JPS61288473A - Photovoltaic device - Google Patents
Photovoltaic deviceInfo
- Publication number
- JPS61288473A JPS61288473A JP60131285A JP13128585A JPS61288473A JP S61288473 A JPS61288473 A JP S61288473A JP 60131285 A JP60131285 A JP 60131285A JP 13128585 A JP13128585 A JP 13128585A JP S61288473 A JPS61288473 A JP S61288473A
- Authority
- JP
- Japan
- Prior art keywords
- light
- receiving surface
- photovoltaic device
- surface electrode
- tco
- 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.)
- Granted
Links
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000004065 semiconductor Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims description 17
- 238000005530 etching Methods 0.000 abstract description 12
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 12
- 238000001000 micrograph Methods 0.000 description 12
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
- Light Receiving Elements (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は光照射を受けると起電力を発生する光起電力装
置に関し、例えば太陽光発電等に利用される。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a photovoltaic device that generates electromotive force when irradiated with light, and is used, for example, in solar power generation.
（ロ） 従来の技術
ガラス等の透光性基板上に受光面電極、半導体光活性層
及び背面電極をこの順序で積層せしめた光起電力装置は
例えば特公昭５３−３７７１８号公報や米国特許第４．
２８１．２０８号明細書に開示された如く既に知られて
いる０通常上記受光面電極として電子ビーム蒸着法、真
空蒸着法、スパッタ法、ＣＶＤ法、スプレー法等によっ
て形成される酸化インジウムスズ（Ｉｒｅ）、酸化スズ
（ＳｎＯｘ）等に代表される透光性導電酸化物（以下Ｔ
ＯＣと称す）の単層或いは積層構造が用いられる。(b) Prior art A photovoltaic device in which a light-receiving surface electrode, a semiconductor photoactive layer, and a back electrode are laminated in this order on a light-transmitting substrate such as glass is disclosed in, for example, Japanese Patent Publication No. 53-37718 and U.S. Pat. 4.
As disclosed in No. 281.208, indium tin oxide (Ire ), translucent conductive oxides (hereinafter referred to as T
(referred to as OC) is used in a single layer or laminated structure.
然し乍ら、斯る工Ｃｏから受光面電極を形成すると、こ
のＴＣＯの屈折率は約２．０前後であるのに対し、それ
と接する半導体光活性層の屈折率は上記２．０より太き
（例えばアモルファスシリコン、アモルファスシリコン
カーバイト、アモル）７スシリコンゲルマニウム等のア
モルファスシリコン系半導体にあっては約４．０前後で
あるために、支持基板側から入射した光は上記屈折率の
差に基づき受光面電極と光活性層との界面に於いて反射
し、光電変換動作する光活性層に入射する光量を減少せ
しめる原因となっていた。However, when the light-receiving surface electrode is formed from such engineered Co, the refractive index of this TCO is around 2.0, whereas the refractive index of the semiconductor photoactive layer in contact with it is thicker than the above-mentioned 2.0 (e.g. For amorphous silicon semiconductors such as amorphous silicon, amorphous silicon carbide, and amorphous silicon germanium, the value is around 4.0, so light incident from the supporting substrate side is received based on the difference in refractive index. This is reflected at the interface between the surface electrode and the photoactive layer, causing a decrease in the amount of light incident on the photoactive layer that performs photoelectric conversion.
昭和６０年春季応用物理学会予稿集第４３９頁２９ｐ−
Ｕ−１４に開示された先行技術は、受光面電極と光活地
層との界面に於ける反射特性が、界面形状に著しく影響
される点に鑑み受光面電極の光活性層側界面を凹凸状と
なし光活性層に入射する光量の増大を図ることを提案し
ている。1985 Spring Proceedings of the Japan Society of Applied Physics, p. 439, p. 29-
In the prior art disclosed in U-14, the photoactive layer-side interface of the light-receiving surface electrode is made uneven in view of the fact that the reflection characteristics at the interface between the light-receiving surface electrode and the photoactive layer are significantly affected by the shape of the interface. It is proposed to increase the amount of light incident on the photoactive layer.
