JPH11145499A - Manufacturing silicon type thin-film photoelectric converter - Google Patents
Manufacturing silicon type thin-film photoelectric converterInfo
- Publication number
- JPH11145499A JPH11145499A JP9307093A JP30709397A JPH11145499A JP H11145499 A JPH11145499 A JP H11145499A JP 9307093 A JP9307093 A JP 9307093A JP 30709397 A JP30709397 A JP 30709397A JP H11145499 A JPH11145499 A JP H11145499A
- Authority
- JP
- Japan
- Prior art keywords
- photoelectric conversion
- film
- silicon
- gas
- conversion layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は薄膜光電変換装置の
製造方法に関し、特に、シリコン系薄膜光電変換装置の
低コスト化と性能改善に関するものである。なお、本明
細書において、「結晶質」と「微結晶」の用語は、部分
的にアモルファス状態を含むものをも意味するものとす
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a thin-film photoelectric conversion device, and more particularly to a method for reducing the cost and improving the performance of a silicon-based thin-film photoelectric conversion device. Note that in this specification, the terms “crystalline” and “microcrystal” also mean those partially including an amorphous state.
【０００２】[0002]
【従来の技術】薄膜光電変換装置の代表的なものとして
アモルファスシリコン系太陽電池があり、アモルファス
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法によって形成されるので、ガラス，ス
テンレス，有機フィルム等の安価な基板上に形成するこ
とができ、低コストの光電変換装置のための有力材料と
して期待されている。また、アモルファスシリコンにお
いては可視光領域での吸収係数が大きいので、５００ｎ
ｍ以下の薄い膜厚のアモルファス光電変換層を用いた太
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 A typical example of a thin film photoelectric conversion device is an amorphous silicon solar cell. An amorphous photoelectric conversion material is usually formed by a plasma CVD method at a low film forming temperature of about 200 ° C. It can be formed on inexpensive substrates such as stainless steel, organic films and the like, and is expected as a promising material for low-cost photoelectric conversion devices. Since amorphous silicon has a large absorption coefficient in the visible light region,
A short circuit current of 15 mA / cm 2 or more has been realized in a solar cell using an amorphous photoelectric conversion layer having a thin film thickness of not more than m.
【０００３】しかし、アモルファスシリコン系材料で
は、Stebler-Wronskey効果と呼ばれるように、光電変換
特性が長期間の光照射によって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
度までである。したがって、アモルファスシリコン系材
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。[0003] However, amorphous silicon-based materials have a problem that the photoelectric conversion characteristics are deteriorated by long-term light irradiation, such as the Stebler-Wronskey effect, and the effective sensitivity wavelength region is about 800 nm. It is. Therefore, in a photoelectric conversion device using an amorphous silicon-based material, its reliability and high performance are limited, and the original advantages that the flexibility of substrate selection and the use of a low-cost process can be sufficiently achieved. Not alive.
【０００４】これに対して、近年では、たとえば多結晶
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さまざ
まな光電変換装置への応用が期待されている。On the other hand, in recent years, photoelectric conversion devices using thin films containing crystalline silicon such as polycrystalline silicon and microcrystalline silicon have been energetically 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.
【０００５】これらの結晶質シリコン薄膜の形成方法と
しては、たとえば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アモルフ
ァス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あるが、
いずれにしても前述のような安価な基板を用いるために
は５５０℃以下のプロセスで行なう必要がある。[0005] As a method for forming these crystalline silicon thin films, for example, thermal annealing or laser annealing is carried out after depositing an amorphous film once on a substrate by a CVD method or a sputtering method, or by depositing an amorphous film by a similar process. There is a method such as aiming for crystallization by
In any case, in order to use an inexpensive substrate as described above, it is necessary to perform the process at 550 ° C. or lower.
【０００６】そのようなプロセスの中でも、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膜が得ら
れるものと期待されている。このような手法で多結晶シ
リコン薄膜を得る場合、結晶質を含む高品質シリコン薄
膜を何らかのプロセスで一旦基板上に形成した後に、こ
れをシード層または結晶化制御層としてその上に成膜を
することによって、比較的低温でも良質の多結晶シリコ
ン薄膜が形成され得る。Among such processes, plasma C
The method of directly depositing a crystalline silicon thin film by the VD method is the easiest to lower the temperature of the process and increase the area of the thin film, and it is expected that a high-quality film can be obtained by a relatively simple process. . When a polycrystalline silicon thin film is obtained by such a method, a high-quality silicon thin film containing a crystalline material is once formed on a substrate by some process, and then formed as a seed layer or a crystallization control layer thereon. Thus, a high-quality polycrystalline silicon thin film can be formed even at a relatively low temperature.
【０００７】一方、水素でシラン系原料ガスを１０倍以
上希釈しかつプラズマ反応室内圧力を１０ｍＴｏｒｒ〜
１Ｔｏｒｒの範囲内に設定してプラズマＣＶＤ法で成膜
することによって、微結晶シリコン薄膜が得られること
はよく知られており、この場合には２００℃前後の温度
でもシリコン薄膜が容易に微結晶化され得る。たとえ
ば、微結晶シリコンのｐｉｎ接合からなる光電変換ユニ
ットを含む光電変換装置がAppl, Phys, Lett., Vol 65,
1994, p.860に記載されている。この光電変換ユニット
は、簡便にプラズマＣＶＤ法で順次積層されたｐ型半導
体層、光電変換層たるｉ型半導体層およびｎ型半導体層
からなり、これらの半導体層のすべてが微結晶シリコン
であることを特徴としている。ところが、高品質の結晶
質シリコン膜、さらには高性能のシリコン系薄膜光電変
換装置を得るためには、従来の製法や条件の下ではその
成膜速度が厚さ方向で１０ｎｍ／分に満たないほど遅
く、アモルファスシリコン膜の場合と同程度かもしくは
それ以下でしかない。On the other hand, the silane-based source gas is diluted 10 times or more with hydrogen and the pressure in the plasma reaction chamber is reduced to 10 mTorr or more.
It is well known that a microcrystalline silicon thin film can be obtained by forming a film by a plasma CVD method at a temperature within a range of 1 Torr. Can be For example, a photoelectric conversion device including a photoelectric conversion unit composed of a microcrystalline silicon pin junction is described in Appl, Phys, Lett., Vol 65,
1994, p.860. This photoelectric conversion unit is composed of a p-type semiconductor layer, an i-type semiconductor layer and an n-type semiconductor layer, which are simply stacked sequentially by a plasma CVD method, and all of these semiconductor layers are microcrystalline silicon. It is characterized by. However, in order to obtain a high-quality crystalline silicon film and a high-performance silicon-based thin-film photoelectric conversion device, the film formation rate is less than 10 nm / min in the thickness direction under conventional manufacturing methods and conditions. About the same as the amorphous silicon film or less.
