JP2005108901A - Photovoltaic element and its manufacturing method - Google Patents

Photovoltaic element and its manufacturing method Download PDF

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JP2005108901A
JP2005108901A JP2003336457A JP2003336457A JP2005108901A JP 2005108901 A JP2005108901 A JP 2005108901A JP 2003336457 A JP2003336457 A JP 2003336457A JP 2003336457 A JP2003336457 A JP 2003336457A JP 2005108901 A JP2005108901 A JP 2005108901A
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film
photovoltaic element
reflective film
photovoltaic
amorphous silicon
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Shin Matsumi
伸 松見
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Sanyo Electric Co Ltd
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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
    • Y02E10/545—Microcrystalline silicon PV cells
    • 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
    • Y02E10/548—Amorphous silicon PV cells

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photovoltaic element which is capable of improving its bonding properties with microcrystal silicon, and to provide its manufacturing method. <P>SOLUTION: A transparent electrode 2, a first photovoltaic element 3 where an amorphous silicon film is used as an optically active layer, a reflecting film 4, a second photovoltaic element 5 where a microcrystal silicon film is used as an optically active layer, and a back electrode 6, are successively formed on a support substrate 1. The first photovoltaic element 3 successively comprises a p-type amorphous silicon carbide film 31, an i-type amorphous silicon film 32, and an n-type amorphous silicon film 33, starting from the transparent electrode 2. The second photovoltaic element 5 successively comprises a p-type microcrystal silicon carbide film 51, an i-type microcrystal silicon film 52, and an n-type microcrystal silicon film 53, starting from the reflecting film 4. In the reflecting film 4 of ZnO, a peak strength on a (002) plane is twice or smaller as high or lower than that by the (004) plane. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、半導体接合を用いた光起電力素子およびその製造方法に関する。   The present invention relates to a photovoltaic device using a semiconductor junction and a method for manufacturing the photovoltaic device.

近年、非晶質シリコン等の薄膜系半導体を光活性層に用いる光起電力素子が開発されている。非晶質シリコンは、原材料が無尽蔵に存在し、製造エネルギーおよび製造コストが低く、多種多様な支持基板を利用でき、高い電圧を取り出すことができ、大面積化が容易であるという特長を有している。その反面、非晶質シリコンを用いた光起電力素子は、結晶系光起電力素子に比較して、光劣化が大きく、光電変換効率が低いという課題がある。   In recent years, photovoltaic devices using thin film semiconductors such as amorphous silicon for photoactive layers have been developed. Amorphous silicon has the features that the raw materials are inexhaustible, the production energy and production cost are low, a wide variety of support substrates can be used, high voltage can be taken out, and the area can be easily increased. ing. On the other hand, the photovoltaic element using amorphous silicon has problems that the photodegradation is large and the photoelectric conversion efficiency is low as compared with the crystalline photovoltaic element.

一方、上述した非晶質シリコンの特長を生かしつつ光劣化を大きく低減できる新たな薄膜光起電力素子として、微結晶シリコンを光活性層に用いる光起電力素子が開発されている。微結晶シリコンは、非晶質シリコンと同様のプロセスで作製することができる。   On the other hand, a photovoltaic element using microcrystalline silicon as a photoactive layer has been developed as a new thin-film photovoltaic element that can greatly reduce photodegradation while taking advantage of the above-described characteristics of amorphous silicon. Microcrystalline silicon can be manufactured by a process similar to that of amorphous silicon.

これらの非晶質シリコンを用いる光起電力素子および微結晶シリコンを用いる光起電力素子を積層した光起電力素子は、幅広い領域の光スペクトルを受光することができる。それにより、光電変換効率が向上する。   A photovoltaic element in which these photovoltaic elements using amorphous silicon and photovoltaic elements using microcrystalline silicon are stacked can receive a light spectrum in a wide range. Thereby, the photoelectric conversion efficiency is improved.

非晶質シリコンを用いる光起電力素子および微結晶シリコンを用いる光起電力素子を積層した光起電力素子においては、非晶質シリコンで発電される光電流と微結晶シリコンで発電される光電流との間に差がある。そのため、非晶質シリコンを用いる光起電力素子と微結晶シリコンを用いる光起電力素子との間に反射膜を設けることにより、光電流のバランスを最適化することができる（例えば、特許文献１参照）。   In a photovoltaic device in which a photovoltaic device using amorphous silicon and a photovoltaic device using microcrystalline silicon are stacked, a photocurrent generated by amorphous silicon and a photocurrent generated by microcrystalline silicon There is a difference between Therefore, the balance of photocurrent can be optimized by providing a reflective film between a photovoltaic element using amorphous silicon and a photovoltaic element using microcrystalline silicon (for example, Patent Document 1). reference).

この場合、光劣化率が大きい非晶質シリコン膜の膜厚を低減させることができるため、光起電力素子全体の変換効率が向上する。
特開昭６３−７７１６７号公報 In this case, since the film thickness of the amorphous silicon film having a large photodegradation rate can be reduced, the conversion efficiency of the entire photovoltaic element is improved.
JP-A 63-77167

しかしながら、非晶質シリコンを用いる光起電力素子と微結晶シリコンを用いる光起電力素子との間に反射膜を挿入すると、微結晶シリコンを用いる光起電力素子と反射膜との接合特性に影響を及ぼし、光起電力素子の直列抵抗が増大する。   However, if a reflective film is inserted between a photovoltaic element using amorphous silicon and a photovoltaic element using microcrystalline silicon, it affects the bonding characteristics between the photovoltaic element using microcrystalline silicon and the reflective film. And the series resistance of the photovoltaic element is increased.

