JPH11261092A - Manufacture of rugged electrode, photovoltaic element and its manufacture - Google Patents
Manufacture of rugged electrode, photovoltaic element and its manufactureInfo
- Publication number
- JPH11261092A JPH11261092A JP10060908A JP6090898A JPH11261092A JP H11261092 A JPH11261092 A JP H11261092A JP 10060908 A JP10060908 A JP 10060908A JP 6090898 A JP6090898 A JP 6090898A JP H11261092 A JPH11261092 A JP H11261092A
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- JP
- Japan
- Prior art keywords
- amorphous semiconductor
- semiconductor layer
- electrode
- layer
- region
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Classifications
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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
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- Photovoltaic Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、凹凸電極の製造
方法及び光起電力素子の製造方法並びに光起電力素子に
関し、特に薄膜光起電力装置の変換効率向上において重
要である光閉じ込め技術に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a concavo-convex electrode, a method for manufacturing a photovoltaic device, and a photovoltaic device.
【０００２】[0002]
【従来の技術】現在、高効率非晶質シリコン（以下、ａ
−Ｓｉという。）光起電力装置に一般的に用いられてい
る光閉じ込め技術は、ガラス基板上の透明電極に凹凸を
持たせており、光を基板側から入射する構造になってい
る（１９９４年５月２０日アドバンスト エレクトロニ
クス１−３ 太陽エネルギー工学：培風館１６３頁）。
即ち、図７に示すように、ガラス基板２１上に表面に凹
凸を有するＳｎＯ2などの透明電極（ＴＣＯ）２２が形
成され、その上にｐ型ａ−Ｓｉ膜２３、ｉ型ａ−Ｓｉ膜
２４及びｎ型ａ−Ｓｉ膜２５がこの順に積層形成され、
更にこの上に裏面金属電極２７が形成されている。2. Description of the Related Art At present, highly efficient amorphous silicon (hereinafter referred to as a
-Si. A light confinement technique generally used for a photovoltaic device has a structure in which light is incident from the substrate side by giving irregularities to a transparent electrode on a glass substrate (May 20, 1994). Japan Advanced Electronics 1-3 Solar Energy Engineering: Baifukan 163 pages).
That is, as shown in FIG. 7, a transparent electrode (TCO) 22 such as SnO 2 having an uneven surface is formed on a glass substrate 21, and a p-type a-Si film 23 and an i-type a-Si film are formed thereon. 24 and an n-type a-Si film 25 are laminated in this order,
Further, a back metal electrode 27 is formed thereon.
【０００３】上記したように、高効率ａ−Ｓｉ光起電力
装置に一般的に用いられている光閉じ込め技術は、ガラ
ス基板２１上の透明電極２２に凹凸を持たせており、光
を基板２１側から入射させる構造となっている。ここ
で、透明電極２２の凹凸形状の一傾斜面である水平面に
対する傾斜角度（３０度）の面を抽出した場合、入射光
の進行方向の変化は図８に示すスネルの法則に従い、下
表１の一般的な光学定数を用いれば１０°〜２０°程度
の範囲に過ぎない。As described above, a light confinement technique generally used in a high-efficiency a-Si photovoltaic device has a structure in which a transparent electrode 22 on a glass substrate 21 has irregularities so that light is emitted from the substrate 21. It is structured to be incident from the side. Here, when a plane having an inclination angle (30 degrees) with respect to the horizontal plane, which is one inclined surface of the uneven shape of the transparent electrode 22, is extracted, the change in the traveling direction of the incident light follows Snell's law shown in FIG. If the general optical constant of is used, it is only in the range of about 10 ° to 20 °.
【０００４】[0004]
【表１】 [Table 1]
【０００５】この原因は、透明電極２２の凹凸形状によ
る光閉じ込め効果は、透明電極２２とａ−Ｓｉ層２３の
界面を光が透過することによる屈折効果であるためであ
る。これに対して、ａ−Ｓｉ層２５と裏面金属電極２７
との界面に凹凸を設けた場合には、反射による散乱のた
めより大きな進行方向の変化、極端に言えば、図９に示
すような真横方向の散乱等が可能となる。これにより、
透明電極２２とガラス基板１との界面への凹凸構造形成
に比べより大きな光閉じ込め効果を期待することができ
る。The reason for this is that the light confinement effect due to the uneven shape of the transparent electrode 22 is a refraction effect due to the transmission of light at the interface between the transparent electrode 22 and the a-Si layer 23. On the other hand, the a-Si layer 25 and the back metal electrode 27
In the case where unevenness is provided at the interface with the substrate, a larger change in the traveling direction due to scattering due to reflection, more specifically, scattering in the lateral direction as shown in FIG. 9 becomes possible. This allows
A larger light confinement effect can be expected as compared with the formation of a concavo-convex structure at the interface between the transparent electrode 22 and the glass substrate 1.
【０００６】上記したようなａ−Ｓｉ層と裏面金属電極
との界面の凹凸形状に関して、極めて単純なモデルを用
いたシミュレーション報告を除き（Ｔ．Ｓａｗａｄａ
ｅｔａｌ．；Ｃｏｎｆｅｒｅｎｃｅ Ｒｅｃｏｒｄ ｏ
ｆ ｔｈｅ ２３ｒｄ ＩＥＥＥ Ｐｈｏｔｏｖｏｌｔ
ａｉｃ Ｓｐｅｃｉａｌｉｓｔｓ Ｃｏｎｆｅｒｅｎｃ
ｅ（１９９３）参照）、理論的に理想的な形状を予測し
たものは見られないのが現状である。[0006] Regarding the irregular shape of the interface between the a-Si layer and the back metal electrode as described above, except for a simulation report using an extremely simple model (T. Sawada)
et al. ; Conference Record o
f the 23rd IEEE Photovoltt
aic Specialists Conferenc
e (see 1993)), the current situation is that no theoretically predicted shape has been predicted.
【０００７】しかし、一般的には図１０に示すように、
ａ−Ｓｉ層２５と裏面金属電極２７との界面に透明電極
からなる拡散防止層２６を設け、この拡散防止層２６の
凹凸形状における高低差を発電に寄与する波長と同程
度、即ち、０．４μｍ〜１．０μｍのサブミクロン（μ
ｍ）オーダーにすると共に、拡散防止層２６内における
光吸収を抑制するために、この膜を極力薄膜化すること
が必要であると考えられている。However, generally, as shown in FIG.