一方、上述の如き一般的なＴＣＯの形成技術によれば、
形成するＴＣＯの平均粒径によって受光面電極の表面形
状が決定されるために、斯るＴＣＯの平均粒径が約２０
０〜１０００人程度であることからして、従来の受光面
電極の表面形状は凹凸の高低差約２００〜１０００Å、
凸部と凸部との間隔約５００〜２０００人と小さな凹凸
形状を呈するに止まっていた。On the other hand, according to the general TCO formation technology as described above,
Since the surface shape of the light-receiving surface electrode is determined by the average particle size of the TCO to be formed, the average particle size of the TCO is approximately 20
Considering that the number of people is approximately 0 to 1,000, the surface shape of the conventional light-receiving surface electrode has an uneven height difference of approximately 200 to 1,000 Å.
The distance between the protrusions was only about 500 to 2,000 people, and the shape was only small.
従って、一般的なＴＣＯを受光面電極とした光起電力装
置にあっては、斯るＴＣＯの受光面電極と光活性層との
界面に於ける反射損失が大きく、光電変換効率を低下せ
しめる要因となっていた。Therefore, in a photovoltaic device using a general TCO as a light-receiving surface electrode, reflection loss at the interface between the TCO light-receiving surface electrode and the photoactive layer is large, which is a factor that reduces photoelectric conversion efficiency. It became.
そこで、更に大きな凹凸を形成するために、ＴＣＯの粒
径を大きくすることが試みられた０例えばＴＣＯの平均
粒径を約２０００〜１００００人とすると、凹凸の高低
差約１０００〜５０００Å、凸部と凸部との間隔約５０
０〜２０００人程度の凹凸形状が得られるものの、この
凹凸形状を実現するためには平均粒径の大きなＴＣＯを
使用しなければならず、比抵抗の増大、光透過率の減少
及び支持基板との密着力の低下を招く原因となり、光起
電力装置の受光面電極としては不適切である。Therefore, attempts have been made to increase the particle size of TCO in order to form even larger unevenness.For example, if the average particle size of TCO is about 2,000 to 10,000 people, the height difference of the unevenness is about 1,000 to 5,000 Å, and the convex part The distance between and the convex part is about 50
Although it is possible to obtain an uneven shape of approximately 0 to 2,000 grains, it is necessary to use TCO with a large average particle size in order to achieve this uneven shape, which increases resistivity, decreases light transmittance, and causes problems with the supporting substrate. This causes a decrease in the adhesion of the material, making it unsuitable for use as a light-receiving surface electrode of a photovoltaic device.
これに対し、上記応用物理学会予稿集に開示された先行
技術によれば支持基板表面に予め凹凸を設け、その凹凸
表面に沿ってＴＣＯを形成することによって、通常の粒
径のＴＣＯを用いても大きな凹凸面を持つ受光面電極が
得られる。ところが、今度は支持基板表面を受光面電極
として要求される数１０００人のオーダに凹凸加工する
ことが非常に難しく量産性が低いと云う欠点である。On the other hand, according to the prior art disclosed in the above-mentioned Proceedings of the Japan Society of Applied Physics, the surface of the support substrate is provided with unevenness in advance, and TCO is formed along the uneven surface. Also, a light-receiving surface electrode having a large uneven surface can be obtained. However, the disadvantage is that it is very difficult to process the surface of the support substrate to the level of several thousand people required for the light-receiving surface electrode, resulting in low mass productivity.
（ハ）発明が解決しようとする問題点
未発明は光起電力装置の受光面電極と半導体光活性層と
の界面に於ける入射光の反射損失と、比抵抗の増大、光
透過率の減少及び支持基板との密着力の低下を同時に解
決しようとするものである。(c) Problems to be solved by the invention What has not yet been invented is the reflection loss of incident light at the interface between the light-receiving surface electrode of the photovoltaic device and the semiconductor photoactive layer, the increase in specific resistance, and the decrease in light transmittance. This is an attempt to simultaneously solve the problem of lower adhesion with the supporting substrate.
