrodes and reducing the cleaning frequency. In addition, since deterioration and abnormal growth of the photoelectric conversion layer can be prevented, it is possible to greatly contribute to higher performance and lower cost of the silicon-based thin film photoelectric conversion device.
【００７７】[0077]
【実施例】以下、本発明に係わる好ましい実施例を参考
例と対比して詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments according to the present invention will be described in detail below in comparison with a reference example.
【００７８】（参考例１）前述した図６の実施の形態に
類似して、参考例１としての結晶質シリコン薄膜太陽電
池を製造した。Reference Example 1 A crystalline silicon thin-film solar cell as Reference Example 1 was manufactured in a manner similar to the embodiment of FIG.
【００７９】まず、長さ１２６ｍｍ、幅１２６ｍｍ、厚
さ１．１ｍｍの寸法のガラス基板１０１上に裏面電極１
１０として、厚さ３００ｎｍのＡｇ膜１０２と厚さ１０
０ｎｍのＺｎＯ膜１０３のそれぞれがスパッタリング法
によって順次形成した。裏面電極１１０上に厚さ１０ｎ
ｍでリンドープされたｎ型微結晶シリコン層１０４、厚
さ３μｍでノンドープの多結晶シリコン薄膜光電変換層
１０５、および厚さ１０ｎｍでボロンドープされたｐ型
微結晶シリコン層１０６をそれぞれプラズマＣＶＤ法に
より成膜し、ｎｉｐ光電変換ユニット１１１を形成し
た。光電変換ユニット１１１上に前面電極１０７とし
て、厚さ８０ｎｍの透明導電性ＩＴＯ膜をスパッタリン
グ法にて堆積し、その上に電流取出のための櫛形Ａｇ電
極１０８を蒸着法およびパターニング技術により形成し
た。First, the back electrode 1 was placed on a glass substrate 101 having dimensions of 126 mm in length, 126 mm in width and 1.1 mm in thickness.
10 is an Ag film 102 having a thickness of 300 nm and a thickness of 10
Each of the 0 nm ZnO films 103 was sequentially formed by a sputtering method. 10n thickness on back electrode 110
An n-type microcrystalline silicon layer 104 doped with m, phosphorus, a non-doped polycrystalline silicon thin film photoelectric conversion layer 105 having a thickness of 3 μm, and a p-type microcrystalline silicon layer 106 having a thickness of 10 nm doped with boron are formed by a plasma CVD method. The film was formed to form a nip photoelectric conversion unit 111. A transparent conductive ITO film having a thickness of 80 nm was deposited as a front electrode 107 on the photoelectric conversion unit 111 by a sputtering method, and a comb-shaped Ag electrode 108 for extracting a current was formed thereon by a vapor deposition method and a patterning technique.
【００８０】前記ｎ型微結晶シリコン層１０４は、ＲＦ
プラズマＣＶＤ法によって堆積した。このときに用いら
れた反応ガスの流量は、シランが５．０ｓｃｃｍ、水素
が２００ｓｃｃｍ、ホスフィンが０．０５ｓｃｃｍであ
った。また、反応容器内の圧力は１Ｔｏｒｒにし、ＲＦ
パワー密度を３０ｍＷ／ｃｍ2に設定した。The n-type microcrystalline silicon layer 104 is made of RF
It was deposited by a plasma CVD method. The flow rates of the reaction gas used at this time were 5.0 sccm for silane, 200 sccm for hydrogen, and 0.05 sccm for phosphine. The pressure inside the reaction vessel was set to 1 Torr, and RF
The power density was set at 30 mW / cm 2 .
【００８１】前記光電変換層１０５は、４００℃の基板
温度と５Ｔｏｒｒの反応容器内圧力の下にプラズマＣＶ
Ｄ法により形成した。このとき用いられた第２電極は第
１電極との対向面に直径０．５ｍｍの拡口穴を有するガ
ス吹き出し穴が１ｃｍの間隔でガス吹き出し板に設けら
れ、基板を保持する第１電極との距離を１．５ｃｍに設
定した。前記第２電極のガス吹き出し穴から吹出された
反応ガスにおいて、シラン／水素の流量比を１／１２０
とし、放電パワーを１２０ｍＷ／ｃｍ2に設定した。The photoelectric conversion layer 105 is formed by applying a plasma CV under a substrate temperature of 400 ° C. and a pressure in the reaction vessel of 5 Torr.