A diffusion prevention layer 26 made of a transparent electrode is provided at the interface between the a-Si layer 25 and the back metal electrode 27, and the height difference in the uneven shape of the diffusion prevention layer 26 is almost equal to the wavelength contributing to power generation, that is, 0. 4 μm to 1.0 μm submicron (μ
It is considered that it is necessary to reduce the thickness of this film as much as possible in order to achieve the order of m) and to suppress light absorption in the diffusion prevention layer 26.
【０００８】[0008]
【発明が解決しようとする課題】従来、ａ−Ｓｉ層と裏
面金属電極との界面に形成する拡散防止層としての透明
電極膜は蒸着、或いはスパッタ法によって形成されてい
る。このため、下地層の形状を強く反映し、ガラス基板
２１上に最初に形成される透明電極２２の凹凸形状の複
製或いはこれより平坦化された構造とならざるを得な
く、発電に寄与する好ましい形状の凹凸を形成すること
ができないと言う問題があった。Conventionally, a transparent electrode film as a diffusion preventing layer formed at the interface between the a-Si layer and the back metal electrode has been formed by vapor deposition or sputtering. For this reason, it is necessary to strongly reflect the shape of the underlying layer and to form a structure in which the concave and convex shape of the transparent electrode 22 first formed on the glass substrate 21 is duplicated or flattened, which contributes to power generation. There was a problem that it was not possible to form irregularities in the shape.
【０００９】また、特開平８−３０６９４４号公報に
は、良好な光散乱効果と裏面での反射効果とを合わせ持
たせた薄膜太陽電池が提案されている。この太陽電池
は、図１１に示すように、ａ−Ｓｉ層の裏面側に位置す
るｎ層の成膜条件を極端な希釈化条件、例えば、ＳｉＨ
4とＨ2との流量比を１：１０以上にすることにより、ｉ
層２４における凹凸形状よりも大きい光散乱用の凹凸形
状を有する非晶質シリコンまたは微結晶シリコン層から
なるｎ層２５ａを形成するものである。Japanese Patent Application Laid-Open No. Hei 8-306944 proposes a thin-film solar cell having both a good light scattering effect and a reflection effect on the back surface. In this solar cell, as shown in FIG. 11, the film forming conditions of the n-layer located on the back side of the a-Si layer are changed to extreme dilution conditions, for example, SiH
By making the flow ratio of 4 to H 2 1:10 or more, i
This is to form an n-layer 25a made of an amorphous silicon or microcrystalline silicon layer having an uneven shape for light scattering larger than the uneven shape of the layer 24.
【００１０】しかしながら、上記方法においても、ｎ層
２５ａが均質なｉ型ａ−Ｓｉ層２４の上に形成される膜
厚数１００Å程度の膜であることから、その凹凸の高低
差には制限があった。However, also in the above method, since the n-layer 25a is a film having a thickness of about several hundreds of degrees formed on the uniform i-type a-Si layer 24, the height difference of the unevenness is limited. there were.
【００１１】この発明は、上述した従来の問題点に鑑み
なされたものにして、光閉じ込め効果に最適な凹凸を有
する凹凸電極及びそれを備えた光起電力素子を提供する
ことを目的とする。SUMMARY OF THE INVENTION The present invention has been made in consideration of the above-described conventional problems, and has as its object to provide a concavo-convex electrode having irregularities optimal for a light confinement effect and a photovoltaic element including the same.
【００１２】[0012]
【課題を解決するための手段】この発明は、表面に凹凸
形状を有する凹凸電極を形成する凹凸電極の製造方法で
あって、非晶質半導体層にエネルギービームを照射し、
前記非晶質半導体層の一部に結晶核領域を形成した後、
前記非晶質半導体層上に結晶性電極を形成することで表
面に凹凸形状を有する凹凸電極を形成することを特徴と
する。SUMMARY OF THE INVENTION The present invention relates to a method for manufacturing an uneven electrode for forming an uneven electrode having an uneven surface, wherein the method comprises irradiating an amorphous semiconductor layer with an energy beam.
After forming a crystal nucleus region in a part of the amorphous semiconductor layer,
An uneven electrode having an uneven surface is formed by forming a crystalline electrode on the amorphous semiconductor layer.
【００１３】上記した構成によれば、非晶質半導体の一
部に形成された結晶核領域が結晶性電極を形成する際の
結晶成長核となり、粒径の大きな結晶性電極を形成する
ことができ、サブμｍオーダーの凹凸形状を光閉じ込め
効果に最適な凹凸電極が得られる。しかも、凹凸電極を
低温で形成できるため、基板に耐熱性の劣る基板を用い
ることができる。According to the above configuration, the crystal nucleus region formed in a part of the amorphous semiconductor becomes a crystal growth nucleus when forming a crystalline electrode, and a crystalline electrode having a large grain size can be formed. As a result, an uneven electrode optimal for the light confinement effect of the uneven shape on the order of sub-μm can be obtained. In addition, since the uneven electrode can be formed at a low temperature, a substrate having poor heat resistance can be used.
【００１４】また、この発明の光起電力素子の製造方法
は、基板上に光入射側電極、非晶質半導体層及び金属電
極を順次形成してなる光起電力素子の製造方法であっ
て、前記非晶質半導体層にエネルギービームを照射し、
非晶質半導体層の一部に結晶核領域を形成した後、この
非晶質半導体層上に凹凸形状を有する透光性の結晶性薄
膜を形成し、この薄膜上に凹凸形状を有する金属電極を
形成することを特徴とする。Further, a method of manufacturing a photovoltaic element according to the present invention is a method of manufacturing a photovoltaic element, comprising forming a light incident side electrode, an amorphous semiconductor layer and a metal electrode on a substrate in order. Irradiating the amorphous semiconductor layer with an energy beam;
After forming a crystal nucleus region in a part of the amorphous semiconductor layer, a light-transmitting crystalline thin film having an uneven shape is formed on the amorphous semiconductor layer, and a metal electrode having an uneven shape is formed on the thin film. Is formed.
【００１５】上記した構成によれば、非晶質半導体の一
部に形成された結晶核領域が結晶性電極を形成する際の
結晶成長核となり、粒径の大きな透光性の結晶性薄膜を
形成することができる。そして、この上に形成される金
属電極にサブμｍオーダーの凹凸形状が形成でき、光閉
じ込め効果に優れた光起電力素子が得られる。According to the above configuration, the crystal nucleus region formed in a part of the amorphous semiconductor becomes a crystal growth nucleus when forming a crystalline electrode, and a light-transmitting crystalline thin film having a large grain size is formed. Can be formed. Then, the metal electrodes formed thereon can be formed with sub-micron-order irregularities, and a photovoltaic element having an excellent light confinement effect can be obtained.