【０００８】他方、低温プラズマＣＶＤ法で比較的高い
５Ｔｏｒｒの圧力条件の下でシリコン膜を形成した例
が、特開平４−１３７７２５に記載されている。しか
し、この事例はガラス等の基板上に直接シリコン薄膜を
堆積させたものであり、特開平４−１３７７２５に開示
された発明に対する比較例であって、その膜の品質は低
くて光電変換装置へ応用できるものではない。On the other hand, an example in which a silicon film is formed under a relatively high pressure of 5 Torr by a low-temperature plasma CVD method is described in JP-A-4-137725. However, in this case, a silicon thin film is directly deposited on a substrate such as glass, and this is a comparative example with respect to the invention disclosed in Japanese Patent Application Laid-Open No. 4-137725. It is not applicable.
【０００９】また、一般にプラズマＣＶＤ法の圧力条件
を高くすれば、プラズマ反応室内にパウダー状の生成物
やダストなどが大量に発生する。その場合、堆積中の膜
表面にそれらのダスト等が飛来して堆積膜中に取り込ま
れる危険性が高く、膜中のピンホールの発生原因とな
る。そして、そのような膜質の劣化を低減するために
は、反応室内のクリーニングを頻繁に行なわなければな
らなくなる。特に、５５０℃以下のような低温条件で成
膜する場合には、反応室圧力を高くした場合のこれらの
問題が顕著となる。しかも、太陽電池のような光電変換
装置の製造においては、大面積の薄膜を堆積させる必要
があるので、製品歩留りの低下や成膜装置維持管理ため
の労力およびコストの増大という深刻な問題を招く。In general, when the pressure conditions of the plasma CVD method are increased, a large amount of powdery products and dust are generated in the plasma reaction chamber. In that case, there is a high risk that the dust or the like will fly to the surface of the film being deposited and be taken into the deposited film, which may cause pinholes in the film. In order to reduce such deterioration of the film quality, the inside of the reaction chamber must be frequently cleaned. In particular, when a film is formed under a low temperature condition such as 550 ° C. or lower, these problems when the pressure in the reaction chamber is increased become remarkable. Moreover, in the manufacture of a photoelectric conversion device such as a solar cell, a large-area thin film needs to be deposited, which causes serious problems such as a decrease in product yield and an increase in labor and cost for maintaining and managing the film formation device. .
【００１０】したがって、薄膜光電変換装置をプラズマ
ＣＶＤ法を用いて製造する場合には、上述のように従来
から１Ｔｏｒｒ以下の圧力条件が用いられている。Therefore, when a thin film photoelectric conversion device is manufactured by the plasma CVD method, a pressure condition of 1 Torr or less has been conventionally used as described above.
【００１１】[0011]
【発明が解決しようとする課題】前述のような結晶質シ
リコン系薄膜光電変換層を含む光電変換装置において
は、以下のような問題がある。すなわち、多結晶シリコ
ンであろうと部分的にアモルファス層を含む微結晶シリ
コンであろうと、太陽電池の光電変換層として用いる場
合には、結晶質シリコンの吸収係数を考えれば、太陽光
を十分に吸収させるためには少なくとも数μｍから数十
μｍもの膜厚が要求される。これは、アモルファスシリ
コン光電変換層の場合に比べれば１桁弱から２桁も厚い
ことになる。The photoelectric conversion device including the crystalline silicon-based thin film photoelectric conversion layer as described above has the following problems. In other words, when used as a photoelectric conversion layer of a solar cell, whether it is polycrystalline silicon or microcrystalline silicon partially containing an amorphous layer, it can sufficiently absorb sunlight in consideration of the absorption coefficient of crystalline silicon. In order to achieve this, a film thickness of at least several μm to several tens μm is required. This means that the thickness is slightly less than one digit to two orders of magnitude as compared with the case of the amorphous silicon photoelectric conversion layer.
【００１２】しかるに、これまでの技術によれば、プラ
ズマＣＶＤ法によって低温で良質の結晶質シリコン系薄
膜を得るためには、温度，反応室内圧力，高周波パワ
ー，ならびにガス流量比というような種々の成膜条件パ
ラメータを検討しても、その成膜速度はアモルファスシ
リコン膜の場合と同程度もしくはそれ以下であって、た
とえば１０ｎｍ／分程度にしかならなかった。この問題
を言い換えれば、結晶質シリコン薄膜光電変換層はアモ
ルファスシリコン光電変換層の何倍から何１０倍もの成
膜時間を要することになり、光電変換装置の製造工程の
スループットの向上が困難となって低コスト化の妨げと
なる。However, according to the prior art, in order to obtain a good-quality crystalline silicon-based thin film at a low temperature by a plasma CVD method, various factors such as temperature, pressure in a reaction chamber, high-frequency power, and gas flow ratio are required. Even when examining the film forming condition parameters, the film forming rate was about the same as or lower than that of the amorphous silicon film, for example, only about 10 nm / min. In other words, the crystalline silicon thin film photoelectric conversion layer requires several times to tens of times the film formation time of the amorphous silicon photoelectric conversion layer, and it is difficult to improve the throughput of the photoelectric conversion device manufacturing process. And hinder cost reduction.
【００１３】上述のような従来技術の課題に鑑み、本発
明の目的は、低温プラズマＣＶＤ法で形成する結晶質シ
リコン系光電変換層の成膜速度を高速化することによっ
て製造工程のスループットを向上させ、かつ光電変換装
置の性能をも改善させることにある。In view of the above-mentioned problems of the prior art, an object of the present invention is to improve the throughput of the manufacturing process by increasing the film formation rate of a crystalline silicon-based photoelectric conversion layer formed by a low-temperature plasma CVD method. And to improve the performance of the photoelectric conversion device.
【００１４】[0014]
【課題を解決するための手段】本発明によるシリコン系
薄膜光電変換装置の製造方法においては、その光電変換
装置が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１導電型半導体層と、結晶質
を含むシリコン系薄膜光電変換層と、逆導電型半導体層
とを含むものであり、その光電変換層をプラズマＣＶＤ
法で堆積する条件として：下地温度が５５０℃以下であ
り；プラズマ反応室内に導入されるガスの主要成分とし
てシラン系ガスと水素ガスを含み、かつシラン系ガスに
対する水素ガスの流量が５０倍以上であり；プラズマ反
応室内の圧力が３Ｔｏｒｒ以上に設定され；そして、成
膜速度は厚さ方向で１６ｎｍ／分以上であることを特徴
としている。In a method of manufacturing a silicon-based thin-film photoelectric conversion device according to the present invention, the photoelectric conversion device includes at least one photoelectric conversion unit formed on a substrate, and the photoelectric conversion unit includes a plasma conversion unit. CVD
A one-conductivity-type semiconductor layer, a silicon-based thin-film photoelectric conversion layer containing a crystalline material, and a reverse-conductivity-type semiconductor layer, which are sequentially laminated by a plasma method.
Conditions for deposition by the method: The base temperature is 550 ° C. or lower; the silane-based gas and the hydrogen gas are contained as main components of the gas introduced into the plasma reaction chamber, and the flow rate of the hydrogen gas to the silane-based gas is 50 times or more. The pressure in the plasma reaction chamber is set to 3 Torr or more; and the film forming rate is 16 nm / min or more in the thickness direction.