本発明の目的は、微結晶シリコンを用いる光起電力素子と反射膜との間の接合特性を改善することができる光起電力素子およびその製造方法を提供することである。   An object of the present invention is to provide a photovoltaic device that can improve the junction characteristics between a photovoltaic device using microcrystalline silicon and a reflective film, and a method for manufacturing the photovoltaic device.

本明細書中における非晶質系半導体は非晶質半導体を主体とする半導体をいい、微結晶系半導体は結晶粒径が１μｍ以下の微結晶を主体とした半導体をいう。   In this specification, an amorphous semiconductor means a semiconductor mainly composed of an amorphous semiconductor, and a microcrystalline semiconductor means a semiconductor mainly composed of microcrystals having a crystal grain size of 1 μm or less.

また、真性の非晶質系半導体膜および微結晶系半導体膜とは、不純物が意図的にドープされていない非晶質系半導体膜および微結晶系半導体膜であり、半導体原料に本来的に含まれる不純物または製造過程において自然に混入する不純物を含む非晶質系半導体膜および微結晶系半導体膜も含む。   Intrinsic amorphous semiconductor films and microcrystalline semiconductor films are amorphous semiconductor films and microcrystalline semiconductor films that are not intentionally doped with impurities, and are inherently included in semiconductor materials. In addition, amorphous semiconductor films and microcrystalline semiconductor films containing impurities that are mixed or impurities naturally mixed in the manufacturing process are also included.

本発明に係る光起電力素子は、一面および他面を有し入射光を反射する反射膜を備え、反射膜の一面側に、半導体膜を光活性層に用いる第１の光起電力素子を備え、反射膜の他面側に、微結晶半導体膜を光活性層に用いる第２の光起電力素子を備え、反射膜の一面を受光面側とするとともに、反射膜の（００２）面におけるＸ線回折強度のピーク値が反射膜の（００４）面におけるＸ線回折強度のピーク値の２倍以下であるものである。   A photovoltaic device according to the present invention includes a reflective film that has one surface and another surface and reflects incident light, and the first photovoltaic device that uses a semiconductor film as a photoactive layer is provided on one surface side of the reflective film. A second photovoltaic element using a microcrystalline semiconductor film as a photoactive layer is provided on the other surface side of the reflective film. One surface of the reflective film is a light-receiving surface side, and the (002) plane of the reflective film is The peak value of the X-ray diffraction intensity is not more than twice the peak value of the X-ray diffraction intensity on the (004) plane of the reflective film.

本発明に係る光起電力素子においては、反射膜の（００２）面におけるＸ線回折強度のピーク値が反射膜の（００４）面におけるＸ線回折強度のピーク値の２倍以下であることにより、反射膜と第２の光起電力素子との接合特性を改善することができる。   In the photovoltaic device according to the present invention, the peak value of the X-ray diffraction intensity on the (002) plane of the reflective film is not more than twice the peak value of the X-ray diffraction intensity on the (004) plane of the reflective film. The junction characteristics between the reflective film and the second photovoltaic element can be improved.

第１の光起電力素子は、非晶質系半導体膜を光活性層に用いてもよい。この場合、第１の光起電力素子と第２の光起電力素子とで幅広い波長領域で光電変換を行うことができる。それにより、光起電力素子の変換効率が向上する。   The first photovoltaic element may use an amorphous semiconductor film for the photoactive layer. In this case, photoelectric conversion can be performed in a wide wavelength region between the first photovoltaic element and the second photovoltaic element. Thereby, the conversion efficiency of the photovoltaic element is improved.

また、他面側から入射した光の一部が反射膜により反射する。それにより、第１の光起電力素子における光電流と第２の光起電力素子における光電流とのバランスを最適化することができる。   Moreover, a part of the light incident from the other surface side is reflected by the reflection film. Thereby, the balance between the photocurrent in the first photovoltaic element and the photocurrent in the second photovoltaic element can be optimized.

さらに、他面側から入射した光の一部が反射膜により反射することから、光劣化率が大きい第１の光起電力素子の膜厚を低減させることができる。それにより、光起電力素子全体の変換効率が向上する。   Furthermore, since a part of the light incident from the other surface side is reflected by the reflection film, the film thickness of the first photovoltaic element having a high light deterioration rate can be reduced. Thereby, the conversion efficiency of the entire photovoltaic device is improved.

反射膜は、酸化亜鉛からなってもよい。この場合、反射膜と第２の光起電力素子との接合特性を改善することができる。   The reflective film may be made of zinc oxide. In this case, the junction characteristics between the reflective film and the second photovoltaic element can be improved.

本発明に係る光起電力素子の製造方法は、一面および他面を有し、入射光を反射し、（００２）面におけるＸ線回折強度のピーク値が（００４）面におけるＸ線回折強度のピーク値の２倍以下である反射膜を形成する工程と、反射膜の受光面側となる一面側に、半導体膜を光活性層に用いる第１の光起電力素子を形成する工程と、反射膜の他面側に、微結晶半導体膜を光活性層に用いる第２の光起電力素子を形成する工程とを備えるものである。   The method for manufacturing a photovoltaic device according to the present invention has one surface and another surface, reflects incident light, and the peak value of the X-ray diffraction intensity on the (002) plane is the X-ray diffraction intensity on the (004) plane. A step of forming a reflective film having a peak value less than or equal to twice, a step of forming a first photovoltaic element using a semiconductor film as a photoactive layer on one side of the reflective film on the light receiving surface side, Forming a second photovoltaic element using a microcrystalline semiconductor film as a photoactive layer on the other surface side of the film.