（ニ） 問題点を解決するための手段本発明は上記問
題点を解決するために、受光面電極は平均粒径約５００
〜２０００人のＩＣＯからなると共に、この受光面電極
は半導体光活性層との界面側に高低差約１０００〜５０
００Å、凸部と凸部との間隔約２０００〜１００００人
の凹凸面を備えたことを特徴とする。(d) Means for Solving the Problems In order to solve the above problems, the present invention provides a light-receiving surface electrode having an average particle diameter of about 500.
Consisting of ~2000 ICOs, this light-receiving surface electrode has a height difference of approximately 1000~50cm on the interface side with the semiconductor photoactive layer.
00 Å and an uneven surface with an interval of about 2,000 to 10,000 angstroms between the protrusions.
（ホ）作用
上述の如く半導体光活性層との界面側に高低差約１００
０〜５０００Å、凸部と凸部との間隔約２０００〜１０
０００人の凹凸面を備えた平均粒径約５００〜２０００
人のＩＣＯからなる受光面電極を用いることによって、
斯る受光面電極は光起電力装置として好適な凹凸形状を
受光面電極と半導体光活性層との界面に形成する。(E) Function As mentioned above, there is a height difference of about 100 on the interface side with the semiconductor photoactive layer.
0 to 5000 Å, distance between convex parts approximately 2000 to 10
Average grain size about 500-2000 with uneven surface of 000
By using a light-receiving surface electrode made of human ICO,
Such a light-receiving surface electrode forms an uneven shape suitable for a photovoltaic device at the interface between the light-receiving surface electrode and the semiconductor photoactive layer.
（へ） 実施例
第１図は本発明光起電力装置の一実施例を模式的に示す
断面図であって、（１）はほぼ平坦な絶縁表面を持つ透
光性の支持基板、（２）は上記支持基板の絶縁表面に沿
って形成されたＩＣＯからなる受光面電極、（３）は上
記受光面電極（２）の凹凸面（２ｔｅｘ）上に例えば前
記先行技術に開示された如きプラズマＣＶＤ法等により
その内部にｐｉｎ、 ｐｎ等の周知の半導体接合が形成
されたアモルファスシリコン系の半導体光活性層、（４
）はこの光活性層（３）の背面に形成きれたアルミニウ
ム（Ａ１）、銀（Ａｇ）或いはＴＣＯ／Ａｇ等の単層或
いは積層構造の背面電極で、上記光活性層（３）に支持
基板（１）及び受光面電極（２）を透過して光照射がな
されると、断る光活性層（３）中に於いて光キャリアが
発生し、この光キャリアの移動により受光面電極（２）
と背面電極（４）との間に起電力が発生する。Embodiment FIG. 1 is a cross-sectional view schematically showing an embodiment of the photovoltaic device of the present invention, in which (1) is a light-transmitting support substrate having a substantially flat insulating surface, (2) ) is a light-receiving surface electrode made of ICO formed along the insulating surface of the support substrate, and (3) is a plasma plate formed on the uneven surface (2tex) of the light-receiving surface electrode (2), for example, as disclosed in the above-mentioned prior art. An amorphous silicon-based semiconductor photoactive layer (4
) is a back electrode of a single layer or a laminated structure made of aluminum (A1), silver (Ag), TCO/Ag, etc. formed on the back surface of the photoactive layer (3). When light is irradiated through (1) and the light-receiving surface electrode (2), photocarriers are generated in the photoactive layer (3), and the movement of these photocarriers causes the light-receiving surface electrode (2) to be irradiated.
An electromotive force is generated between the electrode and the back electrode (4).