Formed by Method D. In the second electrode used at this time, a gas blowing hole having an opening having a diameter of 0.5 mm was provided on the gas blowing plate at an interval of 1 cm on a surface facing the first electrode, and the first electrode holding the substrate and Was set to 1.5 cm. In the reaction gas blown out from the gas blowout hole of the second electrode, the flow ratio of silane / hydrogen is set to 1/120.
And the discharge power was set to 120 mW / cm 2 .
【００８２】このような条件の下において、光電変換層
１０５の成膜速度は１．４μｍ／ｈであった。得られた
光電変換層１０５において、Ｘ線回折の（２２０）回折
ピークに対する（１１１）回折ピークの強度比は１／１
０であり、水素含有量は１．６原子％であった。Under these conditions, the film formation rate of the photoelectric conversion layer 105 was 1.4 μm / h. In the obtained photoelectric conversion layer 105, the intensity ratio of the (111) diffraction peak to the (220) diffraction peak of X-ray diffraction was 1/1.
0 and the hydrogen content was 1.6 atomic%.
【００８３】前記ｐ型微結晶シリコン層１０６のプラズ
マＣＶＤにおいては、反応ガスの流量をシランが１．０
ｓｃｃｍ、水素が５００ｓｃｃｍ、ジボランが０．０１
ｓｃｃｍとした。また、反応容器内の圧力を１Ｔｏｒｒ
にし、ＲＦパワー密度を１５０ｍＷ／ｃｍ2に設定し
た。In the plasma CVD of the p-type microcrystalline silicon layer 106, the flow rate of the
sccm, hydrogen 500 sccm, diborane 0.01
sccm. Further, the pressure in the reaction vessel is set to 1 Torr.
And the RF power density was set to 150 mW / cm 2 .
【００８４】このようにして得られた参考例１の太陽電
池において、図６に示す入射光１０９としてＡＭ１．５
の光を１００ｍＷ／ｃｍ2の光量で照射したときの出力
特性を調べた。その結果、開放端電圧が０．５２０Ｖ、
短絡電流密度が２７．４ｍＡ／ｃｍ2、曲線因子が７
５．１％、変換効率が１０．７％であった。In the solar cell of Reference Example 1 thus obtained, the incident light 109 shown in FIG.
Was irradiated at a light amount of 100 mW / cm 2 . As a result, the open-end voltage is 0.520V,
Short-circuit current density is 27.4 mA / cm 2 and fill factor is 7
The conversion efficiency was 5.1% and the conversion efficiency was 10.7%.
【００８５】また、前記プラズマＣＶＤ装置により前述
したのと同様な条件の下で光電変換層１０５を連続して
成膜し、１５０時間経過（約２１０μｍの成膜に相当）
後に成膜した光電変換層１０５を有する太陽電池につい
て、入射光１０９としてＡＭ１．５の光を１００ｍＷ／
ｃｍ2の光量で照射したときの出力特性を調べた。その
結果、開放端電圧が０．４１１Ｖ、短絡電流密度が２
０．３ｍＡ／ｃｍ2、曲線因子が５２．３％、変換効率
が５．３％であった。このように従来のプラズマＣＶＤ
装置を連続的に稼動して成膜された光電変換層１０５を
有する太陽電池において、前記出力特性が低下するのは
その装置の上部側に配置した中空状の第２電極における
ガス吹き出し板に反応ガスの生成物であるパウダーが付
着し、このパウダーが剥離、落下して下部側の第１電極
上の基板の下地層（ｎ型微結晶シリコン層１０４）に付
着し、この下地層に成膜される光電変換層１０５の膜質
等を劣化させたためである。Further, the photoelectric conversion layer 105 is continuously formed by the plasma CVD apparatus under the same conditions as described above, and 150 hours elapse (corresponding to a film formation of about 210 μm).