本発明に係る光起電力素子の製造方法においては、（００２）面におけるＸ線回折強度のピーク値が（００４）面におけるＸ線回折強度のピーク値の２倍以下である反射膜の一面側に半導体を光活性層に用いる第１の光起電力素子が形成され、反射膜の他面側に微結晶半導体膜を光活性層に用いる第２の光起電力素子が形成される。   In the method for manufacturing a photovoltaic device according to the present invention, the one side of the reflective film in which the peak value of the X-ray diffraction intensity on the (002) plane is not more than twice the peak value of the X-ray diffraction intensity on the (004) plane A first photovoltaic element using a semiconductor for the photoactive layer is formed, and a second photovoltaic element using a microcrystalline semiconductor film for the photoactive layer is formed on the other surface side of the reflective film.

本発明に係る方法により製造された光起電力素子においては、反射膜の（００２）面におけるＸ線回折強度のピーク値が反射膜の（００４）面におけるＸ線回折強度のピーク値の２倍以下であることにより、反射膜と第２の光起電力素子との接合特性を改善することができる。   In the photovoltaic device manufactured by the method according to the present invention, the peak value of the X-ray diffraction intensity on the (002) plane of the reflective film is twice the peak value of the X-ray diffraction intensity on the (004) plane of the reflective film. By being below, the junction characteristic of a reflecting film and a 2nd photovoltaic element can be improved.

本発明に係る光起電力素子においては、反射膜と第２の光起電力素子との接合特性を改善することができる。   In the photovoltaic element according to the present invention, the junction characteristics between the reflective film and the second photovoltaic element can be improved.

以下、第１の実施の形態について説明する。   Hereinafter, the first embodiment will be described.

図１は、本実施の形態に係る光起電力素子１００の構造を示す模式的断面図である。   FIG. 1 is a schematic cross-sectional view showing the structure of the photovoltaic device 100 according to the present embodiment.

図１に示すように、支持基板１上に、透明電極２、非晶質シリコン膜を光活性層に用いる第１の光起電力素子３、反射膜４、微結晶シリコン膜を光活性層に用いる第２の光起電力素子５および裏面電極６が順に形成されている。   As shown in FIG. 1, on a support substrate 1, a transparent electrode 2, a first photovoltaic element 3 using an amorphous silicon film as a photoactive layer, a reflective film 4, and a microcrystalline silicon film as a photoactive layer. The second photovoltaic element 5 and the back electrode 6 to be used are formed in order.

第１の光起電力素子３は、透明電極２側からｐ型非晶質シリコンカーバイド（炭化シリコン）膜３１、ｉ型非晶質シリコン膜３２およびｎ型非晶質シリコン膜３３を順に含む。第２の光起電力素子５は、反射膜４側からｐ型微結晶シリコン膜５１、ｉ型微結晶シリコン膜５２およびｎ型微結晶シリコン膜５３を順に含む。図１の光起電力素子１００では、支持基板１が受光面になる。   The first photovoltaic element 3 includes a p-type amorphous silicon carbide (silicon carbide) film 31, an i-type amorphous silicon film 32, and an n-type amorphous silicon film 33 in this order from the transparent electrode 2 side. The second photovoltaic element 5 includes a p-type microcrystalline silicon film 51, an i-type microcrystalline silicon film 52, and an n-type microcrystalline silicon film 53 in this order from the reflective film 4 side. In the photovoltaic element 100 of FIG. 1, the support substrate 1 becomes a light receiving surface.

支持基板１は、ガラス、プラスチック等の透光性基板からなる。透明電極２は、ＩＴＯ（酸化インジウム錫）、ＳｎＯ2 （酸化錫）、ＺｎＯ（酸化亜鉛）等の金属酸化物からなる。 The support substrate 1 is made of a translucent substrate such as glass or plastic. The transparent electrode 2 is made of a metal oxide such as ITO (indium tin oxide), SnO 2 (tin oxide), or ZnO (zinc oxide).

本実施の形態では、反射膜４は、ＺｎＯからなる。光起電力素子１００の直列抵抗を増加させないために、反射膜４のＺｎＯにおいては、ＸＲＤ（Ｘ線回折：X-Ray diffraction）において次式で表される（００２）面によるピーク強度と（００４）面によるピーク強度との比（以下、ピーク強度比Ｚと呼ぶ）が２以下であることが好ましい。   In the present embodiment, the reflective film 4 is made of ZnO. In order not to increase the series resistance of the photovoltaic element 100, in the ZnO of the reflective film 4, the peak intensity due to the (002) plane represented by the following equation in XRD (X-Ray diffraction) and (004) ) The ratio with respect to the peak intensity by the plane (hereinafter referred to as peak intensity ratio Z) is preferably 2 or less.

ピーク強度比Ｚ ＝ （（００２）面によるＸＲＤピーク強度）／（（００４）面によるＸＲＤピーク強度）・・・（１）
裏面電極６は、Ａｕ（金）、Ａｇ（銀）、Ａｌ（アルミニウム）、Ｃｕ（銅）、Ｔｉ（チタン）、Ｗ（タングステン）、Ｎｉ（ニッケル）等からなり、常温での電気抵抗率が５０．０μΩ・ｃｍ以下の材料が好ましい。 Peak intensity ratio Z = (XRD peak intensity due to (002) plane) / (XRD peak intensity due to (004) plane) (1)
The back electrode 6 is made of Au (gold), Ag (silver), Al (aluminum), Cu (copper), Ti (titanium), W (tungsten), Ni (nickel), etc., and has an electrical resistivity at room temperature. A material of 50.0 μΩ · cm or less is preferable.