【００１６】また、この発明の光起電力素子の製造方法
は、基板上に裏面電極、非晶質半導体層及び光入射側電
極を順次形成する光起電力素子の製造方法であって、前
記基板上に非晶質半導体層を形成し、この非晶質半導体
層にエネルギービームを照射することで前記非晶質半導
体層の一部に結晶核領域を形成した後、この非晶質半導
体層上に結晶性裏面電極を形成することを特徴とする。Further, a method of manufacturing a photovoltaic element according to the present invention is a method of manufacturing a photovoltaic element in which a back electrode, an amorphous semiconductor layer, and a light incident side electrode are sequentially formed on a substrate. An amorphous semiconductor layer is formed thereon, and a crystal nucleus region is formed in a part of the amorphous semiconductor layer by irradiating the amorphous semiconductor layer with an energy beam. And forming a crystalline back electrode thereon.
【００１７】上記した構成によれば、いわゆる逆タイプ
の光起電力素子おいて、最適な光閉じ込め効果を有する
金属電極を備えた素子が容易に得られる。According to the above-described structure, a so-called reverse type photovoltaic element having a metal electrode having an optimum light confinement effect can be easily obtained.
【００１８】上記した結晶核領域は、前記非晶質半導体
層が結晶化されてなる領域及び／または非晶質半導体層
を構成する非晶質半導体層の微粉末が非晶質半導体層上
に付着してなる領域で構成される。The above-mentioned crystal nucleus region is a region where the amorphous semiconductor layer is crystallized and / or the fine powder of the amorphous semiconductor layer constituting the amorphous semiconductor layer is formed on the amorphous semiconductor layer. It is composed of a region that is attached.
【００１９】この発明の光起電力素子は、基板上に光入
射側電極、非晶質半導体層及び金属電極を順次形成した
光起電力素子であって、前記非晶質半導体層上に、一部
に結晶核領域が形成された結晶粒径制御層が設けられ、
この結晶粒径制御層上に透光性の結晶性薄膜を介して金
属電極が設けられていることを特徴とする。A photovoltaic device according to the present invention is a photovoltaic device in which a light incident electrode, an amorphous semiconductor layer and a metal electrode are sequentially formed on a substrate. A crystal grain size control layer in which a crystal nucleus region is formed in a portion is provided,
A metal electrode is provided on the crystal grain size control layer via a light-transmitting crystalline thin film.
【００２０】また、この発明の光起電力素子は、基板上
に裏面電極、非晶質半導体層及び光入射側電極を順次形
成した光起電力素子であって、前記基板上に一部に結晶
核領域が形成された結晶粒径制御層が設けられ、この結
晶粒径制御層上に結晶性の裏面電極が設けられているこ
とを特徴とする。A photovoltaic element according to the present invention is a photovoltaic element in which a back electrode, an amorphous semiconductor layer and a light incident side electrode are sequentially formed on a substrate, and a crystal is partially formed on the substrate. A crystal grain size control layer in which a nucleus region is formed is provided, and a crystalline back electrode is provided on the crystal grain size control layer.
【００２１】[0021]
【発明の実施の形態】以下、この発明の実施の形態につ
き図面を参照して説明する。図１は、この発明の第１の
実施の形態にかかる光起電力素子の概略構造を示す断面
図である。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a sectional view showing a schematic structure of a photovoltaic device according to a first embodiment of the present invention.
【００２２】図１に示すように、ガラスなどからなる透
光性絶縁性基板１上にサブミクロン（μｍ）オーダの凹
凸が形成されたＳｎＯ2、ＺｎＯ2などからなる透明電極
膜（ＴＣＯ）２が形成されている。この透電極膜２上に
光活性層となるｐ型アモルファスシリコンカーバイドま
たはｐ型微結晶シリコンからなるｐ型ａ−Ｓｉ層３、ｉ
型ａ−Ｓｉ層４、ｎ型アモルファスシリコンまたはｎ型
微結晶シリコンからなるｎ型ａ−Ｓｉ層５が順次プラズ
マＣＶＤ法、光ＣＶＤ法などの気相成長法により形成さ
れている。As shown in FIG. 1, a transparent electrode film (TCO) 2 made of SnO 2 , ZnO 2, etc., having irregularities on the order of submicrons (μm) formed on a translucent insulating substrate 1 made of glass or the like. Are formed. On the transparent electrode film 2, a p-type a-Si layer 3, i made of p-type amorphous silicon carbide or p-type microcrystalline silicon serving as a photoactive layer
A type a-Si layer 4 and an n-type a-Si layer 5 made of n-type amorphous silicon or n-type microcrystalline silicon are sequentially formed by a vapor phase growth method such as a plasma CVD method and a photo CVD method.
【００２３】そして、このｎ型ａ−Ｓｉ層５の表面に
は、レーザ光などのエネルギービームを照射することで
再結晶領域６ａ及び／または微細ａ−Ｓｉ粒子６ｂが付
着した結晶粒径制御層６が形成されている。この結晶粒
径制御層６上に拡散防止層となるＩＴＯ等の結晶性透明
電極層７が設けられる。この結晶性透明電極層７は結晶
粒径制御層６の再結晶領域６ａや微細ａ−Ｓｉ粒子６ｂ
を結晶成長核として成長することから粒径の大きな透明
電極となり、サブμｍオーダーの凹凸形状が形成され
る。そして、この透明電極層７上に銀（Ａｇ）、アルミ
ニウム（Ａｌ）等の裏面金属電極８が設けられ、薄膜光
起電力素子が形成される。The surface of the n-type a-Si layer 5 is irradiated with an energy beam such as a laser beam so that the recrystallized region 6a and / or the fine a-Si particles 6b adhere to the crystal grain size control layer. 6 are formed. On this crystal grain size control layer 6, a crystalline transparent electrode layer 7 of ITO or the like to be a diffusion preventing layer is provided. The crystalline transparent electrode layer 7 includes a recrystallized region 6a of the crystal grain size control layer 6 and fine a-Si particles 6b.