Regarding the solar cell having the photoelectric conversion layer 105 formed later, light of AM1.5 was applied as the incident light 109 at 100 mW /
Output characteristics when irradiated with a light amount of cm 2 were examined. As a result, the open-circuit voltage was 0.411 V and the short-circuit current density was 2
0.3 mA / cm 2 , fill factor was 52.3%, and conversion efficiency was 5.3%. Thus, the conventional plasma CVD
In the solar cell having the photoelectric conversion layer 105 formed by continuously operating the device, the output characteristic is deteriorated due to the reaction with the gas blowing plate in the hollow second electrode disposed on the upper side of the device. Powder, which is a product of gas, adheres, and the powder peels off, falls, and adheres to the underlying layer (n-type microcrystalline silicon layer 104) of the substrate on the lower first electrode, and forms a film on this underlying layer. This is because the film quality or the like of the photoelectric conversion layer 105 is deteriorated.
【００８６】（実施例１）光電変換層１０５のプラズマ
ＣＶＤ装置として以下に説明するもの用いた以外、参考
例１と同じ条件の下で太陽電池を製造した。Example 1 A solar cell was manufactured under the same conditions as in Reference Example 1, except that a plasma CVD apparatus for the photoelectric conversion layer 105 was used as described below.
【００８７】すなわち、実施例１においては前述した図
１〜図３に示す構造のプラズマＣＶＤ装置を用い、第１
電極３と対向する前面にガス吹き出し板２７を有する中
空状の第２電極２５が配置され、このガス吹き出し板２
７上に直径０．５ｍｍの拡口穴２８を有する第１ガス吹
き出し穴３０を１ｃｍの間隔で開口するとともに、これ
ら第１ガス吹き出し穴３０間に図３に示すように直径１
の円柱状第２ガス吹き出し穴３１を開口した構造を有す
る。That is, in the first embodiment, the first plasma CVD apparatus having the structure shown in FIGS.
A hollow second electrode 25 having a gas blowing plate 27 on the front surface facing the electrode 3 is disposed.
A first gas outlet 30 having an opening 28 with a diameter of 0.5 mm is opened at intervals of 1 cm on the nozzle 7, and the first gas outlet 30 has a diameter of 1 mm between the first gas outlets 30 as shown in FIG.
Has a structure in which the cylindrical second gas blowing hole 31 is opened.
【００８８】このようプラズマＣＶＤにおいて、光電変
換層１０５の成膜速度は３．０μｍ／ｈであった。In the plasma CVD, the film formation rate of the photoelectric conversion layer 105 was 3.0 μm / h.
【００８９】得られた光電変換層１０５において、Ｘ線
回折の（２２０）回折ピークに対する（１１１）回折ピ
ークの強度比は１／１０であり、水素含有量は１．３原
子％であった。In the obtained photoelectric conversion layer 105, the intensity ratio of the (111) diffraction peak to the (220) diffraction peak in X-ray diffraction was 1/10, and the hydrogen content was 1.3 atomic%.
【００９０】この実施例１の太陽電池において、図６に
示す入射光１０９としてＡＭ１．５の光を１００ｍＷ／
ｃｍ2の光量で照射したときの出力特性を調べた。その
結果、開放端電圧が０．５１９Ｖ、短絡電流密度が２
７．２ｍＡ／ｃｍ2、曲線因子が７４．８％、変換効率
が１０．５％であった。In the solar cell of the first embodiment, the incident light 109 shown in FIG.
Output characteristics when irradiated with a light amount of cm 2 were examined. As a result, the open-circuit voltage was 0.519 V and the short-circuit current density was 2
7.2 mA / cm 2 , fill factor was 74.8%, and conversion efficiency was 10.5%.