透明電極２の膜厚は、例えば５００〜１０００ｎｍであり、第１の光起電力素子３の膜厚は例えば０．３μｍであり、ｐ型非晶質シリコンカーバイド膜３１の膜厚は例えば２０ｎｍであり、ｉ型非晶質シリコン膜３２の膜厚は例えば２００〜２５０ｎｍであり、ｎ型非晶質シリコン膜３３の膜厚は例えば３０ｎｍであるが、これらに限られない。   The film thickness of the transparent electrode 2 is, for example, 500 to 1000 nm, the film thickness of the first photovoltaic element 3 is, for example, 0.3 μm, and the film thickness of the p-type amorphous silicon carbide film 31 is, for example, 20 nm. The thickness of the i-type amorphous silicon film 32 is, for example, 200 to 250 nm, and the thickness of the n-type amorphous silicon film 33 is, for example, 30 nm, but is not limited thereto.

また、反射膜４の膜厚は例えば２０ｎｍであり、第２の光起電力素子５の膜厚は例えば１．５μｍであり、ｐ型微結晶シリコン膜５１の膜厚は例えば２０ｎｍであり、ｉ型微結晶シリコン膜５２の膜厚は例えば１４００〜１５００ｎｍであり、ｎ型微結晶シリコン膜５３の膜厚は例えば３０ｎｍであり、裏面電極６の膜厚は例えば３００ｎｍであるが、これらに限られない。   The thickness of the reflective film 4 is, for example, 20 nm, the thickness of the second photovoltaic element 5 is, for example, 1.5 μm, the thickness of the p-type microcrystalline silicon film 51 is, for example, 20 nm, and i The thickness of the type microcrystalline silicon film 52 is, for example, 1400 to 1500 nm, the thickness of the n-type microcrystalline silicon film 53 is, for example, 30 nm, and the thickness of the back electrode 6 is, for example, 300 nm. Absent.

次に、光起電力素子１００の製造方法について説明する。まず、チャンバ内で支持基板１上に熱ＣＶＤ（化学蒸着）法により透明電極２を形成する。   Next, a method for manufacturing the photovoltaic element 100 will be described. First, the transparent electrode 2 is formed on the support substrate 1 in the chamber by a thermal CVD (chemical vapor deposition) method.

次いで、真空チャンバ内にＳｉＨ4 （シラン）ガス、Ｈ2 （水素）ガス、Ｂ2 Ｈ6 （ジボラン）ガスおよびＣＨ4 （メタン）ガスを導入し、プラズマＣＶＤ法により透明電極２上にｐ型非晶質シリコンカーバイド膜３１を形成する。続いて、真空チャンバ内にＳｉＨ4 ガスおよびＨ2 ガスを導入し、ｐ型非晶質シリコンカーバイド膜３１上にプラズマＣＶＤ法によりｉ型非晶質シリコン膜３２を形成する。続いて、真空チャンバ内にＳｉＨ4 ガス、Ｈ2 ガスおよびＰＨ3 ガスを導入し、ｉ型非晶質シリコン膜３２上にプラズマＣＶＤ法によりｎ型非晶質シリコン膜３３を形成する。 Next, SiH 4 (silane) gas, H 2 (hydrogen) gas, B 2 H 6 (diborane) gas and CH 4 (methane) gas are introduced into the vacuum chamber, and p-type is formed on the transparent electrode 2 by plasma CVD. An amorphous silicon carbide film 31 is formed. Subsequently, SiH 4 gas and H 2 gas are introduced into the vacuum chamber, and an i-type amorphous silicon film 32 is formed on the p-type amorphous silicon carbide film 31 by plasma CVD. Subsequently, SiH 4 gas, H 2 gas and PH 3 gas are introduced into the vacuum chamber, and an n-type amorphous silicon film 33 is formed on the i-type amorphous silicon film 32 by plasma CVD.

次に、スパッタリング法により、反射膜４を形成する。スパッタガスにはＡｒ（アルゴン）等の不活性ガスを用い、ターゲットにはＺｎＯを用いる。ＺｎＯの成膜温度（基板温度）は、１００℃〜１５０℃程度が好ましい。   Next, the reflective film 4 is formed by sputtering. An inert gas such as Ar (argon) is used as the sputtering gas, and ZnO is used as the target. The deposition temperature (substrate temperature) of ZnO is preferably about 100 ° C to 150 ° C.

次いで、真空チャンバ内にＳｉＨ4 ガス、Ｈ2 ガスおよびＢ2 Ｈ6 ガスを導入し、反射膜４上にプラズマＣＶＤ法によりｐ型微結晶シリコン膜５１を形成する。続いて、真空チャンバ内にＳｉＨ4 ガスおよびＨ2 ガスを導入して、ｐ型微結晶シリコン膜５１上にプラズマＣＶＤ法によりｉ型微結晶シリコン膜５２を形成する。続いて、真空チャンバ内にＳｉＨ4 ガス、Ｈ2 ガスおよびＰＨ3 ガスを導入し、ｉ型微結晶シリコン膜５２上にプラズマＣＶＤ法によりｎ型微結晶シリコン膜５３を形成する。次に、スパッタリング法により、裏面電極６を形成する。 Next, SiH 4 gas, H 2 gas, and B 2 H 6 gas are introduced into the vacuum chamber, and a p-type microcrystalline silicon film 51 is formed on the reflective film 4 by plasma CVD. Subsequently, SiH 4 gas and H 2 gas are introduced into the vacuum chamber, and an i-type microcrystalline silicon film 52 is formed on the p-type microcrystalline silicon film 51 by plasma CVD. Subsequently, SiH 4 gas, H 2 gas and PH 3 gas are introduced into the vacuum chamber, and an n-type microcrystalline silicon film 53 is formed on the i-type microcrystalline silicon film 52 by plasma CVD. Next, the back electrode 6 is formed by sputtering.

図２（ａ）および図２（ｂ）は、ＺｎＯの（００２）面および（００４）面のＸＲＤピーク強度の一例を示す図である。図２（ｂ）は、図２（ａ）の縦軸のスケールを拡大させたものである。   FIGS. 2A and 2B are diagrams showing examples of XRD peak intensities of the (002) plane and the (004) plane of ZnO. FIG. 2B is an enlarged scale of the vertical axis of FIG.