【００１５】[0015]
【発明の実施の形態】図１は、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
的な斜視図で図解している。この装置の基板２０１には
ステンレス等の金属、有機フィルム、または低融点の安
価なガラス等が用いられ得る。FIG. 1 is a schematic perspective view illustrating a silicon-based thin-film photoelectric conversion device manufactured according to one embodiment of the present invention. As the substrate 201 of this apparatus, a metal such as stainless steel, an organic film, a low-melting-point inexpensive glass, or the like can be used.
【００１６】基板２０１上の裏面電極２１０は、下記の
薄膜（Ａ）と（Ｂ）のうちの１以上を含み、たとえば蒸
着法やスパッタリング法によって形成され得る。 （Ａ） Ｔｉ，Ｃｒ，Ａｌ，Ａｇ，Ａｕ，ＣｕおよびＰ
ｔから選択された少なくとも１以上の金属またはこれら
の合金からなる金属薄膜。 （Ｂ） ＩＴＯ，ＳｎＯ2 およびＺｎＯから選択された
少なくとも１以上の酸化物からなる透明導電性薄膜。The back electrode 210 on the substrate 201 includes one or more of the following thin films (A) and (B), and can be formed by, for example, an evaporation method or a sputtering method. (A) Ti, Cr, Al, Ag, Au, Cu and P
a metal thin film made of at least one metal selected from t or an alloy thereof. (B) A transparent conductive thin film made of at least one oxide selected from ITO, SnO 2 and ZnO.
【００１７】裏面電極２１０上には光電変換ユニット２
１１の内の１導電型半導体層２０４がプラズマＣＶＤ法
にて堆積される。この１導電型半導体層２０４として
は、たとえば導電型決定不純物原子であるリンが０．０
１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％以上ドープされたｐ型シリコン層な
どが用いられ得る。しかし、１導電型半導体層２０４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
子としてはたとえば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。導電型シリ
コン系薄膜２０４は、多結晶，微結晶，またはアモルフ
ァスのいずれでもよく、その膜厚は１〜１００ｎｍの範
囲内に設定され、より好ましくは２〜３０ｎｍの範囲内
に設定される。On the back electrode 210, the photoelectric conversion unit 2
One of the 11 conductive type semiconductor layers 204 is deposited by a plasma CVD method. The one-conductivity-type semiconductor layer 204 contains, for example, 0.0% of phosphorus as a conductivity-type determining impurity atom.
An n-type silicon layer doped with 1 atomic% or more or a p-type silicon layer doped with boron at 0.01 atomic% or more can be used. However, these conditions for the one conductivity type semiconductor layer 204 are not limited. For example, the impurity atoms may be aluminum or the like in the p-type silicon layer, or may be an alloy material such as silicon carbide or silicon germanium. Good. The conductive silicon-based thin film 204 may be polycrystalline, microcrystalline, or amorphous, and its thickness is set in the range of 1 to 100 nm, and more preferably in the range of 2 to 30 nm.
【００１８】結晶質を含むシリコン系薄膜の光電変換層
２０５としては、ノンドープのｉ型多結晶シリコン薄膜
や体積結晶化分率８０％以上のｉ型微結晶シリコン薄
膜、または微量の不純物を含む弱ｐ型もしくは弱ｎ型で
光電変換効率を十分に備えているシリコン系薄膜材料が
使用され得る。また、光電変換層２０５はこれらの材料
に限定されず、シリコンカーバイドやシリコンゲルマニ
ウム等の合金材料を用いてもよい。光電変換層２０５の
膜厚は０．５〜２０μｍの範囲内にあり、結晶質シリコ
ン薄膜光電変換層として必要かつ十分な膜厚を有してい
る。As the silicon-based thin film photoelectric conversion layer 205 containing crystalline material, a non-doped i-type polycrystalline silicon thin film, an i-type microcrystalline silicon thin film having a volume crystallization fraction of 80% or more, or a weakly A p-type or weak n-type silicon-based thin film material having sufficient photoelectric conversion efficiency can be used. Further, the photoelectric conversion layer 205 is not limited to these materials, and an alloy material such as silicon carbide or silicon germanium may be used. The thickness of the photoelectric conversion layer 205 is in the range of 0.5 to 20 μm, and has a necessary and sufficient thickness as a crystalline silicon thin film photoelectric conversion layer.
【００１９】結晶質シリコン系光電変換層２０５の成膜
は、通常に広く用いられている平行平板型ＲＦプラズマ
ＣＶＤ法で行なわれ得るほか、周波数が１５０ＭＨｚ以
下でＲＦ帯からＶＨＦ帯までの高周波電源を用いたプラ
ズマＣＶＤ法で行なわれてもよい。The formation of the crystalline silicon-based photoelectric conversion layer 205 can be performed by a parallel plate type RF plasma CVD method widely used in general, and a high frequency power supply having a frequency of 150 MHz or less and an RF band to a VHF band. May be performed by the plasma CVD method using
【００２０】なお、これらのプラズマＣＶＤ法における
結晶質シリコン系光電変換層２０５の成膜温度は、上述
した安価な基板が使用され得る５５０℃以下である。Note that the film forming temperature of the crystalline silicon-based photoelectric conversion layer 205 in these plasma CVD methods is 550 ° C. or lower at which the above-mentioned inexpensive substrate can be used.
【００２１】結晶質シリコン系薄膜光電変換層２０５
は、プラズマＣＶＤ法における反応室内圧力が３Ｔｏｒ
ｒ以上で、より好ましくは５Ｔｏｒｒ以上の条件下で堆
積される。また、そのときの高周波パワー密度は２０ｍ
Ｗ／ｃｍ2 以上であることが好ましく、５０ｍＷ／ｃｍ
2 以上であることがより好ましい。さらに、反応室内に
導入されるガスの主成分としてシラン系ガスと水素ガス
を含み、かつシラン系ガスに対する水素ガスの流量は５
０倍以上にされる。シラン系ガスとしてはモノシラン，
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。また、これらに加えて希ガス等
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。Crystalline silicon based thin film photoelectric conversion layer 205
Means that the pressure in the reaction chamber in the plasma CVD method is 3 Torr
r or more, more preferably 5 Torr or more. The high frequency power density at that time is 20 m
W / cm 2 or more, preferably 50 mW / cm 2
More preferably, it is 2 or more. Further, the gas introduced into the reaction chamber contains silane-based gas and hydrogen gas as main components, and the flow rate of hydrogen gas to the silane-based gas is 5 to 5.
It is made 0 times or more. Monosilane as the silane-based gas,
Disilane and the like are preferable, and in addition, silicon halide gas such as silicon tetrafluoride, silicon tetrachloride, and dichlorosilane may be used. In addition, an inert gas such as a rare gas, preferably helium, neon, or argon may be used.