【００９１】また、前記プラズマＣＶＤ装置により前述
したのと同様な条件の下で光電変換層１０５を連続して
成膜し、８０時間経過（約２４０μｍの成膜に相当）後
に成膜した光電変換層１０５を有する太陽電池につい
て、入射光１０９としてＡＭ１．５の光を１００ｍＷ／
ｃｍ2の光量で照射したときの出力特性を調べた。その
結果、開放端電圧が０．５２０Ｖ、短絡電流密度が２
７．０ｍＡ／ｃｍ2、曲線因子が７４．４％、変換効率
が１０．４％であった。この結果から、連続成膜後の光
電変換層１０５を有する太陽電池においても初期に成膜
された光電変換層１０５を有する太陽電池とほぼ同様な
出力特性を示すことがわかる。The photoelectric conversion layer 105 was continuously formed by the plasma CVD apparatus under the same conditions as described above, and after 80 hours (corresponding to a film formation of about 240 μm). Regarding the solar cell having the layer 105, the light of AM1.5 was applied as the incident light 109 at 100 mW /
Output characteristics when irradiated with a light amount of cm 2 were examined. As a result, the open-circuit voltage was 0.520 V and the short-circuit current density was 2
7.0 mA / cm 2 , fill factor was 74.4%, and conversion efficiency was 10.4%. From this result, it is understood that the solar cell having the photoelectric conversion layer 105 after the continuous film formation has almost the same output characteristics as the solar cell having the photoelectric conversion layer 105 formed in the initial stage.
【００９２】なお、図１〜図３に示す構造のプラズマＣ
ＶＤ装置の代わりに図４または図５に示す構造のプラズ
マＣＶＤ装置を用いても実施例１とほぼ同様な結果が得
られた。The plasma C having the structure shown in FIGS.
Even when a plasma CVD apparatus having the structure shown in FIG. 4 or 5 was used instead of the VD apparatus, substantially the same results as in Example 1 were obtained.
【００９３】[0093]
【発明の効果】以上詳述したように本発明によれば、成
膜中に第２電極のガス吹き出し板へのパウダー付着を抑
制してクリーニング頻度を低減しつつ、前記ガス吹き出
し板のパウダーが剥離、落下して第１電極の基板または
成膜途中の薄膜に付着するのを抑制して薄膜の膜質劣
化、異常成長を防止できるため、太陽電池の光電変換装
置、液晶表示装置等の膜形成に有効に適用することが可
能なプラズマＣＶＤ装置を提供できる。As described above in detail, according to the present invention, the powder of the gas blow-out plate is reduced while the frequency of cleaning is reduced by suppressing the powder from adhering to the gas blow-out plate during film formation. Since the film quality of the thin film can be prevented from deteriorating and abnormally growing by preventing the film from peeling and dropping and adhering to the substrate of the first electrode or the thin film being formed, the formation of a film for a photoelectric conversion device of a solar cell, a liquid crystal display device, etc. And a plasma CVD apparatus that can be effectively applied to the present invention.
【００９４】本発明は、安価な基板上にシリコン系光電
変換層を有する光電変換ユニットを積層する際、前記プ
ラズマＣＶＤ装置を用いて高品位のシリコン系光電変換
層を成膜して製造工程のスループットの向上および性能
改善を達成したシリコン系薄膜光電変換装置の製造方法
を提供できる。According to the present invention, when a photoelectric conversion unit having a silicon-based photoelectric conversion layer is laminated on an inexpensive substrate, a high-quality silicon-based photoelectric conversion layer is formed using the plasma CVD apparatus, and the manufacturing process is performed. A method for manufacturing a silicon-based thin-film photoelectric conversion device that achieves an improvement in throughput and an improvement in performance can be provided.
【図１】本発明に係わるプラズマＣＶＤ装置を示す概略
図。FIG. 1 is a schematic view showing a plasma CVD apparatus according to the present invention.
【図２】図１のプラズマＣＶＤ装置の要部断面図。FIG. 2 is a sectional view of a main part of the plasma CVD apparatus of FIG.
【図３】図２のIII−III矢視図。FIG. 3 is a view taken in the direction of arrows III-III in FIG. 2;
【図４】本発明に係わる別のプラズマＣＶＤ装置の要部
断面図。FIG. 4 is a cross-sectional view of a main part of another plasma CVD apparatus according to the present invention.
【図５】本発明に係わるさらに別のプラズマＣＶＤ装置
の要部断面図。FIG. 5 is a cross-sectional view of a main part of still another plasma CVD apparatus according to the present invention.