Is grown as a crystal growth nucleus to form a transparent electrode having a large particle size, and a submicron-order unevenness is formed. Then, on the transparent electrode layer 7, a back metal electrode 8 of silver (Ag), aluminum (Al), or the like is provided, and a thin-film photovoltaic element is formed.
【００２４】さて、この発明では、ｎ型ａ−Ｓｉ層５表
面にレーザ光などのエネルギービームを照射することに
より、ａ−Ｓｉ層５を一部溶融し、再結晶化させたり、
或いはａ−Ｓｉ層５の表面に微細ａ−Ｓｉ粒子を再生・
再付着させることで結晶粒径制御層６を形成する。In the present invention, by irradiating the surface of the n-type a-Si layer 5 with an energy beam such as a laser beam, the a-Si layer 5 is partially melted and recrystallized.
Alternatively, fine a-Si particles are reproduced on the surface of the a-Si layer 5.
The crystal grain size control layer 6 is formed by reattaching.
【００２５】この結晶粒径制御層６の再結晶領域６ａ及
び／または微細ａ−Ｓｉ粒子６ｂを結晶粒径制御層６上
に後から形成される透明電極層７の結晶成長核とするこ
とにより、粒径の大きな透明電極層が形成され、サブμ
ｍオーダーの凹凸形状を有する透明電極層７が得られ
る。即ち、結晶の成長核である再結晶領域６ａ及び／ま
たは微細ａ−Ｓｉ粒子６ｂを分散して形成することによ
り、従来方法に比べて高低差の大きな凹凸形状を得るこ
とが可能となる。The recrystallized region 6a and / or the fine a-Si particles 6b of the crystal grain size control layer 6 are used as crystal growth nuclei of a transparent electrode layer 7 formed later on the crystal grain size control layer 6. , A transparent electrode layer with a large particle size is formed,
The transparent electrode layer 7 having m-order unevenness is obtained. That is, by dispersing and forming the recrystallized region 6a and / or the fine a-Si particles 6b, which are the growth nuclei of the crystal, it is possible to obtain a large uneven shape having a height difference as compared with the conventional method.
【００２６】照射するレーザ光の条件としては、ａ−Ｓ
ｉ層表面が溶融する最低エネルギーと溶融・再結晶層が
ｎ型ａ−Ｓｉ層５を貫通することのない最大エネルギー
との間で決まる。図２は、一例として波長：２７９ｎｍ
の紫外線レーザを用いた場合のレーザ照射時の熱伝導解
析シミュレーションを行った結果を示す。図３に示すよ
うに、ｎ型ａ−Ｓｉ層５上から波長２４９ｎｍの紫外線
レーザを照射し、そのエネルギーを変化させた時のシミ
ュレーションである。The condition of the laser beam to be applied is as follows: aS
It is determined between the minimum energy at which the surface of the i-layer is melted and the maximum energy at which the molten / recrystallized layer does not penetrate the n-type a-Si layer 5. FIG. 2 shows an example in which the wavelength is 279 nm.
3 shows the results of a heat conduction analysis simulation performed at the time of laser irradiation when an ultraviolet laser is used. As shown in FIG. 3, a simulation is performed when an ultraviolet laser having a wavelength of 249 nm is irradiated from above the n-type a-Si layer 5 and the energy is changed.
【００２７】図２に示すように、波長２４９ｎｍの紫外
線レーザの場合、０．１０〜０．３０Ｊ／ｃｍ2の範囲
が適当であることが分かる。As shown in FIG. 2, in the case of an ultraviolet laser having a wavelength of 249 nm, a range of 0.10 to 0.30 J / cm 2 is found to be appropriate.
【００２８】尚、レーザ波長は上記に限定されるもので
はなく、エキシマレーザ、ＹＡＧレーザ、ＹＡＧレーザ
の２倍、３倍高調波、Ａｒレーザ等を用いることがで
き、照射エネルギー条件として、ａ−Ｓｉ層表面が溶融
する最低エネルギーと溶融・再結晶層がｎ型ａ−Ｓｉ層
を貫通しない最大エネルギーとの間で適宜選択すればよ
い。The laser wavelength is not limited to the above, and an excimer laser, a YAG laser, a harmonic twice as high as that of the YAG laser, an Ar laser, or the like can be used. What is necessary is just to select suitably between the minimum energy at which the surface of the Si layer melts and the maximum energy at which the molten / recrystallized layer does not penetrate the n-type a-Si layer.
【００２９】次に、この発明の具体的実施例を図４及び
図５に従い説明する。図４及び図５に示すように、ガラ
ス基板１上に膜厚８０００オングストロームの凹凸形状
を有するＳｎＯ2からなる透明電極膜（ＴＣＯ）２を形
成し、この上に膜厚１００オングストロームのｐ型ａ−
ＳｉＣ層３、膜厚３０００オングストロームのｉ型ａ−
Ｓｉ層４及び膜厚２００オングストロームのｎ型ａ−Ｓ
ｉ層５を順次プラズマＣＶＤ法により形成する。そし
て、このｎ型ａ−Ｓｉ層５上から波長２４９ｎｍのエキ
シマレーザ光を照射エネルギー密度：０．２５Ｊ／ｃｍ
2で照射し、ｎ型ａ−Ｓｉ層５の一部を再結晶化させて
結晶粒径制御層６を形成させる。この後、結晶粒径制御
層６上にＤＣスパッタ法を用いて膜厚１０００オングス
トロームのＩＴＯ膜からなる透明電極層７を形成した。
このＤＣスパッタ法は、基板温度１７０℃で行った。こ
の結果、０．５〜１．０μｍの高低差を有する凹凸形状
を有する透明電極層７を形成することができた。この透
明電極層７の凹凸形状はレーザ照射エネルギー及び回数
を制御し、再結晶領域の大きさ及び密度を変化させるこ
とによりできる。Next, a specific embodiment of the present invention will be described with reference to FIGS. As shown in FIGS. 4 and 5, a transparent electrode film (TCO) 2 made of SnO 2 having an uneven shape with a thickness of 8000 Å is formed on a glass substrate 1, and a p-type a film having a thickness of 100 Å is formed thereon. −
SiC layer 3, 3000 angstrom i-type a-
N-type a-S with Si layer 4 and thickness of 200 Å
The i-layer 5 is sequentially formed by a plasma CVD method. An excimer laser beam having a wavelength of 249 nm is irradiated from above the n-type a-Si layer 5 with an irradiation energy density of 0.25 J / cm.