図２（ａ）および図２（ｂ）の縦軸はＸＲＤピーク強度を示し、図２（ａ）および図２（ｂ）の横軸はＸ線の入射角度を示す。   2A and 2B, the vertical axis indicates the XRD peak intensity, and the horizontal axis in FIGS. 2A and 2B indicates the X-ray incident angle.

図２（ａ）および図２（ｂ）に示すように、ＺｎＯは、Ｘ線の入射角度２θ＝３４．３４度で（００２）面によるピークが存在し、Ｘ線の入射角度２θ＝７２．４７度で（００４）面によるピークが存在する。   As shown in FIGS. 2A and 2B, ZnO has a peak due to the (002) plane at an X-ray incident angle 2θ = 34.34 degrees, and an X-ray incident angle 2θ = 72. There is a peak due to the (004) plane at 47 degrees.

本実施の形態に係る光起電力素子１００においては、上記のように、反射膜４として上式（１）で示されるピーク強度比Ｚが２以下であるＺｎＯを用いる。   In the photovoltaic device 100 according to the present embodiment, as described above, ZnO having a peak intensity ratio Z represented by the above formula (1) of 2 or less is used as the reflective film 4.

本実施の形態に係る光起電力素子１００においては、第１の光起電力素子３と第２の光起電力素子５との間に反射膜４が設けられているため、入射光の一部が反射膜４により反射して第１の光起電力素子３に入射するフォトン数が増加する。それにより、第１の光起電力素子３で発生する光電流が増加する。   In the photovoltaic element 100 according to the present embodiment, since the reflective film 4 is provided between the first photovoltaic element 3 and the second photovoltaic element 5, a part of the incident light The number of photons reflected by the reflective film 4 and incident on the first photovoltaic element 3 increases. Thereby, the photocurrent generated in the first photovoltaic element 3 increases.

したがって、第１の光起電力素子３の膜厚を低減させることができる。その結果、第１の光起電力素子３における光劣化率を低減させることができるため、光起電力素子１００全体の光劣化率が低減し、変換効率が向上する。   Therefore, the film thickness of the first photovoltaic element 3 can be reduced. As a result, since the light deterioration rate in the first photovoltaic element 3 can be reduced, the light deterioration rate of the entire photovoltaic element 100 is reduced, and the conversion efficiency is improved.

また、反射膜４に用いるＺｎＯのピーク強度比Ｚが２以下であることから、反射膜４とｐ型微結晶シリコン膜５１との間の接合特性に影響を及ぼさない。それにより、光起電力素子１００の直列抵抗は増加しない。   Further, since the peak intensity ratio Z of ZnO used for the reflective film 4 is 2 or less, the junction characteristics between the reflective film 4 and the p-type microcrystalline silicon film 51 are not affected. Thereby, the series resistance of the photovoltaic element 100 does not increase.

以上のことから、本実施の形態に係る光起電力素子１００においては、変換効率が最大限に向上される。   From the above, in the photovoltaic device 100 according to the present embodiment, the conversion efficiency is improved to the maximum.

なお、本実施の形態のｎ型非晶質シリコン膜３３およびｎ型微結晶シリコン膜５３には不純物としてＰ（リン）をドープしたが、それに限られない。例えば、不純物としてＡｓ（ヒ素）等のＶ族元素を不純物としてドープしてもよい。   Although the n-type amorphous silicon film 33 and the n-type microcrystalline silicon film 53 of this embodiment are doped with P (phosphorus) as an impurity, the present invention is not limited to this. For example, a V group element such as As (arsenic) may be doped as an impurity.

また、ｐ型非晶質シリコンカーバイド膜３１およびｐ型微結晶シリコン膜５１には不純物としてＢ（ボロン）をドープしたが、それに限られない。例えば、Ａｌ（アルミニウム）、Ｇａ（ガリウム）等のIII 族元素を不純物としてドープしてもよい。   The p-type amorphous silicon carbide film 31 and the p-type microcrystalline silicon film 51 are doped with B (boron) as an impurity, but are not limited thereto. For example, a group III element such as Al (aluminum) or Ga (gallium) may be doped as an impurity.

また、ｎ型非晶質シリコン膜３１、ｉ型非晶質シリコン膜３２およびｎ型非晶質シリコン膜３３は微結晶シリコンを含んでもよい。   The n-type amorphous silicon film 31, the i-type amorphous silicon film 32, and the n-type amorphous silicon film 33 may contain microcrystalline silicon.

また、本実施の形態のｐ型非晶質シリコンカーバイド膜３１、ｉ型非晶質シリコン膜３２、ｎ型非晶質シリコン膜３３、ｐ型微結晶シリコン膜５１、ｉ型微結晶シリコン膜５２およびｎ型微結晶シリコン膜５３の代わりに、例えば、ＳｉＣ（炭化シリコン）、ＳｉＧｅ（シリコンゲルマニウム）、Ｇｅ（ゲルマニウム）等のような他のＩＶ族元素を用いてもよい。   In addition, the p-type amorphous silicon carbide film 31, the i-type amorphous silicon film 32, the n-type amorphous silicon film 33, the p-type microcrystalline silicon film 51, and the i-type microcrystalline silicon film 52 of the present embodiment. Instead of the n-type microcrystalline silicon film 53, other group IV elements such as SiC (silicon carbide), SiGe (silicon germanium), Ge (germanium), etc. may be used.