【図６】本発明の１つの実施の形態により製造されるシ
リコン系薄膜光電変換装置を模式的に示す斜視図。FIG. 6 is a perspective view schematically showing a silicon-based thin-film photoelectric conversion device manufactured according to one embodiment of the present invention.
【図７】従来のプラズマＣＶＤ装置を示す概略図。FIG. 7 is a schematic view showing a conventional plasma CVD apparatus.
【図８】図７のプラズマＣＶＤ装置の要部断面図。FIG. 8 is a sectional view of a main part of the plasma CVD apparatus of FIG. 7;
２１…反応容器、 ２２…排気管、 ２３…第１電極、 ２５…第２電極、 ２７…ガス吹き出し板、 ３０，３１、３６，３８…ガス吹き出し穴、 ３２…基板、 ３３…プラズマ、 ３７，３９…凹部、 １０２…Ａｇ等の薄膜、 １０３…ＺｎＯ等の薄膜 １０４…一導電型半導体層、 １０５…結晶質シリコン系光電変換層、 １０６…逆導電型半導体層、 １０７…ＩＴＯ等の透明導電膜、 １１０…裏面電極、 １１１…結晶質シリコン系光電変換ユニット。 DESCRIPTION OF SYMBOLS 21 ... Reaction container, 22 ... Exhaust pipe, 23 ... 1st electrode, 25 ... 2nd electrode, 27 ... Gas blowing plate, 30, 31, 36, 38 ... Gas blowing hole, 32 ... Substrate, 33 ... Plasma, 37, 39: recess, 102: thin film of Ag, etc. 103: thin film of ZnO, etc. 104: semiconductor layer of one conductivity type, 105: photoelectric conversion layer of crystalline silicon, 106: semiconductor layer of opposite conductivity type, 107: transparent conductive material of ITO, etc. Film: 110: back electrode; 111: crystalline silicon-based photoelectric conversion unit.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4K030 AA06 AA17 BA29 EA06 FA03 KA17 LA16 5F045 AA08 AB03 AC01 AD09 BB15 CA13 DP03 EF05 EF07 EF08 5F051 AA03 AA04 AA05 BA05 BA14 BA17 CA07 CA08 CA15 CA22 CA23 CA24 FA02 FA04 FA06 FA18 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4K030 AA06 AA17 BA29 EA06 FA03 KA17 LA16 5F045 AA08 AB03 AC01 AD09 BB15 CA13 DP03 EF05 EF07 EF08 5F051 AA03 AA04 AA05 BA05 BA14 BA17 CA07 CA08 CA15 CA22 CA23 FA24 FA02 FA04
Claims (3)
電極と、 前記反応容器内に前記第１電極に対向して配置された中
空状の第２電極と、 前記第２電極内に反応ガスを供給するためのガス供給手
段と、 前記第２電極に電力を印加するための電源とを具備し、 前記中空状の第２電極は、前記第１電極と対向する面に
多数の異形のガス吹き出し穴が開口されたガス吹き出し
板を有することを特徴とするプラズマＣＶＤ装置。A reaction container having an exhaust member; and a first container disposed in the reaction container and holding a substrate to be processed.
An electrode; a hollow second electrode disposed in the reaction vessel so as to face the first electrode; gas supply means for supplying a reaction gas into the second electrode; A power supply for applying electric power, wherein the hollow second electrode has a gas blowing plate in which a number of irregularly shaped gas blowing holes are opened on a surface facing the first electrode. Plasma CVD apparatus.
電極と、 前記反応容器内に前記第１電極に対向して配置された中
空状の第２電極と、 前記第２電極内に反応ガスを供給するためのガス供給手
段と、 前記第２電極に電力を印加するための電源とを具備し、 前記中空状の第２電極は、前記第１電極と対向する面に
複数のガス吹き出し穴が開口され、かつこれらガス吹き
出し穴間にこの穴と異なる寸法の複数の凹部が設けられ
たガス吹き出し板を有することを特徴とするプラズマＣ
ＶＤ装置。2. A reaction container having an exhaust member, a first container disposed in the reaction container and holding a substrate to be processed.