而して、本発明の特徴は上記支持基板（１）のほぼ平坦
な絶縁表面に配置され先覚変換動作する半導体光活性層
（３）と接する界面側が凹凸面（２ｔａｘ ）をなす受
光面電極（２）の構造にある。即ち、本発明光起電力装
置の受光面電極（２）として用いられるＴＣＯは通常の
形成方法により得られる約５００〜２０００人の平均粒
径であるにも拘らず、高低差（ｈ）約１０００〜５００
０Å、凸部と凸部との間隔（ｄ）約２０００〜１０００
０人のほぼ三角錐状凹凸面（２ｔａｘ）を備えている。The feature of the present invention is that the light-receiving surface electrode (2tax) is disposed on the substantially flat insulating surface of the support substrate (1) and has an uneven surface (2tax) on the interface side in contact with the semiconductor photoactive layer (3) that performs a preconversion operation. 2). That is, although the TCO used as the light-receiving surface electrode (2) of the photovoltaic device of the present invention has an average particle size of about 500 to 2,000 particles obtained by a normal forming method, the height difference (h) is about 1,000. ~500
0 Å, distance between convex parts (d) approximately 2000 to 1000
It has a roughly triangular pyramid-shaped uneven surface (2 tax).
第２図は乃至第４図は斯る凹凸面（２ｔａｘ）の加工方
法を模式的に表わしている。先ず第２図の如く、ガラス
等の透光性支持基板（１）のほぼ平坦な絶縁表面に沿っ
て周知の電子ビーム蒸着法、真空蒸着法、スパッタ法、
ＣＶＤ法、スプレー法等によって形成された平均粒径約
５００〜２０００人の１６０層（５）被着した電極基板
を準備する。上記１６０層（５）は、例えば基板温度３
００°Ｃ１酸素分圧４ｘ１０−’Ｔｏｒｒの形成条件に
基づいて電子ビーム蒸着法により得られた５％の５ｎＯ
ｘをドープしたＩＴＯからなり、上述の如く約５００〜
２０００人の平均粒径を備え、膜厚約１５００〜７００
０人に被着されている。FIGS. 2 to 4 schematically show a method of processing such an uneven surface (2 tax). First, as shown in FIG. 2, a well-known electron beam evaporation method, vacuum evaporation method, sputtering method, or
An electrode substrate having 160 layers (5) deposited thereon having an average particle size of about 500 to 2000 particles formed by a CVD method, a spray method, or the like is prepared. For example, the 160 layers (5) have a substrate temperature of 3
5% 5nO obtained by electron beam evaporation method based on formation conditions of 00°C1 oxygen partial pressure 4x10-'Torr
It is made of ITO doped with
Equipped with an average particle size of 2000 and a film thickness of about 1500 to 700.
Covered by 0 people.
第３図の工程では、上記支持基板（１）のほぼ平坦面に
沿って被着されていた１６０層（５）がその露出面から
支持基板（１）に向ってエツチング処理が施される。使
用されるエツチング液としては上記ＩＴＯの１６０層（
５）に対してＨＣＩ ： Ｈ＊０ ： ＦｅＣ１５＝
５００ｏｃ： ６００ｃｃ ： １００ｇのものが好適
であり、他に王水も利用可能である。斯るエツチング処
理に於いて、１６０層〈５〉はその露出面から順次エツ
チング除去されるものの１６０層（５）のエツチングレ
ートの異方性に起因して、先ず第３図に示す如くエツチ
ングレートの高い部分からエツチングが始まるために、
断面台形状となる。In the process shown in FIG. 3, the 160 layer (5) deposited along the substantially flat surface of the support substrate (1) is etched from its exposed surface toward the support substrate (1). The etching solution used was the above-mentioned ITO 160 layer (
5) for HCI: H*0: FeC15=
500oc: 600cc: 100g is suitable, and aqua regia can also be used. In this etching process, the 160 layer (5) is etched away sequentially from its exposed surface, but due to the anisotropy of the etching rate of the 160 layer (5), the etching rate is first reduced as shown in FIG. Because etching starts from the high part of the
It has a trapezoidal cross section.