【００２２】本発明は、以上のような結晶質シリコン系
光電変換層２０５の形成条件において、その成膜速度が
１６ｎｍ／分以上にされ得ることを特徴としている。The present invention is characterized in that, under the above-described conditions for forming the crystalline silicon-based photoelectric conversion layer 205, the film formation rate can be increased to 16 nm / min or more.
【００２３】この結晶質シリコン系薄膜光電変換層２０
５に含まれる結晶粒の多くは、下地層２０４から上方に
柱状に延びて成長している。これらの多くの結晶粒は膜
面に平行に（１１０）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（１１
１）回折ピークの強度比は１／１０以下であることが好
ましく、１／２０以下であることがより好ましい。ま
た、下地層である１導電型層２０４の表面形状が実質的
に平面である場合でも、光電変換層２０５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。This crystalline silicon-based thin film photoelectric conversion layer 20
Many of the crystal grains included in 5 extend upward from the base layer 204 in a columnar shape and grow. Many of these grains have a (110) preferred crystal orientation plane parallel to the film plane, and their X
(11) for the (220) diffraction peak determined by X-ray diffraction
1) The intensity ratio of the diffraction peak is preferably 1/10 or less, more preferably 1/20 or less. Further, even when the surface shape of the one-conductivity-type layer 204 that is the underlying layer is substantially flat, the surface after the formation of the photoelectric conversion layer 205 has minute gaps of about one digit smaller than the film thickness. A surface texture structure having irregularities is formed.
【００２４】また、得られる結晶質シリコン系薄膜２０
５は、２次イオン質量分析法により求められる水素含有
量が０．５原子％以上で３０原子％以下の範囲内にある
ことが好ましく、１原子％以上で２０原子％以下の範囲
内にあることがより好ましい。The obtained crystalline silicon-based thin film 20
5 is preferably such that the hydrogen content determined by secondary ion mass spectrometry is in the range of 0.5 atomic% to 30 atomic%, preferably 1 atomic% to 20 atomic%. Is more preferable.
【００２５】本発明における結晶質シリコン系薄膜光電
変換層２０５の形成方法では、従来の３Ｔｏｒｒ未満の
圧力条件に比べれば高圧力であるので、膜中のイオンダ
メージが極力低減できる。したがって、成膜速度を速め
るために高周波パワーを高くしたりガス流量を増加させ
ても、堆積膜表面でのイオンダメージが少なくて、良質
の膜が高速度で形成され得る。また、高圧力条件で成膜
を行なえば反応室内のパウダー生成による汚染が懸念さ
れるが、原料ガスが水素のような高熱伝導性ガスで大量
に希釈されているので、このような問題も起こりにく
い。In the method of forming the crystalline silicon-based thin film photoelectric conversion layer 205 according to the present invention, since the pressure is higher than the conventional pressure condition of less than 3 Torr, ion damage in the film can be reduced as much as possible. Therefore, even if the high-frequency power is increased or the gas flow rate is increased in order to increase the film formation speed, ion damage on the surface of the deposited film is small, and a high-quality film can be formed at a high speed. In addition, if film formation is performed under high pressure conditions, there is a concern that contamination due to powder generation in the reaction chamber may occur.However, such a problem also occurs because the raw material gas is diluted in large quantities with a high heat conductive gas such as hydrogen. Hateful.
【００２６】さらに、以下のような理由により、本発明
では、従来法の場合に比べて高品質の結晶質シリコン系
薄膜２０５が得られる。まず、成膜速度が速いので、反
応室内に残留している酸素や窒素等の不純物原子が膜中
に取り込まれる割合が減少する。また、膜成長初期にお
ける結晶核生成時間が短いために相対的に核発生密度が
減少し、大粒径で強く結晶配向した結晶粒が形成されや
すくなる。さらに、高圧力で成膜すれば、結晶粒界や粒
内の欠陥が水素でパッシベーションされやすく、それら
の欠陥密度も減少する。Further, for the following reason, in the present invention, a crystalline silicon-based thin film 205 having higher quality than that of the conventional method can be obtained. First, since the deposition rate is high, the rate at which impurity atoms such as oxygen and nitrogen remaining in the reaction chamber are taken into the film decreases. Further, since the crystal nucleus generation time in the early stage of film growth is short, the nucleus generation density is relatively reduced, and crystal grains having a large grain size and strong crystal orientation are easily formed. Further, when a film is formed under a high pressure, the crystal grain boundaries and defects in the grains are easily passivated by hydrogen, and the defect density thereof is reduced.
【００２７】光電変換層２０５上には、その下地層２０
４とは逆タイプの導電型半導体層２０６としてのシリコ
ン系薄膜がプラズマＣＶＤ法によって堆積される。この
逆導電型シリコン系薄膜２０６としては、たとえば導電
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。しかし、逆導電型半導体層２０６についてのこれ
らの条件は限定的なものではなく、不純物原子としては
たとえば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。この逆導電型シリコン
系薄膜２０６は、多結晶，微結晶，またはアモルファス
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。On the photoelectric conversion layer 205, the underlying layer 20
A silicon-based thin film as a conductive semiconductor layer 206 of a type opposite to that of No. 4 is deposited by a plasma CVD method. As the reverse conductivity type silicon-based thin film 206, for example, a p-type silicon thin film doped with boron, which is a conductivity type determining impurity atom, in an amount of 0.01 atomic% or more, or an n-type silicon film doped with phosphorus in an amount of 0.01 atomic% or more, A thin film or the like can be used. However, these conditions for the opposite conductivity type semiconductor layer 206 are not limited. For example, aluminum may be used as impurity atoms in p-type silicon, or a film of an alloy material such as silicon carbide or silicon germanium may be used. You may. The reverse conductivity type silicon-based thin film 206 may be polycrystalline, microcrystalline, or amorphous, and the thickness is set in a range of 3 to 100 nm, and more preferably, in a range of 5 to 50 nm. .
【００２８】光電変換ユニット１１１上には、ＩＴＯ，
ＳｎＯ2 ，ＺｎＯ等から選択された少なくとも１以上の
層からなる透明導電性酸化膜が形成され、さらにこの上
にグリッド電極として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
合金の層を含む櫛形状の金属電極２０８がスパッタリン
グ法または蒸着法によって形成され、これによって図１
に示されているような光電変換装置が完成する。On the photoelectric conversion unit 111, ITO,
A transparent conductive oxide film composed of at least one layer selected from SnO 2 , ZnO or the like is formed, and a grid electrode formed on the transparent conductive oxide film is at least one selected from Al, Ag, Au, Cu, Pt or the like. A comb-shaped metal electrode 208 including a layer of a metal or an alloy thereof is formed by a sputtering method or an evaporation method.
Is completed.
【００２９】図２は、本発明のもう１つの実施の形態に
おいて製造されるタンデム型シリコン系薄膜光電変換装
置を模式的な斜視図で図解している。図２のタンデム型
光電変換装置においては、図１の場合と同様に基板４０
１上の複数の層４０２〜４０６が、図１の基板２０１上
の複数の層２０２〜２０６に対応して同様に形成され
る。FIG. 2 is a schematic perspective view illustrating a tandem-type silicon-based thin film photoelectric conversion device manufactured in another embodiment of the present invention. In the tandem-type photoelectric conversion device of FIG.