Irradiated with 2, it is recrystallized a part of the n-type a-Si layer 5 to form a crystal grain diameter control layer 6. Thereafter, a transparent electrode layer 7 made of an ITO film having a thickness of 1000 angstrom was formed on the crystal grain size control layer 6 by DC sputtering.
This DC sputtering method was performed at a substrate temperature of 170 ° C. As a result, a transparent electrode layer 7 having a concavo-convex shape having a height difference of 0.5 to 1.0 μm could be formed. The uneven shape of the transparent electrode layer 7 can be achieved by controlling the laser irradiation energy and the number of times, and changing the size and density of the recrystallization region.
【００３０】次に、この実施例で得られた透明電極層７
上に裏面金属電極８として膜厚２０００オングストロー
ムのＡｇ層をＤＣスパッタ法により形成した。また、比
較のためにエキシマレーザ光を照射せずに、ｎ型ａ−Ｓ
ｉ層上にＩＴＯ膜を形成し、その上にＡｇからなる裏面
電極を形成した以外はこの発明の実施の形態と同様に形
成した光起電力装置を準備し、両者の出力特性を比較し
た。その結果を表２に示す。Next, the transparent electrode layer 7 obtained in this embodiment
An Ag layer having a thickness of 2000 Å was formed as a back metal electrode 8 on the upper surface by DC sputtering. For comparison, an n-type a-S
A photovoltaic device was prepared in the same manner as in the embodiment of the present invention except that an ITO film was formed on the i-layer and a back electrode made of Ag was formed thereon, and the output characteristics of both were compared. Table 2 shows the results.
【００３１】[0031]
【表２】 （評価条件：ＡＭ−１．５，１００ｍＷ／ｃｍ2）[Table 2] (Evaluation conditions: AM-1.5, 100 mW / cm 2 )
【００３２】表２より、この発明によれば光閉じ込め効
果により、発生電流（Ｉｓｃ）が１４．３ｍＡから１
４．６ｍＡに増加していることが確認できた。According to Table 2, according to the present invention, the generated current (Isc) is reduced from 14.3 mA to 1 due to the light confinement effect.
It was confirmed that it increased to 4.6 mA.
【００３３】上記した実施の形態は、光が基板側から入
射する構造の光起電力素子、いわゆる順タイプの光起電
力素子について説明したが、非透光性基板に金属電極を
形成し、順に半導体層、透光性電極を形成して、透明電
極側から光を入射する構造の光起電力素子、いわゆる逆
タイプの光起電力素子においてもこの発明が適用でき
る。従来透明電極側から光を入射するタイプにおいて、
光閉じ込めは主に金属電極の凹凸で制御されるが、この
凹凸形成は金属電極を高温下で形成するなどの条件が必
要であるとともに、その凹凸形状も適した形状が得られ
ないのが実情であった。この発明は、低温にて、基板上
に適した凹凸を有する金属電極を形成するものである。In the above-described embodiment, a photovoltaic element having a structure in which light is incident from the substrate side, that is, a so-called forward type photovoltaic element, has been described. The present invention can also be applied to a photovoltaic element having a structure in which a semiconductor layer and a translucent electrode are formed and light enters from the transparent electrode side, that is, a so-called reverse type photovoltaic element. Conventionally, in the type where light is incident from the transparent electrode side,
Light confinement is mainly controlled by the unevenness of the metal electrode. However, the formation of the unevenness requires conditions such as forming the metal electrode at a high temperature, and the actual shape of the unevenness cannot be obtained. Met. The present invention is to form a metal electrode having suitable irregularities on a substrate at a low temperature.
【００３４】以下、図６に従いこの発明の第２の実施の
形態につき説明する。図６は、この発明の第２の実施の
形態を製造工程別に示した断面図である。Hereinafter, a second embodiment of the present invention will be described with reference to FIG. FIG. 6 is a sectional view showing the second embodiment of the present invention for each manufacturing process.
【００３５】まず、基板１０上に膜厚１００オングスト
ローム以上のａ−Ｓｉ層１１をプラズマＣＶＤなどによ
り形成する。この基板１０は、後述する工程で温度処理
に耐える程度の基板で有れば良く、耐熱性が劣ると言わ
れているポリイミドなどの基板を用いることができる。
そして、このａ−Ｓｉ層１１上にレーザ光などのエネル
ギービームを照射する（図６（ａ）参照）。First, an a-Si layer 11 having a thickness of 100 Å or more is formed on a substrate 10 by plasma CVD or the like. The substrate 10 only needs to be a substrate that can withstand temperature treatment in a step described later, and a substrate of polyimide or the like, which is said to have low heat resistance, can be used.
Then, an energy beam such as a laser beam is irradiated onto the a-Si layer 11 (see FIG. 6A).
【００３６】このレーザ光の照射により、ａ−Ｓｉ層１
１が再結晶化及び／またはａ−Ｓｉ膜上に微細ａ−Ｓｉ
粒子が付着することにより結晶粒径制御層１１ａが形成
される。この結晶粒径制御層１１ａ上にＡｇ等の結晶性
金属電極１２がスパッタ法などにより形成される。この
結晶性金属電極は結晶粒径制御層１１ａの再結晶領域や
微細ａ−Ｓｉ粒子を結晶成長核として成長することから
粒径の大きな金属電極となり、表面にサブμｍオーダー
の凹凸形状が形成される（図６（ｂ）参照）。By the irradiation of the laser beam, the a-Si layer 1
1 is recrystallized and / or fine a-Si on a-Si film
The grain size control layer 11a is formed by the attachment of the grains. A crystalline metal electrode 12 of Ag or the like is formed on the crystal grain size control layer 11a by a sputtering method or the like. Since this crystalline metal electrode grows using the recrystallized region of the crystal grain size control layer 11a and the fine a-Si grains as crystal growth nuclei, it becomes a metal electrode having a large grain size, and a sub-micron-order unevenness is formed on the surface. (See FIG. 6B).