第４図は第３図のエツチング処理が終了した状態を示し
ている。即ち、斯るエツチング処理はＩＣ０層（５）の
厚み方向の途中までとし、その露出面が光起電力装置の
受光面電極（２）として好適な微細な凹凸を持つまで行
ない、例えば高低差約１０００〜５０００Å、凸部と凸
部の間隔的２０００〜ｔｏｏｏ。FIG. 4 shows a state in which the etching process shown in FIG. 3 has been completed. That is, such etching treatment is carried out to the middle of the thickness direction of the IC0 layer (5), and is performed until the exposed surface has minute irregularities suitable for the light-receiving surface electrode (2) of the photovoltaic device. 1000-5000 Å, spacing between protrusions 2000-toooo.
人のほぼ三角錐状の凹凸面（２ｔｅｘ）が付与きれた受
光面電極（２）が形成される０例えば上記エツチング液
、液温的２５°Ｃの条件に於いて２０〜４０分程度で程
度微細な凹凸面（２ｔｅｘ）が得られる。A light-receiving surface electrode (2) with a roughly triangular pyramid-shaped uneven surface (2 tex) is formed.For example, using the above etching solution, it takes about 20 to 40 minutes at a liquid temperature of 25°C. A finely uneven surface (2 tex) is obtained.
第５図及び第６図は上記エツチング処理により凹凸化さ
れる前の１６０層（５）の粒子構造を示す走査顕微鏡写
真であって、第５図は断面状態であり、第６図は露出面
に対して傾斜角８０度の方向から臨んだ状態で、両者の
倍率は等しくなく写真の下段に夫々のスケールが記しで
ある。第７図及び第８図は上記第５図及び第６図に示さ
れた１６０層（５）を上記エツチング処理により凹凸化
した後の受光面電極（２）の粒子構造を示す走査顕微鏡
写真であって、第７図は第５図と同倍率の断面状態であ
り、第８図は第６図と同倍率の露出面（凹凸面（２ｔｅ
ｘ））に対して傾斜角８０度の方向から臨んだ状態であ
る。Figures 5 and 6 are scanning micrographs showing the grain structure of the 160 layer (5) before it is made uneven by the etching process, with Figure 5 showing the cross-sectional state and Figure 6 showing the exposed surface. When viewed from a direction with an inclination angle of 80 degrees, the magnifications of both are not equal, and the respective scales are indicated at the bottom of the photograph. Figures 7 and 8 are scanning micrographs showing the particle structure of the light-receiving surface electrode (2) after the 160 layer (5) shown in Figures 5 and 6 has been made uneven by the etching process. 7 shows the cross-sectional state at the same magnification as FIG. 5, and FIG. 8 shows the exposed surface (uneven surface (2te) at the same magnification as FIG.
This is a state viewed from a direction with an inclination angle of 80 degrees with respect to x)).
尚、参考までに第９図及び第１０図に第３図に相当する
凹凸加工の途中状態に於ける１６０層（５）の粒子構造
の断面状態及び傾斜角８０度の方向から臨んだ状態の走
査顕微鏡写真を示す。For reference, Figures 9 and 10 show the cross-sectional state of the grain structure of the 160 layer (5) in the middle of roughening processing, which corresponds to Figure 3, and the state viewed from the direction with an inclination angle of 80 degrees. A scanning micrograph is shown.
この顕微鏡写真からＩＣ０層（５）の異方性エツチング
レートにより、その露出面から支持基板（１）方向に均
一にエツチング除去されることなく凹凸面（２ｔｅｘ）
が形成されていることは明らかである。This micrograph shows that due to the anisotropic etching rate of the IC0 layer (5), the exposed surface is not uniformly etched away in the direction of the support substrate (1), resulting in an uneven surface (2 tex).
It is clear that a is formed.