また、反射膜４に用いるＺｎＯとしては、不純物としてＢ（ボロン），Ａｌ（アルミニウム），Ｇａ（ガリウム）がドープされたものを用いてもよい。   Moreover, as ZnO used for the reflective film 4, you may use what doped B (boron), Al (aluminum), and Ga (gallium) as an impurity.

また、ｉ型微結晶シリコン膜５２を形成せずに、ｐ型微結晶シリコン膜上にｎ型微結晶シリコン膜が形成されてもよい。   Alternatively, an n-type microcrystalline silicon film may be formed on the p-type microcrystalline silicon film without forming the i-type microcrystalline silicon film 52.

（第２の実施の形態）
図３は、第２の実施の形態に係る光起電力素子１００ａの構造を示す模式的断面図である。 (Second Embodiment)
FIG. 3 is a schematic cross-sectional view showing the structure of the photovoltaic element 100a according to the second embodiment.

図３に示すように、支持基板１上に、裏面電極６、微結晶シリコン膜を光活性層に用いる第２の光起電力素子５、反射膜４、非晶質シリコンを光活性層に用いる第１の光起電力素子３および透明電極２が順に形成されている。   As shown in FIG. 3, on the support substrate 1, a back electrode 6, a second photovoltaic element 5 using a microcrystalline silicon film as a photoactive layer, a reflective film 4, and amorphous silicon are used as a photoactive layer. The 1st photovoltaic element 3 and the transparent electrode 2 are formed in order.

第１の光起電力素子３は、反射膜４側からｎ型非晶質シリコン膜３３、ｉ型非晶質シリコン膜３２およびｐ型非晶質シリコンカーバイド膜３１を順に含む。第２の光起電力素子５は、裏面電極６側からｎ型微結晶シリコン膜５３、ｉ型微結晶シリコン膜５２およびｐ型微結晶シリコン膜５１を順に含む。図３の光起電力素子１００ａにおいては、透明電極２が受光面である。   The first photovoltaic element 3 includes an n-type amorphous silicon film 33, an i-type amorphous silicon film 32, and a p-type amorphous silicon carbide film 31 in this order from the reflective film 4 side. The second photovoltaic element 5 includes an n-type microcrystalline silicon film 53, an i-type microcrystalline silicon film 52, and a p-type microcrystalline silicon film 51 in this order from the back electrode 6 side. In the photovoltaic element 100a of FIG. 3, the transparent electrode 2 is a light receiving surface.

本実施の形態に係る光起電力素子１００ａにおいても、上記のように、反射膜４として上式（１）で示されるピーク強度比Ｚが２以下であるＺｎＯを用いる。   Also in the photovoltaic device 100a according to the present embodiment, ZnO having a peak intensity ratio Z represented by the above formula (1) of 2 or less is used as the reflective film 4 as described above.

本実施の形態に係る光起電力素子１００ａにおいては、第１の光起電力素子３と第２の光起電力素子５との間に反射膜４が設けられているため、入射光の一部が反射膜４により反射して第１の光起電力素子３に入射するフォトン数が増加する。それにより、第１の光起電力素子３で発生する光電流が増加する。   In the photovoltaic element 100a according to the present embodiment, since the reflective film 4 is provided between the first photovoltaic element 3 and the second photovoltaic element 5, a part of the incident light The number of photons reflected by the reflective film 4 and incident on the first photovoltaic element 3 increases. Thereby, the photocurrent generated in the first photovoltaic element 3 increases.

したがって、第１の光起電力素子３の膜厚を低減させることができる。その結果、第１の光起電力素子３における光劣化率を低減させることができるため、光起電力素子１００全体の光劣化率が低減し、変換効率が向上する。   Therefore, the film thickness of the first photovoltaic element 3 can be reduced. As a result, since the light deterioration rate in the first photovoltaic element 3 can be reduced, the light deterioration rate of the entire photovoltaic element 100 is reduced, and the conversion efficiency is improved.

また、反射膜４に用いるＺｎＯのピーク強度比Ｚが２以下であることから、反射膜４とｐ型微結晶シリコン膜５１との間の接合特性に影響を及ぼさない。それにより、光起電力素子１００ａの直列抵抗は増加しない。   Further, since the peak intensity ratio Z of ZnO used for the reflective film 4 is 2 or less, the junction characteristics between the reflective film 4 and the p-type microcrystalline silicon film 51 are not affected. Thereby, the series resistance of the photovoltaic element 100a does not increase.

以上のことから、本実施の形態に係る光起電力素子１００ａにおいては、変換効率が最大限に向上される。   From the above, in the photovoltaic device 100a according to the present embodiment, the conversion efficiency is improved to the maximum.

以下の実施例１〜３および比較例１，２では図１の光起電力素子を作製し、反射膜４のＸＲＤ強度比Ｚおよび光起電力素子全体の直列抵抗を測定した。   In the following Examples 1 to 3 and Comparative Examples 1 and 2, the photovoltaic elements shown in FIG. 1 were produced, and the XRD intensity ratio Z of the reflective film 4 and the series resistance of the entire photovoltaic elements were measured.

（実施例１〜３）
実施例１〜３では、図１の反射膜４の成膜温度を変えて光起電力素子を作製し、反射膜４の成膜温度およびピーク強度比Ｚが光起電力素子の直列抵抗に及ぼす影響を調べた。実施例１〜３の反射膜４の成膜温度は、それぞれ１００℃、１２０℃および１５０℃とした。また、ターゲットにはＡｌが５ｗｔ％ドープされたＺｎＯを用いた。さらに、圧力は０．７Ｐａであり、スパッタ時の放電電力は６ｋＷとした。実施例１〜３の光起電力素子のその他の作製条件を表１に示す。 (Examples 1-3)
In Examples 1 to 3, photovoltaic elements are manufactured by changing the film formation temperature of the reflective film 4 in FIG. 1, and the film formation temperature and the peak intensity ratio Z of the reflective film 4 affect the series resistance of the photovoltaic elements. The effect was investigated. The film formation temperatures of the reflective films 4 of Examples 1 to 3 were 100 ° C., 120 ° C., and 150 ° C., respectively. Further, ZnO doped with 5 wt% Al was used as a target. Furthermore, the pressure was 0.7 Pa, and the discharge power during sputtering was 6 kW. Table 1 shows other production conditions for the photovoltaic elements of Examples 1 to 3.