A plurality of layers 402 to 406 on one are similarly formed corresponding to the plurality of layers 202 to 206 on the substrate 201 of FIG.
【００３０】しかし、図２のタンデム型光電変換層にお
いては、第１の光電変換ユニット４１１上に重ねて、プ
ラズマＣＶＤ法にて第２の光電変換ユニット４１２がさ
らに形成される。第２の光電変換ユニット４１２は、第
１の光電変換ユニット４１１上に順次積層された第１導
電型の微結晶またはアモルファスのシリコン系薄膜４１
３、実質的に真性半導体であるアモルファスシリコン系
薄膜光電変換層４１４、および逆導電型の微結晶または
アモルファスのシリコン系薄膜４１５を含んでいる。However, in the tandem-type photoelectric conversion layer shown in FIG. 2, a second photoelectric conversion unit 412 is further formed on the first photoelectric conversion unit 411 by a plasma CVD method. The second photoelectric conversion unit 412 is a microcrystalline or amorphous silicon-based thin film 41 of the first conductivity type which is sequentially stacked on the first photoelectric conversion unit 411.
3. It includes an amorphous silicon-based thin film photoelectric conversion layer 414, which is substantially an intrinsic semiconductor, and a microcrystalline or amorphous silicon-based thin film 415 of the opposite conductivity type.
【００３１】第２の光電変換ユニット４１２上には、前
面透明電極４０７および櫛形状金属電極４０８が図１中
の対応する要素２０７および２０８と同様に形成され、
これによって図２のタンデム型光電変換装置が完成す
る。A front transparent electrode 407 and a comb-shaped metal electrode 408 are formed on the second photoelectric conversion unit 412 in the same manner as the corresponding elements 207 and 208 in FIG.
Thus, the tandem photoelectric conversion device shown in FIG. 2 is completed.
【００３２】また、本発明のさらに他の実施の形態とし
て、図３に示されているようなガラス基板側光入射タイ
プのタンデム型シリコン系薄膜光電変換装置が製造され
得る。この図３の光電変換装置においては、まず透明基
板６０１上に図２中の透明導電層４０７に対応する層６
０７が形成される。そして、この透明導電層６０７上に
は、図２中の複数の層４０２〜４０６と４１３〜４１５
にそれぞれ対応する複数の層６０２〜６０６と６１３〜
６１５が積層順序を逆にして堆積される。このとき、図
３中の各層６０２〜６０７と６１３〜６１５は図２中の
対応する各層４０２〜４０７と４１３〜４１５に準じて
同様に形成され得る。Further, as still another embodiment of the present invention, a glass substrate side light incident type tandem silicon-based thin film photoelectric conversion device as shown in FIG. 3 can be manufactured. In the photoelectric conversion device of FIG. 3, first, a layer 6 corresponding to the transparent conductive layer 407 in FIG.
07 is formed. Then, on the transparent conductive layer 607, a plurality of layers 402 to 406 and 413 to 415 in FIG.
602 to 606 and 613 to
615 is deposited with the stacking order reversed. At this time, each of the layers 602 to 607 and 613 to 615 in FIG. 3 can be similarly formed according to the corresponding layers 402 to 407 and 413 to 415 in FIG.
【００３３】以上述べた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上
で従来から最も大きな課題であったのは、大きな膜厚を
必要とする結晶質光電変換層（２０５，４０５，６０
５）の製造工程であったことは言うまでもない。しかし
ながら、本発明によれば、その結晶質光電変換層の成膜
速度が大幅に向上し、しかも、より良質の膜が得られる
ことから、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。Among the series of manufacturing steps of the silicon-based thin film photoelectric conversion device described above, the biggest problem in improving the throughput has been the crystalline photoelectric conversion layer requiring a large film thickness. (205,405,60
Needless to say, the manufacturing process was 5). However, according to the present invention, the film formation rate of the crystalline photoelectric conversion layer is greatly improved, and a higher quality film can be obtained. Can greatly contribute to
【００３４】[0034]
【実施例】以下において、本発明のいくつかの実施例に
よるシリコン系薄膜光電変換装置としてのシリコン系薄
膜太陽電池が、比較例による太陽電池とともに説明され
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a silicon-based thin-film solar cell as a silicon-based thin-film photoelectric conversion device according to some embodiments of the present invention will be described together with a solar cell according to a comparative example.
【００３５】（実施例１）図１の実施の形態に対応し
て、実施例１としての結晶質シリコン薄膜太陽電池が作
製された。まず、ガラス基板２０１上に裏面電極２１０
として、厚さ３００ｎｍのＡｇ膜２０２とその上の厚さ
１００ｎｍのＺｎＯ膜２０３のそれぞれがスパッタリン
グ法によって形成された。裏面電極２１０上には、厚さ
３０ｎｍでリンドープされたｎ型微結晶シリコン層２０
４、厚さ３μｍでノンドープの多結晶シリコン薄膜光電
変換層２０５、および厚さ１５ｎｍでボロンドープされ
たｐ型微結晶シリコン層２０６がそれぞれＲＦプラズマ
ＣＶＤ法により成膜され、ｎｉｐ光電変換ユニット２１
１が形成された。光電変換ユニット２１１上には、前面
電極２０７として、厚さ８０ｎｍの透明導電性ＩＴＯ膜
がスパッタリング法にて堆積され、その上に電流取出の
ための櫛形Ａｇ電極２０８が蒸着法にて堆積された。(Example 1) A crystalline silicon thin-film solar cell as Example 1 was manufactured corresponding to the embodiment of FIG. First, a back electrode 210 is formed on a glass substrate 201.
An Ag film 202 having a thickness of 300 nm and a ZnO film 203 having a thickness of 100 nm on the Ag film 202 were formed by a sputtering method. On the back electrode 210, an n-type microcrystalline silicon layer 20 doped with phosphorus and having a thickness of 30 nm is formed.
4. A non-doped polycrystalline silicon thin-film photoelectric conversion layer 205 having a thickness of 3 μm and a boron-doped p-type microcrystalline silicon layer 206 having a thickness of 15 nm are formed by RF plasma CVD, respectively.
1 was formed. On the photoelectric conversion unit 211, a transparent conductive ITO film having a thickness of 80 nm was deposited as a front electrode 207 by a sputtering method, and a comb-shaped Ag electrode 208 for current extraction was deposited thereon by a vapor deposition method. .