【００３７】この金属電極１２上に光活性層となるｎ型
アモルファスシリコンまたはｎ型微結晶シリコンからな
るｎ型ａ−Ｓｉ層１３、ｉ型ａ−Ｓｉ層１４、ｐ型アモ
ルファスシリコンカーバイドまたはｐ型微結晶シリコン
からなるｐ型ａ−Ｓｉ層１５が順次プラズマＣＶＤ法、
光ＣＶＤ法などの気相成長法により形成されている。そ
して、ｐ型ａ−Ｓｉ層１５上にＳｎＯ2、ＺｎＯ2、ＩＴ
Ｏなどからなる透明導電膜（ＴＣＯ）１６が形成され、
光起電力素子が得られる（図６（ｃ）参照）。On this metal electrode 12, an n-type a-Si layer 13, an i-type a-Si layer 14, made of n-type amorphous silicon or n-type microcrystalline silicon serving as a photoactive layer, p-type amorphous silicon carbide or p-type A p-type a-Si layer 15 made of microcrystalline silicon is sequentially formed by a plasma CVD method,
It is formed by a vapor phase growth method such as a photo CVD method. Then, on the p-type a-Si layer 15, SnO 2 , ZnO 2 , IT
A transparent conductive film (TCO) 16 made of O or the like is formed,
A photovoltaic element is obtained (see FIG. 6C).
【００３８】さて、この発明では、ａ−Ｓｉ層１１の表
面にレーザ光などのエネルギービームを照射することに
より、ａ−Ｓｉ層を一部溶融し、再結晶化させたり、或
いはａ−Ｓｉ層表面に微細ａ−Ｓｉ粒子を再生・再付着
させた結晶粒径制御層１１ａを形成する。In the present invention, the surface of the a-Si layer 11 is irradiated with an energy beam such as a laser beam to partially melt and recrystallize the a-Si layer. A crystal grain size control layer 11a in which fine a-Si particles are regenerated and reattached on the surface is formed.
【００３９】この結晶粒径制御層１１ａの再結晶領域及
び微細ａ−Ｓｉ粒子を結晶粒径制御層１１ａ上に後から
形成される金属電極層１２の結晶成長核とすることによ
り、粒径の大きな金属電極層１２が形成され、高低差が
１μｍ以下のサブμｍオーダーの凹凸形状を有する金属
電極層１２が得られる。即ち、結晶の成長核である微結
晶領域及び微細ａ−Ｓｉ粒子が分散して形成されること
により、容易に高低差の大きな凹凸形状を得ることが可
能となる。The recrystallized region and the fine a-Si particles of the crystal grain size control layer 11a are used as crystal growth nuclei of the metal electrode layer 12 which is formed later on the crystal grain size control layer 11a. The large metal electrode layer 12 is formed, and the metal electrode layer 12 having a submicron-order unevenness with a height difference of 1 μm or less can be obtained. That is, since the microcrystalline region and the fine a-Si particles, which are the crystal growth nuclei, are dispersed and formed, it is possible to easily obtain a large uneven shape having a large difference in elevation.
【００４０】照射するレーザ光の条件としては、ａ−Ｓ
ｉ層１１の表面が溶融する最低エネルギー以上のレーザ
光を照射すればよい。The condition of the laser beam to be applied is as follows: a-S
What is necessary is just to irradiate the laser beam of the minimum energy or more which the surface of the i layer 11 melts.
【００４１】次に、この発明の具体的実施例を説明す
る。ポリイミド基板１０上に膜厚１００オングストロー
ムのａ−Ｓｉ層１１を形成し、このａ−Ｓｉ層１１上に
大気中で波長２４９ｎｍのＫｒＦエキシマレーザ光を照
射エネルギー密度：０．２０Ｊ／ｃｍ2で３０ショット
照射し、ａ−Ｓｉ層１１全面を再結晶化させて結晶粒径
制御層１１ａを形成させる。その後、基板温度２００℃
以下でＤＣスパッタ法により銀（Ａｇ）からなる金属電
極１２を形成する。この結果、０．５〜１．０μｍの高
低差を有する凹凸形状を有する金属電極膜が形成でき
た。この金属電極膜の凹凸形状はレーザ照射エネルギー
及び回数を制御し、再結晶領域の大きさ及び密度を変化
させることによりできる。Next, a specific embodiment of the present invention will be described. An a-Si layer 11 having a thickness of 100 angstroms is formed on a polyimide substrate 10, and a KrF excimer laser beam having a wavelength of 249 nm is irradiated on the a-Si layer 11 in the atmosphere at an irradiation energy density of 0.20 J / cm 2 for 30 minutes. Shot irradiation is performed, and the entire surface of the a-Si layer 11 is recrystallized to form a crystal grain size control layer 11a. After that, the substrate temperature is 200 ° C.
Hereinafter, a metal electrode 12 made of silver (Ag) is formed by a DC sputtering method. As a result, a metal electrode film having a concavo-convex shape having a height difference of 0.5 to 1.0 μm was formed. The uneven shape of the metal electrode film can be formed by controlling the laser irradiation energy and the number of times, and changing the size and density of the recrystallization region.
【００４２】この上に膜厚２００オングストロームのｎ
型ａ−Ｓｉ層１３、膜厚３０００オングストロームのｉ
型ａ−Ｓｉ層１４及び膜厚１００オングストロームのｐ
型ａ−Ｓｉ層５を順次プラズマＣＶＤ法により形成す
る。そして、このｐ型ａ−Ｓｉ層５上にＤＣスパッタ法
を用いて膜厚１０００オングストロームのＩＴＯ膜１６
を形成することにより、この発明の光起電力素子が得ら
れた。On top of this, a 200 angstrom thick n
Type a-Si layer 13, 3000 angstrom thick i
Type a-Si layer 14 and 100 angstrom thick p
The mold a-Si layer 5 is sequentially formed by a plasma CVD method. Then, a 1000 Å thick ITO film 16 is formed on the p-type a-Si layer 5 by DC sputtering.
Was formed, whereby the photovoltaic element of the present invention was obtained.
【００４３】次に、この実施例で得られた光起電力素子
と、比較のためにエキシマレーザ光を照射せずに、ａ−
Ｓｉ層１１上に金属膜を形成した以外はこの発明の実施
の形態と同様に形成した光起電力装置を準備し、両者の
出力特性を比較した。その結果を表３に示す。Next, for comparison, the photovoltaic device obtained in this example was irradiated with excimer laser light,
A photovoltaic device was prepared in the same manner as in the embodiment of the present invention except that a metal film was formed on the Si layer 11, and the output characteristics of both were compared. Table 3 shows the results.