Figure 2005108901
Figure 2005108901

（比較例１，２）
比較例１，２では、図１の反射膜４の成膜温度を変えて光起電力素子を作製した。比較例１，２の反射膜４の成膜温度は、それぞれ１８０℃、２４０℃とした。比較例１，２のその他の作製条件は実施例１〜３と同様である。 (Comparative Examples 1 and 2)
In Comparative Examples 1 and 2, photovoltaic elements were fabricated by changing the deposition temperature of the reflective film 4 in FIG. The deposition temperatures of the reflective films 4 of Comparative Examples 1 and 2 were 180 ° C. and 240 ° C., respectively. Other manufacturing conditions of Comparative Examples 1 and 2 are the same as those of Examples 1 to 3.

（評価１）
実施例１〜３および比較例１，２で形成された反射膜４のＺｎＯのピーク強度比Ｚを測定した。図４に実施例１〜３および比較例１，２のピーク強度比Ｚを示す。図４の横軸はＺｎＯの成膜温度を示し、図４の縦軸はピーク強度比Ｚを示す。 (Evaluation 1)
The peak intensity ratio Z of ZnO of the reflective film 4 formed in Examples 1 to 3 and Comparative Examples 1 and 2 was measured. FIG. 4 shows the peak intensity ratio Z of Examples 1 to 3 and Comparative Examples 1 and 2. The horizontal axis in FIG. 4 indicates the ZnO film forming temperature, and the vertical axis in FIG. 4 indicates the peak intensity ratio Z.

図４に示すように、ＺｎＯの成膜温度の増加とともにＺｎＯのピーク強度比Ｚも比例的に増加した。また、実施例１〜３で形成されたＺｎＯのピーク強度比Ｚは２以下となり、比較例１，２で形成されたＺｎＯのピーク強度比Ｚは２を超える値となった。   As shown in FIG. 4, the ZnO peak intensity ratio Z also increased proportionally with increasing ZnO deposition temperature. Moreover, the peak intensity ratio Z of ZnO formed in Examples 1 to 3 was 2 or less, and the peak intensity ratio Z of ZnO formed in Comparative Examples 1 and 2 was a value exceeding 2.

（比較例３）
比較例３では、図１の光起電力素子を作製する際に反射膜４を形成せずに非晶質シリコン膜を光活性層に用いる第１の光起電力素子３上に微結晶シリコン膜を光活性層に用いる第２の光起電力素子５を形成した。その他の作製条件は、実施例１〜３と同様である。 (Comparative Example 3)
In Comparative Example 3, a microcrystalline silicon film is formed on the first photovoltaic element 3 that uses an amorphous silicon film as a photoactive layer without forming the reflective film 4 when producing the photovoltaic element of FIG. A second photovoltaic element 5 using the above in the photoactive layer was formed. Other manufacturing conditions are the same as in Examples 1 to 3.

（評価２）
実施例１〜３および比較例１〜３の光起電力素子の直列抵抗を測定した。図５に実施例１〜３および比較例１〜３の光起電力素子の直列抵抗を示す。図５の横軸は、ピーク強度比Ｚを示す。図５の縦軸は、比較例３の光起電力素子の直列抵抗を１として規格化した場合の実施例１〜３および比較例１，２の光起電力素子の直列抵抗の値を示す。 (Evaluation 2)
The series resistance of the photovoltaic elements of Examples 1 to 3 and Comparative Examples 1 to 3 was measured. FIG. 5 shows the series resistance of the photovoltaic elements of Examples 1 to 3 and Comparative Examples 1 to 3. The horizontal axis of FIG. 5 shows the peak intensity ratio Z. The vertical axis in FIG. 5 indicates the value of the series resistance of the photovoltaic elements of Examples 1 to 3 and Comparative Examples 1 and 2 when the series resistance of the photovoltaic element of Comparative Example 3 is normalized as 1.

図５に示すように、ピーク強度比Ｚが２以下であれば、直列抵抗は比較例３と変わらなかったが、ピーク強度比が２を超える比較例１，２の光起電力素子は直列抵抗が大きく増加した。   As shown in FIG. 5, when the peak intensity ratio Z is 2 or less, the series resistance is the same as that of Comparative Example 3, but the photovoltaic elements of Comparative Examples 1 and 2 having a peak intensity ratio of more than 2 are series resistance. Increased significantly.

以上のことから、ＺｎＯの成膜温度を変化させることによりＺｎＯのピーク強度比が変化し、ピーク強度比Ｚが２以下であれば光起電力素子の直列抵抗が増大しないことがわかった。   From the above, it was found that the peak intensity ratio of ZnO was changed by changing the deposition temperature of ZnO, and that the series resistance of the photovoltaic device would not increase if the peak intensity ratio Z was 2 or less.

これは、ピーク強度比が２を超えると、ＺｎＯの結晶性が高まり熱膨張係数が低くなるため、反射膜４とｐ型微結晶シリコン膜５１との接合界面において内部応力によるひずみが大きくなるためであると考えられる。   This is because when the peak intensity ratio exceeds 2, the crystallinity of ZnO increases and the thermal expansion coefficient decreases, so that strain due to internal stress increases at the junction interface between the reflective film 4 and the p-type microcrystalline silicon film 51. It is thought that.