【００３６】多結晶シリコン薄膜光電変換層２０５は、
１３．５６ＭＨｚの高周波電源を用いたＲＦプラズマＣ
ＶＤ法により堆積された。そのときに用いられた反応ガ
スにおいてはシランと水素の流量比が１：６０で混合さ
れ、反応室内圧力は３．０Ｔｏｒｒにされた。また、放
電パワー密度は８０ｍＷ／ｃｍ2 で、成膜温度は４００
℃に設定された。このような成膜条件の下では、多結晶
シリコン薄膜光電変換層２０５の成膜速度は１６ｎｍ／
分であった。また、この光電変換層２０５について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１／１６であり、２次イオン質量
分析法から求めた水素含有量は０．８原子％であった。The polycrystalline silicon thin film photoelectric conversion layer 205 is
RF plasma C using 13.56 MHz high frequency power supply
Deposited by VD method. In the reaction gas used at that time, the flow ratio of silane and hydrogen was mixed at 1:60, and the pressure in the reaction chamber was set to 3.0 Torr. The discharge power density was 80 mW / cm 2 and the film formation temperature was 400
° C was set. Under such film forming conditions, the film forming speed of the polycrystalline silicon thin film photoelectric conversion layer 205 is 16 nm /
Minutes. In addition, (111) of the photoelectric conversion layer 205 with respect to the (220) diffraction peak obtained by X-ray diffraction was obtained.
The diffraction peak intensity ratio was 1/16, and the hydrogen content determined by secondary ion mass spectrometry was 0.8 atomic%.
【００３７】この実施例１の多結晶シリコン薄膜太陽電
池に入射光２０９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においては、開
放端電圧が０．４９８Ｖ、短絡電流密度が２７．０ｍＡ
／ｃｍ2 、曲線因子が７１．５％、そして変換効率が
９．６％であった。In the polycrystalline silicon thin-film solar cell of the first embodiment, an incident light 209 of AM1.5 light of 100 mW /
With respect to output characteristics when irradiated with a light amount of cm 2 , the open-circuit voltage was 0.498 V and the short-circuit current density was 27.0 mA.
/ Cm 2 , fill factor 71.5%, and conversion efficiency 9.6%.
【００３８】（実施例２）実施例２においては、実施例
１に類似した多結晶シリコン薄膜太陽電池が作製され
た。すなわち、この実施例２において、多結晶シリコン
薄膜光電変換層２０５の成膜条件が変更されたことを除
けば、他の層の成膜条件およびデバイス構造は実施例１
の場合と全く同じであった。(Example 2) In Example 2, a polycrystalline silicon thin film solar cell similar to Example 1 was produced. That is, except that the film forming conditions of the polycrystalline silicon thin film photoelectric conversion layer 205 in Example 2 were changed, the film forming conditions and device structure of other layers were the same as those in Example 1.
Was exactly the same as
【００３９】実施例２における多結晶シリコン薄膜光電
変換層２０５は、１３．５６ＭＨｚの高周波電源を用い
たＲＦプラズマＣＶＤ法により堆積された。反応ガスに
おいてはシランと水素の流量比が１：１２０で混合さ
れ、反応室内圧力は５．０Ｔｏｒｒにされた。また、放
電パワー密度は１２０ｍＷ／ｃｍ2 で、成膜温度は４０
０℃に設定された。このような成膜条件の下では、多結
晶シリコン薄膜光電変換層２０５の成膜速度は２３ｎｍ
／分であった。また、この光電変換層２０５についてＸ
線回折で求めた（２２０）回折ピークに対する（１１
１）回折ピークの強度比は１／３０であり、２次イオン
質量分析法から求めた水素含有量は１．６原子％であっ
た。The polycrystalline silicon thin film photoelectric conversion layer 205 in Example 2 was deposited by RF plasma CVD using a 13.56 MHz high frequency power supply. In the reaction gas, the flow ratio of silane and hydrogen was mixed at 1: 120, and the pressure in the reaction chamber was adjusted to 5.0 Torr. The discharge power density was 120 mW / cm 2 and the film formation temperature was 40 mW / cm 2.
It was set to 0 ° C. Under such film forming conditions, the film forming speed of the polycrystalline silicon thin film photoelectric conversion layer 205 is 23 nm.
/ Min. Further, regarding this photoelectric conversion layer 205, X
(11) for the (220) diffraction peak determined by X-ray diffraction
1) The intensity ratio of the diffraction peak was 1/30, and the hydrogen content determined by secondary ion mass spectrometry was 1.6 atomic%.
【００４０】この実施例２の多結晶シリコン薄膜太陽電
池に入射光２０９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においては、開
放端電圧が０．５２０Ｖ、短絡電流密度が２７．４ｍＡ
／ｃｍ2 、曲線因子が７５．１％、そして変換効率が１
０．５％であった。In the polycrystalline silicon thin-film solar cell of the second embodiment, an incident light 209 was irradiated with AM1.5 light at 100 mW /
With respect to output characteristics when irradiated with a light amount of cm 2 , the open-circuit voltage was 0.520 V and the short-circuit current density was 27.4 mA.
/ Cm 2 , fill factor 75.1%, and conversion efficiency 1
0.5%.
【００４１】（実施例３〜８）実施例３〜８として、多
結晶シリコン薄膜光電変換層２０５の成膜条件が表１に
示された条件に変更されたことを除けば実施例１および
２と同様にガラス基板上に多結晶シリコン薄膜太陽電池
が作製された。これらの実施例３〜８において形成され
た多結晶シリコン薄膜光電変換層２０５の物性およびそ
れを含んで製造された太陽電池の特性が表２に示されて
いる。なお、表１と表２において、実施例１と２に関す
る成膜条件、その条件により形成された膜の物性および
その膜を含む太陽電池の各種特性も併記されている。(Examples 3 to 8) As Examples 3 to 8, Examples 1 and 2 were performed except that the film forming conditions of the polycrystalline silicon thin film photoelectric conversion layer 205 were changed to the conditions shown in Table 1. A polycrystalline silicon thin-film solar cell was fabricated on a glass substrate in the same manner as described above. Table 2 shows the physical properties of the polycrystalline silicon thin-film photoelectric conversion layers 205 formed in Examples 3 to 8 and the characteristics of solar cells manufactured using the same. In Tables 1 and 2, the film forming conditions relating to Examples 1 and 2, physical properties of a film formed under the conditions, and various characteristics of a solar cell including the film are also described.
【００４２】[0042]
【表１】 [Table 1]
【００４３】[0043]
【表２】 [Table 2]
【００４４】（比較例１〜４）比較例１〜４として、表
３に示された成膜条件の下で多結晶シリコン薄膜光電変
換層が形成されたことを除けば実施例１〜８の場合と同
様にガラス基板上に多結晶シリコン薄膜太陽電池が作製
された。そして、この比較例１〜４において形成された
多結晶シリコン薄膜の物性およびそれを含む太陽電池の
種々の特性が表４に示されている。Comparative Examples 1 to 4 Comparative Examples 1 to 4 were the same as those of Examples 1 to 8 except that the polycrystalline silicon thin film photoelectric conversion layer was formed under the film forming conditions shown in Table 3. As in the case, a polycrystalline silicon thin film solar cell was fabricated on a glass substrate. Table 4 shows the physical properties of the polycrystalline silicon thin films formed in Comparative Examples 1 to 4 and various characteristics of solar cells including the same.