【００４４】[0044]
【表３】 （評価条件：ＡＭ−１．５，１００ｍＷ／ｃｍ2）[Table 3] (Evaluation conditions: AM-1.5, 100 mW / cm 2 )
【００４５】表３より、この発明によれば光閉じ込め効
果により、発生電流（Ｉｓｃ）が１４．２ｍＡから１
４．９ｍＡに増加していることが確認でき、変換効率が
約５％向上した。As shown in Table 3, according to the present invention, the generated current (Isc) is reduced from 14.2 mA to 1 due to the light confinement effect.
It was confirmed that the value increased to 4.9 mA, and the conversion efficiency was improved by about 5%.
【００４６】上記した第２の実施の形態においては、基
板１０上の結晶粒径制御層１１ａ上にＡｇなどの結晶性
金属電極層１２を形成しているが、結晶粒径制御層１１
ａ上にＩＴＯ等の透明電極をスパッタ法などで形成し、
この透明電極表面にサブμｍオーダーの凹凸を形成し、
この上に金属電極膜を低温で形成することで、金属電極
膜上に光閉じ込め効果に最適な凹凸を形成することがで
きる。また、金属電極とａ−Ｓｉ層との間に拡散防止用
の透明電極を設けても良い。In the above-described second embodiment, the crystalline metal electrode layer 12 made of Ag or the like is formed on the crystal grain size control layer 11a on the substrate 10.
A transparent electrode such as ITO is formed on a by sputtering or the like,
Sub-micron order irregularities are formed on the surface of this transparent electrode,
By forming a metal electrode film thereon at a low temperature, it is possible to form irregularities optimal for a light confinement effect on the metal electrode film. Further, a transparent electrode for preventing diffusion may be provided between the metal electrode and the a-Si layer.
【００４７】[0047]
【発明の効果】以上説明したように、この発明によれ
ば、表面に光り閉じ込め用の凹凸形状を有する凹凸電極
を容易に形成することができ、光閉じ込め効果に優れた
光起電力素子を提供することができる。また、上記凹凸
電極は低温で形成することができるため、例えばポリイ
ミド等の耐熱性の劣る基板を用いることが可能となり、
安価な光起電力素子が提供できる。As described above, according to the present invention, a concavo-convex electrode having a concavo-convex shape for confining light on its surface can be easily formed, and a photovoltaic element excellent in light confinement effect can be provided. can do. Further, since the uneven electrode can be formed at a low temperature, it is possible to use a substrate having poor heat resistance, such as polyimide,
An inexpensive photovoltaic element can be provided.
【図１】この発明の第１の実施の形態にかかる光起電力
素子の概略構造を示す断面図である。FIG. 1 is a cross-sectional view showing a schematic structure of a photovoltaic device according to a first embodiment of the present invention.
【図２】波長：２７９ｎｍの紫外線レーザを用いた場合
のレーザ照射時の熱伝導解析シミュレーションを行った
結果を示す図である。FIG. 2 is a diagram showing a result of performing a heat conduction analysis simulation at the time of laser irradiation when an ultraviolet laser having a wavelength of 279 nm is used.
【図３】この発明の光起電力素子におけるａ−Ｓｉ層上
にレーザを照射した状態の概略構造を示す断面図であ
る。FIG. 3 is a cross-sectional view showing a schematic structure of a photovoltaic element of the present invention in a state where a laser is irradiated onto an a-Si layer.
【図４】この発明の第１の実施の形態にかかる光起電力
素子の概略構造を示す断面図である。FIG. 4 is a sectional view showing a schematic structure of a photovoltaic element according to the first embodiment of the present invention.
【図５】この発明の第１の実施の形態にかかる光起電力
素子の概略構造を示す断面図である。FIG. 5 is a cross-sectional view showing a schematic structure of a photovoltaic device according to the first embodiment of the present invention.
【図６】この発明の第２の実施の形態を製造工程別に示
した断面図である。FIG. 6 is a cross-sectional view showing a second embodiment of the present invention for each manufacturing step.
【図７】従来の光起電力素子を示す概略断面図である。FIG. 7 is a schematic sectional view showing a conventional photovoltaic element.
【図８】光の入射角と出射角との関係を示す図であるFIG. 8 is a diagram showing a relationship between an incident angle and an outgoing angle of light.
【図９】従来の光起電力素子を示す概略断面図である。FIG. 9 is a schematic sectional view showing a conventional photovoltaic element.
【図１０】従来の光起電力素子を示す概略断面図であ
る。FIG. 10 is a schematic sectional view showing a conventional photovoltaic element.
【図１１】従来の光起電力素子を示す概略断面図であ
る。FIG. 11 is a schematic sectional view showing a conventional photovoltaic element.
１ ガラス基板（透光性絶縁性基板） ２ 透明電極膜 ３ ｐ型ａ−Ｓｉ層 ４ ｉ型ａ−Ｓｉ層 ５ ｎ型ａ−Ｓｉ層 ６ 結晶粒径制御層 ７ 結晶性透明電極 REFERENCE SIGNS LIST 1 glass substrate (translucent insulating substrate) 2 transparent electrode film 3 p-type a-Si layer 4 i-type a-Si layer 5 n-type a-Si layer 6 crystal grain size control layer 7 crystalline transparent electrode
Claims (11)
する凹凸電極の製造方法であって、非晶質半導体層にエ
ネルギービームを照射し、前記非晶質半導体層の一部に
結晶核領域を形成した後、前記非晶質半導体層上に結晶
性電極を形成することで表面に凹凸形状を有する凹凸電
極を形成することを特徴とする凹凸電極の製造方法。1. A method for manufacturing a concave / convex electrode in which a concave / convex electrode having a concave / convex shape is formed on a surface thereof, the method comprising irradiating an amorphous semiconductor layer with an energy beam, and forming a crystal nucleus region on a part of the amorphous semiconductor layer. Forming a crystalline electrode on the amorphous semiconductor layer to form an uneven electrode having an uneven shape on the surface.
が結晶化されてなる領域であることを特徴とする請求項
１に記載の凹凸電極の製造方法。2. The method according to claim 1, wherein the crystal nucleus region is a region formed by crystallizing the amorphous semiconductor layer.
を構成する非晶質半導体層の微粉末が非晶質半導体層上
に付着してなる領域であることを特徴とする請求項１ま
たは２に記載の凹凸電極の製造方法。3. The crystal nucleus region is a region in which fine powder of an amorphous semiconductor layer constituting the amorphous semiconductor layer adheres to the amorphous semiconductor layer. 3. The method for producing an uneven electrode according to 1 or 2.