以上のように、本発明に係る光起電力素子においては、反射膜４とｐ型微結晶シリコン膜５１との接合特性を改善することができる。したがって、本発明に係る光起電力素子は、半導体接合を用いた光起電力素子およびその製造する用途に適している。   As described above, in the photovoltaic device according to the present invention, the junction characteristics between the reflective film 4 and the p-type microcrystalline silicon film 51 can be improved. Therefore, the photovoltaic device according to the present invention is suitable for a photovoltaic device using a semiconductor junction and an application for manufacturing the photovoltaic device.

第１の実施の形態に係る光起電力素子の構造を示す模式的断面図である。It is typical sectional drawing which shows the structure of the photovoltaic element which concerns on 1st Embodiment. ＺｎＯの（００２）面および（００４）面のＸＲＤピーク強度の一例を示す図である。It is a figure which shows an example of the XRD peak intensity of the (002) plane and (004) plane of ZnO. 第２の実施の形態に係る光起電力素子の構造を示す模式的断面図である。It is typical sectional drawing which shows the structure of the photovoltaic element which concerns on 2nd Embodiment. 実施例１〜３および比較例１，２のピーク強度比Ｚを示す図である。It is a figure which shows the peak intensity ratio Z of Examples 1-3 and Comparative Examples 1 and 2. FIG. 実施例１〜３および比較例１〜３の光起電力素子の直列抵抗を示す図である。It is a figure which shows the series resistance of the photovoltaic element of Examples 1-3 and Comparative Examples 1-3.

符号の説明Explanation of symbols

１ 支持基板
２ 透明電極
３ 第１の光起電力素子
４ 反射膜
５ 第２の光起電力素子
６ 裏面電極
３１ ｐ型非晶質シリコンカーバイド膜
３２ ｉ型非晶質シリコン膜
３３ ｎ型非晶質シリコン膜
５１ ｐ型微結晶シリコン膜
５２ ｉ型微結晶シリコン膜
５３ ｎ型微結晶シリコン膜
１００ 光起電力素子
DESCRIPTION OF SYMBOLS 1 Support substrate 2 Transparent electrode 3 1st photovoltaic element 4 Reflective film 5 2nd photovoltaic element 6 Back surface electrode 31 p-type amorphous silicon carbide film 32 i-type amorphous silicon film 33 n-type amorphous Silicon film 51 p-type microcrystalline silicon film 52 i-type microcrystalline silicon film 53 n-type microcrystalline silicon film 100 photovoltaic device

Claims (4)

一面および他面を有し入射光を反射する反射膜を備え、
前記反射膜の前記一面側に、半導体膜を光活性層に用いる第１の光起電力素子を備え、
前記反射膜の前記他面側に、微結晶半導体膜を光活性層に用いる第２の光起電力素子を備え、
前記反射膜の前記一面を受光面側とするとともに、
前記反射膜の（００２）面におけるＸ線回折強度のピーク値が前記反射膜の（００４）面におけるＸ線回折強度のピーク値の２倍以下であることを特徴とする光起電力素子。 A reflective film having one side and the other side to reflect incident light;
A first photovoltaic element using a semiconductor film as a photoactive layer on the one surface side of the reflective film;
A second photovoltaic element using a microcrystalline semiconductor film as a photoactive layer on the other surface side of the reflective film;
While the one surface of the reflective film is the light receiving surface side,
The photovoltaic element, wherein the peak value of the X-ray diffraction intensity on the (002) plane of the reflective film is not more than twice the peak value of the X-ray diffraction intensity on the (004) plane of the reflective film. 前記第１の光起電力素子は、非晶質系半導体膜を光活性層に用いることを特徴とする請求項１記載の光起電力素子。 2. The photovoltaic element according to claim 1, wherein the first photovoltaic element uses an amorphous semiconductor film as a photoactive layer. 前記反射膜は、酸化亜鉛からなることを特徴とする請求項１または２記載の光起電力素子。 The photovoltaic element according to claim 1, wherein the reflective film is made of zinc oxide. 一面および他面を有し、入射光を反射し、（００２）面におけるＸ線回折強度のピーク値が（００４）面におけるＸ線回折強度のピーク値の２倍以下である反射膜を形成する工程と、
前記反射膜の受光面側となる前記一面側に、半導体膜を光活性層に用いる第１の光起電力素子を形成する工程と、
前記反射膜の前記他面側に、微結晶半導体膜を光活性層に用いる第２の光起電力素子を形成する工程とを備えたことを特徴とする光起電力素子の製造方法。


A reflective film having one surface and the other surface that reflects incident light and has a peak value of X-ray diffraction intensity on the (002) plane that is less than or equal to twice the peak value of X-ray diffraction intensity on the (004) plane is formed. Process,
Forming a first photovoltaic element using a semiconductor film as a photoactive layer on the one surface side which is a light receiving surface side of the reflective film;
Forming a second photovoltaic element using a microcrystalline semiconductor film as a photoactive layer on the other surface side of the reflective film. A method for producing a photovoltaic element, comprising:


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CN102157575A (en) * 2011-03-28 2011-08-17 天津师范大学 Novel transparent conducting oxide thin film with multi-layer film structure and manufacturing method thereof
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JP2006310503A (en) * 2005-04-28 2006-11-09 Sanyo Electric Co Ltd Laminate type photovoltaic device
EP1717868A3 (en) * 2005-04-28 2015-03-04 Sanyo Electric Co., Ltd. Stacked photovoltaic device
JP2007012833A (en) * 2005-06-30 2007-01-18 Sanyo Electric Co Ltd Stacked photovoltaic device
JP4688589B2 (en) * 2005-06-30 2011-05-25 三洋電機株式会社 Stacked photovoltaic device
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