【００４５】[0045]
【表３】 [Table 3]
【００４６】[0046]
【表４】 [Table 4]
【００４７】表３および表４からわかるように、比較例
１においては従来の成膜条件で光電変換層が形成されて
いるので成膜速度が遅く、その光電変換層を含む太陽電
池も実施例に比べて光電変換効率が低くなっている。比
較例２では、放電パワーが増大されているので光電変換
層の成膜速度が大きくなっているが、その光電変換層を
含む太陽電池の光電変換効率は大幅に小さくなってい
る。比較例３においては、反応室圧力と放電パワーの両
方が増大されているので光電変換層の成膜速度が大きく
なっているが、シランと水素の流量比が従来通りなの
で、その光電変換層を含む太陽電池の光電変換効率はさ
らに小さくなっている。比較例４においては、放電パワ
ーが増大されているが水素に対するシランのガス流量比
が大幅に小さくされかつ圧力が従来通りであるので、光
電変換層の成膜速度が小さくなっているとともに、その
光電変換層を含む太陽電池の変換効率がさらに小さくな
っている。As can be seen from Tables 3 and 4, in Comparative Example 1, since the photoelectric conversion layer was formed under the conventional film forming conditions, the film formation rate was low, and the solar cell including the photoelectric conversion layer was also used in Example 1. , The photoelectric conversion efficiency is lower. In Comparative Example 2, although the discharge power was increased, the deposition rate of the photoelectric conversion layer was increased, but the photoelectric conversion efficiency of the solar cell including the photoelectric conversion layer was significantly reduced. In Comparative Example 3, the film formation rate of the photoelectric conversion layer was increased because both the reaction chamber pressure and the discharge power were increased. However, since the flow ratio of silane to hydrogen was the same as before, the photoelectric conversion layer was The photovoltaic conversion efficiencies of the solar cells that contain them are even smaller. In Comparative Example 4, although the discharge power was increased, the gas flow ratio of silane to hydrogen was greatly reduced and the pressure was the same as before, so that the film formation rate of the photoelectric conversion layer was reduced, and The conversion efficiency of the solar cell including the photoelectric conversion layer is further reduced.
【００４８】（実施例９）上述のような実施例１〜８に
示された低温で高速に結晶質シリコン系薄膜光電変換層
２０５を形成する工程を含む結晶質シリコン薄膜太陽電
池の製造方法は、その製造プロセスがほぼ類似している
アモルファスシリコン系光電変換ユニットをさらに積層
したタンデム型の太陽電池の作製にも有用である。図２
の実施の形態に対応するこの実施例９では、多結晶シリ
コン薄膜光電変換ユニット４１１上に０．３μｍ厚さの
ノンドープ層からなるアモルファスシリコン光電変換層
４１４を含むアモルファス光電変換ユニット４１２を積
層したタンデム型太陽電池において、上記の実施例１と
同様の光照射条件の下で、１．４０Ｖの開放端電圧、１
３．４ｍＡ／ｃｍ2 の短絡電流密度、および１４．０％
の変換効率が得られた。(Embodiment 9) The method for manufacturing a crystalline silicon thin-film solar cell including the step of forming the crystalline silicon-based thin-film photoelectric conversion layer 205 at a low temperature and a high speed as shown in the above-described Examples 1 to 8 is The present invention is also useful for manufacturing a tandem-type solar cell in which an amorphous silicon-based photoelectric conversion unit whose manufacturing process is substantially similar is further laminated. FIG.
In the ninth embodiment corresponding to the embodiment of the present invention, a tandem in which an amorphous photoelectric conversion unit 412 including an amorphous silicon photoelectric conversion layer 414 made of a non-doped layer having a thickness of 0.3 μm is stacked on a polycrystalline silicon thin film photoelectric conversion unit 411. In the solar cell, under the same light irradiation conditions as in Example 1, the open-circuit voltage of 1.40 V, 1
A short circuit current density of 3.4 mA / cm 2 and 14.0%
Conversion efficiency was obtained.
【００４９】[0049]
【発明の効果】以上のように、本発明によれば、結晶質
を含むシリコン系薄膜光電変換層をプラズマＣＶＤ法に
よって低温で形成する際に従来技術に比べて成膜速度を
大幅に向上させることができ、しかもよりよい膜質が得
られるので、シリコン系薄膜光電変換装置の高性能化と
低コスト化の両方に大きく貢献することができる。As described above, according to the present invention, when a silicon-based thin film photoelectric conversion layer containing a crystalline material is formed at a low temperature by a plasma CVD method, the film forming speed is greatly improved as compared with the conventional technique. And a better film quality can be obtained, which can greatly contribute to both high performance and low cost of the silicon-based thin film photoelectric conversion device.
【図１】本発明の１つの実施の形態による結晶質シリコ
ン系薄膜光電変換装置を示す模式的な斜視図である。FIG. 1 is a schematic perspective view showing a crystalline silicon-based thin film photoelectric conversion device according to one embodiment of the present invention.
【図２】本発明のもう１つの実施の形態による非晶質シ
リコン薄膜／結晶質シリコン薄膜型のタンデム型光電変
換装置を示す模式的な斜視図である。FIG. 2 is a schematic perspective view showing an amorphous silicon thin film / crystalline silicon thin film type tandem photoelectric conversion device according to another embodiment of the present invention.
【図３】本発明のさらに他の実施の形態による非晶質シ
リコン薄膜／結晶質シリコン薄膜型のタンデム型光電変
換装置を示す模式的な斜視図である。FIG. 3 is a schematic perspective view showing an amorphous silicon thin film / crystalline silicon thin film tandem-type photoelectric conversion device according to still another embodiment of the present invention.