及び金属電極を順次形成してなる光起電力素子の製造方
法であって、前記非晶質半導体層にエネルギービームを
照射し、非晶質半導体層の一部に結晶核領域を形成した
後、この非晶質半導体層上に凹凸形状を有する透光性の
結晶性薄膜を形成し、この薄膜上に凹凸形状を有する金
属電極を形成することを特徴とする光起電力素子の製造
方法。4. A method for manufacturing a photovoltaic element, comprising: forming a light incident side electrode, an amorphous semiconductor layer, and a metal electrode on a substrate in order, and irradiating the amorphous semiconductor layer with an energy beam. After forming a crystal nucleus region in a part of the amorphous semiconductor layer, a light-transmitting crystalline thin film having an uneven shape is formed on the amorphous semiconductor layer, and a metal having an uneven shape is formed on the thin film. A method for manufacturing a photovoltaic device, comprising forming an electrode.
が結晶化されてなる領域であることを特徴とする請求項
４に記載の光起電力素子の製造方法。5. The method according to claim 4, wherein the crystal nucleus region is a region formed by crystallizing the amorphous semiconductor layer.
を構成する非晶質半導体層の微粉末が非晶質半導体層上
に付着してなる領域であることを特徴とする請求項４ま
たは５に記載の光起電力素子の製造方法。6. The crystal nucleus region is a region in which fine powder of an amorphous semiconductor layer forming the amorphous semiconductor layer is attached to the amorphous semiconductor layer. 6. The method for manufacturing a photovoltaic device according to 4 or 5.
光入射側電極を順次形成する光起電力素子の製造方法で
あって、前記基板上に非晶質半導体層を形成し、この非
晶質半導体層にエネルギービームを照射することで前記
非晶質半導体層の一部に結晶核領域を形成した後、この
非晶質半導体層上に結晶性裏面電極を形成することを特
徴とする光起電力素子の製造方法。7. A method for manufacturing a photovoltaic device, wherein a back electrode, an amorphous semiconductor layer, and a light incident side electrode are sequentially formed on a substrate, wherein the amorphous semiconductor layer is formed on the substrate. Forming a crystal nucleus region in a part of the amorphous semiconductor layer by irradiating the amorphous semiconductor layer with an energy beam, and then forming a crystalline back electrode on the amorphous semiconductor layer. Of manufacturing a photovoltaic element.
が結晶化されてなる領域であることを特徴とする請求項
７に記載の光起電力素子の製造方法。8. The method according to claim 7, wherein the crystal nucleus region is a region formed by crystallizing the amorphous semiconductor layer.
を構成する非晶質半導体層の微粉末が非晶質半導体層上
に付着してなる領域であることを特徴とする請求項７ま
たは８に記載の光起電力素子の製造方法。9. The crystal nucleus region is a region in which fine powder of an amorphous semiconductor layer constituting the amorphous semiconductor layer adheres to the amorphous semiconductor layer. 9. The method for manufacturing a photovoltaic device according to 7 or 8.
層及び金属電極を順次形成した光起電力素子であって、
前記非晶質半導体層上に、一部に結晶核領域が形成され
た結晶粒径制御層が設けられ、この結晶粒径制御層上に
透光性の結晶性薄膜を介して金属電極が設けられている
ことを特徴とする光起電力素子。10. A photovoltaic device in which a light incident electrode, an amorphous semiconductor layer, and a metal electrode are sequentially formed on a substrate,
A crystal grain size control layer in which a crystal nucleus region is formed partially is provided on the amorphous semiconductor layer, and a metal electrode is provided on the crystal grain size control layer via a light-transmitting crystalline thin film. A photovoltaic device, characterized in that it is made.
び光入射側電極を順次形成した光起電力素子であって、
前記基板上に一部に結晶核領域が形成された結晶粒径制
御層が設けられ、この結晶粒径制御層上に結晶性の裏面
電極が設けられていることを特徴とする光起電力素子。11. A photovoltaic device in which a back electrode, an amorphous semiconductor layer and a light incident side electrode are sequentially formed on a substrate,
A photovoltaic element, comprising: a crystal grain size control layer in which a crystal nucleus region is partially formed on the substrate; and a crystalline back electrode provided on the crystal grain size control layer. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06090898A JP3607495B2 (en) | 1998-03-12 | 1998-03-12 | Method for producing crystalline electrode having irregular shape and method for producing photovoltaic element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06090898A JP3607495B2 (en) | 1998-03-12 | 1998-03-12 | Method for producing crystalline electrode having irregular shape and method for producing photovoltaic element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11261092A true JPH11261092A (en) | 1999-09-24 |
| JP3607495B2 JP3607495B2 (en) | 2005-01-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003065461A1 (en) * | 2002-01-31 | 2003-08-07 | Nippon Sheet Glass Company, Limited | Substrate for photoelectric conversion device |
| KR100927725B1 (en) | 2008-01-25 | 2009-11-18 | 삼성에스디아이 주식회사 | Solar cell and manufacturing method thereof |
| KR101108988B1 (en) * | 2010-04-16 | 2012-02-06 | 금호전기주식회사 | Cigs solar cell module having front transparent electrode with surface crystalline relief structure and manufacturing method thereof |
| US8399760B2 (en) | 2008-01-11 | 2013-03-19 | Samsung Sdi Co., Ltd. | Solar cell having improved electrode structure reducing shading loss |
| KR101368905B1 (en) * | 2007-12-20 | 2014-02-28 | 주성엔지니어링(주) | Method for manufacturing Thin film type Solar Cell |
-
1998
- 1998-03-12 JP JP06090898A patent/JP3607495B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003065461A1 (en) * | 2002-01-31 | 2003-08-07 | Nippon Sheet Glass Company, Limited | Substrate for photoelectric conversion device |
| KR101368905B1 (en) * | 2007-12-20 | 2014-02-28 | 주성엔지니어링(주) | Method for manufacturing Thin film type Solar Cell |
| US8399760B2 (en) | 2008-01-11 | 2013-03-19 | Samsung Sdi Co., Ltd. | Solar cell having improved electrode structure reducing shading loss |
| KR100927725B1 (en) | 2008-01-25 | 2009-11-18 | 삼성에스디아이 주식회사 | Solar cell and manufacturing method thereof |
| KR101108988B1 (en) * | 2010-04-16 | 2012-02-06 | 금호전기주식회사 | Cigs solar cell module having front transparent electrode with surface crystalline relief structure and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3607495B2 (en) | 2005-01-05 |
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