An electrode; a hollow second electrode disposed in the reaction vessel so as to face the first electrode; gas supply means for supplying a reaction gas into the second electrode; A power source for applying electric power, wherein the hollow second electrode has a plurality of gas blowing holes opened on a surface facing the first electrode, and is different from the holes between the gas blowing holes. A plasma C having a gas blowing plate provided with a plurality of concave portions having dimensions.
VD device.
電変換ユニットを含み、この光電変換ユニットはプラズ
マＣＶＤ法によって順次積層された一導電型半導体層
と、シリコン系薄膜光電変換層と、逆導電型半導体層と
を含むシリコン系薄膜光電変換装置を製造するに際し、 前記ユニットのうちのいずれかの層は、請求項１または
２記載のプラズマＣＶＤ装置の反応容器内の第１電極に
前記基板を保持するとともに、電源から中空状の第２電
極に電力を供給し、かつシラン系ガスと水素ガスを含む
反応ガスを前記中空状の第２電極におけるガス吹き出し
板のガス吹き出し穴を通して前記第１電極の基板に向け
て吹き出し、前記基板と前記第２電極間にプラズマを発
生させることにより成膜されることを特徴とするシリコ
ン系薄膜光電変換装置の製造方法。3. A photoelectric conversion unit including at least one photoelectric conversion unit formed on a substrate, wherein the photoelectric conversion unit includes a one-conductivity-type semiconductor layer, a silicon-based thin-film photoelectric conversion layer, and a reverse conductive layer that are sequentially stacked by a plasma CVD method. In manufacturing a silicon-based thin film photoelectric conversion device including a mold semiconductor layer, any one of the units is formed by attaching the substrate to a first electrode in a reaction vessel of the plasma CVD device according to claim 1 or 2. While holding, a power is supplied from a power supply to the hollow second electrode, and a reaction gas containing a silane-based gas and a hydrogen gas is passed through a gas blowing hole of a gas blowing plate in the hollow second electrode. A silicon-based thin-film photoelectric conversion device, which is formed by blowing toward a substrate and generating plasma between the substrate and the second electrode. The method of production.
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| JP27279999A JP4451946B2 (en) | 1999-09-27 | 1999-09-27 | Plasma CVD apparatus and method for manufacturing silicon-based thin film photoelectric conversion apparatus |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009228054A (en) * | 2008-03-21 | 2009-10-08 | Shimadzu Corp | Plasma electrode and plasma chemical vapor deposition system |
| US7741144B2 (en) | 2007-11-02 | 2010-06-22 | Applied Materials, Inc. | Plasma treatment between deposition processes |
| KR20110021652A (en) * | 2009-08-25 | 2011-03-04 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Method of manufacturing photoelectric conversion device |
| JP2011054950A (en) * | 2009-08-07 | 2011-03-17 | Semiconductor Energy Lab Co Ltd | Method for manufacturing microcrystalline semiconductor film and thin film transistor |
| US20120132366A1 (en) * | 2010-11-25 | 2012-05-31 | Industrial Technology Research Institute | Plasma processing apparatus |
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1999
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7741144B2 (en) | 2007-11-02 | 2010-06-22 | Applied Materials, Inc. | Plasma treatment between deposition processes |
| JP2009228054A (en) * | 2008-03-21 | 2009-10-08 | Shimadzu Corp | Plasma electrode and plasma chemical vapor deposition system |
| JP2011054950A (en) * | 2009-08-07 | 2011-03-17 | Semiconductor Energy Lab Co Ltd | Method for manufacturing microcrystalline semiconductor film and thin film transistor |
| KR20110021652A (en) * | 2009-08-25 | 2011-03-04 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Method of manufacturing photoelectric conversion device |
| JP2011071499A (en) * | 2009-08-25 | 2011-04-07 | Semiconductor Energy Lab Co Ltd | Method of manufacturing photoelectric converter |
| KR101722903B1 (en) * | 2009-08-25 | 2017-04-04 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Method of manufacturing photoelectric conversion device |
| US20120132366A1 (en) * | 2010-11-25 | 2012-05-31 | Industrial Technology Research Institute | Plasma processing apparatus |
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