２０１，４０１，６０１：ガラス等の基板 ２０２，４０２，６０２：Ａｇ等の膜 ２０３，４０３，６０３：ＺｎＯ等の膜 ２０４，４０４，６０４：たとえばｎ型の第１導電型微
結晶シリコン層 ２０５，４０５，６０５：結晶質シリコン光電変換層 ２０６，４０６，６０６：たとえばｐ型の逆導電型多結
晶シリコン層 ２０７，４０７，６０７：ＩＴＯ等の透明導電膜 ２０８，４０８：Ａｇ等の櫛形電極 ２０９，４０９，６０９：照射光 ２１０，４１０，６１０：裏面電極 ２１１，４１１，６１１：結晶質シリコン光電変換ユニ
ット ４１２，６１２：アモルファスシリコン光電変換ユニッ
ト ４１３，６１３：たとえばｎ型の第１導電型シリコン系
層 ４１４，６１４：ｉ型のアモルファスシリコン光電変換
層 ４１５，６１５：たとえばｐ型の逆導電型シリコン系層201, 401, 601: Substrates made of glass or the like 202, 402, 602: Films made of Ag or the like 203, 403, 603: Films made of ZnO or the like 204, 404, 604: For example, n-type first conductivity type microcrystalline silicon layer 205, 405, 605: crystalline silicon photoelectric conversion layers 206, 406, 606: for example, p-type reverse conductivity type polycrystalline silicon layers 207, 407, 607: transparent conductive films 208, 408: comb electrodes 209, such as Ag 409, 609: Irradiation light 210, 410, 610: Back electrode 211, 411, 611: Crystalline silicon photoelectric conversion unit 412, 612: Amorphous silicon photoelectric conversion unit 413, 613: For example, n-type first conductivity type silicon-based layer 414, 614: i-type amorphous silicon photoelectric conversion layer 415, 615: for example, p Opposite conductivity type silicon-based layer of
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｌ 31/04 Ｗ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI H01L 31/04 W
Claims (5)
であって、 前記光電変換装置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１導電型半導体
層と、結晶質を含む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ものであり、 前記光電変換層を前記プラズマＣＶＤ法で堆積する条件
として、 下地温度が５５０℃以下であり、 プラズマ反応室内に導入されるガスの主成分としてシラ
ン系ガスと水素ガスを含み、かつシラン系ガスに対する
水素ガスの流量が５０倍以上であり、 前記プラズマ反応室内の圧力が３Ｔｏｒｒ以上に設定さ
れ、 そして、成膜速度は厚さ方向で１６ｎｍ／分以上である
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。1. A method for manufacturing a silicon-based thin-film photoelectric conversion device, wherein the photoelectric conversion device includes at least one photoelectric conversion unit formed on a substrate, and the photoelectric conversion units are sequentially stacked by a plasma CVD method. And a silicon-based thin-film photoelectric conversion layer containing crystalline material and a reverse conductivity type semiconductor layer. The conditions for depositing the photoelectric conversion layer by the plasma CVD method include: 550 ° C. or lower; a silane-based gas and a hydrogen gas as main components of the gas introduced into the plasma reaction chamber; and a flow rate of the hydrogen gas to the silane-based gas is 50 times or more; A silicon-based thin-film photoelectric conversion device characterized by being set at 3 Torr or more, and having a film formation rate of 16 nm / min or more in the thickness direction. Construction method.
ｒ以上に設定されることを特徴とする請求項１に記載の
シリコン系薄膜光電変換装置の製造方法。2. The pressure in the plasma reaction chamber is 5 Torr.
2. The method for manufacturing a silicon-based thin-film photoelectric conversion device according to claim 1, wherein the value is set to r or more.
は体積結晶化分率８０％以上の微結晶シリコン膜であ
り、０．５原子％以上で３０原子％以下の水素を含有
し、そして０．５〜２０μｍの範囲内の膜厚を有してい
ることを特徴とする請求項１または２に記載のシリコン
系薄膜光電変換装置の製造方法。3. The photoelectric conversion layer is a polycrystalline silicon film or a microcrystalline silicon film having a volume crystallization fraction of 80% or more, containing 0.5 atomic% to 30 atomic% of hydrogen, and 3. The method according to claim 1, wherein the thickness of the silicon-based thin-film photoelectric conversion device is in the range of 0.5 to 20 [mu] m.
１０）の優先結晶配向面を有し、そのＸ線回折における
（２２０）回折ピークに対する（１１１）回折ピークの
強度比が１／１０以下であることを特徴とする請求項１
から３のいずれかの項に記載のシリコン系薄膜光電変換
装置の製造方法。4. The photoelectric conversion layer according to claim 1, wherein said photoelectric conversion layer is parallel to said film surface.
10. A crystallographic plane having a preferred crystal orientation of (10), wherein the intensity ratio of the (111) diffraction peak to the (220) diffraction peak in X-ray diffraction is 1/10 or less.
4. The method for manufacturing a silicon-based thin-film photoelectric conversion device according to any one of items 3 to 3.
系光電変換ユニットとを積層することによってタンデム
型の光電変換装置にすることを特徴とする請求項１から
４のいずれかの項に記載のシリコン系薄膜光電変換装置
の製造方法。5. The tandem-type photoelectric conversion device by laminating the photoelectric conversion unit and an amorphous silicon-based photoelectric conversion unit. A method for manufacturing a silicon-based thin-film photoelectric conversion device.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30709397A JP3364137B2 (en) | 1997-11-10 | 1997-11-10 | Method for manufacturing silicon-based thin film photoelectric conversion device |
| AU96494/98A AU9649498A (en) | 1997-11-10 | 1998-10-28 | Method of producing silicon thin-film photoelectric transducer and plasma cvd apparatus used for the method |
| EP98950423A EP1041646B1 (en) | 1997-11-10 | 1998-10-28 | Method of producing silicon thin-film photoelectric transducer |
| US09/554,164 US6337224B1 (en) | 1997-11-10 | 1998-10-28 | Method of producing silicon thin-film photoelectric transducer and plasma CVD apparatus used for the method |
| PCT/JP1998/004875 WO1999025029A1 (en) | 1997-11-10 | 1998-10-28 | Method of producing silicon thin-film photoelectric transducer and plasma cvd apparatus used for the method |
| EP10173539A EP2251913A3 (en) | 1997-11-10 | 1998-10-28 | Method of Manufacturing Silicon-Based Thin Film Photoelectric Converter and Plasma CVD Apparatus Used for Such Method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30709397A JP3364137B2 (en) | 1997-11-10 | 1997-11-10 | Method for manufacturing silicon-based thin film photoelectric conversion device |
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| Publication Number | Publication Date |
|---|---|
| JPH11145499A true JPH11145499A (en) | 1999-05-28 |
| JP3364137B2 JP3364137B2 (en) | 2003-01-08 |
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ID=17964949
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001135841A (en) * | 1999-08-24 | 2001-05-18 | Canon Inc | Method of manufacturing photovoltaic device |
| JP2001274429A (en) * | 2000-03-23 | 2001-10-05 | Kanegafuchi Chem Ind Co Ltd | Hybrid thin film photoelectric converter and producing method therefor |
| DE102007024986A1 (en) * | 2007-05-28 | 2008-12-04 | Forschungszentrum Jülich GmbH | Temperature-stable TCO layer, method of manufacture and application |
| US9112088B2 (en) | 2010-04-22 | 2015-08-18 | Kyocera Corporation | Method for manufacturing a thin-film solar cell using a plasma between parallel electrodes |
-
1997
- 1997-11-10 JP JP30709397A patent/JP3364137B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001135841A (en) * | 1999-08-24 | 2001-05-18 | Canon Inc | Method of manufacturing photovoltaic device |
| JP2001274429A (en) * | 2000-03-23 | 2001-10-05 | Kanegafuchi Chem Ind Co Ltd | Hybrid thin film photoelectric converter and producing method therefor |
| DE102007024986A1 (en) * | 2007-05-28 | 2008-12-04 | Forschungszentrum Jülich GmbH | Temperature-stable TCO layer, method of manufacture and application |
| US9112088B2 (en) | 2010-04-22 | 2015-08-18 | Kyocera Corporation | Method for manufacturing a thin-film solar cell using a plasma between parallel electrodes |
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| Publication number | Publication date |
|---|---|
| JP3364137B2 (en) | 2003-01-08 |
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