この様にして凹凸面（２ｔａｘ）が付与されたＴＣＯの
受光面電極（２）を組込んだ光起電力装置を評価するた
めに、斯る凹凸面（２ｔｅｘ）に上記特公昭５３−３７
７１８号公報に示されたｐｉｎ接合を有するアモルファ
スシリコンの半導体光活性層（３）とアルミニウム電極
の背面電極（４）とを順次積層した光起電力装置を作製
し、その反射率をほぼ可視光帯域に亘って測定したとこ
ろ、第１１図の反射特性を得た。一方、斯る本発明の凹
凸加工きれた工ＣＯを受光面電極（２）とした光起電力
装置に代って、第２図及び第７図、第８図に示した凹凸
加工する以前の１０層（５）を受光面電極とした光起電
力装置の反射特性を測定し、その結果が第１２図に示し
である。斯る第１２図の反射特性を見ると、約４５０ｎ
ｍ、約６５０ｎｍ以上の波長に対して断続的に２０％以
上の反射率を呈していたのに対し、本発明による凹凸な
受光面電極（２）を用いた光起電力装置に於いては約４
００〜８００ｎｍの可視光帯域に亘ってほぼ一定した１
０％以下の反射率を呈するに止まった。この反射率の低
域は光電変換作用をなす半導体光活性層（３〉内に多く
の光を入射せしめることを意味し、この様な光起電力装
置にあっては光電変換率を上昇せしめることができる。In order to evaluate a photovoltaic device incorporating a TCO light-receiving surface electrode (2) provided with an uneven surface (2tax) in this way, the above-mentioned Japanese Patent Publication No. 53-37 was applied to the uneven surface (2tex).
A photovoltaic device was fabricated in which an amorphous silicon semiconductor photoactive layer (3) having a pin junction and a back electrode (4) of an aluminum electrode were sequentially laminated as shown in Publication No. When measurements were made over the band, the reflection characteristics shown in FIG. 11 were obtained. On the other hand, instead of a photovoltaic device using the unevenly processed CO of the present invention as the light-receiving surface electrode (2), a photovoltaic device using the unevenly processed CO as shown in FIGS. 2, 7, and 8, The reflection characteristics of a photovoltaic device using the 10th layer (5) as a light-receiving surface electrode were measured, and the results are shown in FIG. Looking at the reflection characteristics in Figure 12, it is approximately 450n.
In contrast, in the photovoltaic device using the uneven light-receiving surface electrode (2) of the present invention, the reflectance was intermittently over 20% for wavelengths of approximately 650 nm or more. 4
1, which is almost constant over the visible light band from 00 to 800 nm.
The reflectance remained below 0%. This low range of reflectance means that more light is allowed to enter the semiconductor photoactive layer (3) that performs photoelectric conversion, and in such photovoltaic devices, it increases the photoelectric conversion rate. I can do it.
第１３図乃至第１６図は本発明の比較例として従来の技
術の項で述べた支持基板（１）に予め凹凸表面（１ｔｅ
ｘ）を付与し、その凹凸表面（ｌｔａｘ）上に１０層（
５）を形成したものを示し、第１３図は模式的断面図、
第１４図はそのＴＣＯ層（５）の粒子構造の断面状態を
示す走査顕微鏡写真、第１５図は同じく粒子構造を傾斜
角８０度の方向から臨んだ走査顕微鏡写真及び第１６図
は斯る粒子構造のＴＣＯ層〈５）を光起電力装置の受光
面電極としたときの反射特性図である。斯る走査顕微鏡
写真の倍率は、第１４図は第５図及び第７図と同じであ
り、第１５図は第６図及び第８図と同一である。また反
射特性を測定する光起電力装置の半導体光活性層（３）
及びアルミニウムの背面電極（４）ともに第１１図、第
１２図のものと同時に形成きれている。従って、この先
行技術に開示されたＴＣＯ層（５）を光起電力装置の受
光面電極として用いても、本発明の凹凸加工きれた受光
面電極（２）を備えた光起電力装置の反射特性に対して
特に６００ｎｍの長波長帯域で劣っていることが明らか
である。13 to 16 show a support substrate (1) having an uneven surface (1te) as a comparative example of the present invention.
x) and 10 layers (
5) is shown, and FIG. 13 is a schematic cross-sectional view,
Fig. 14 is a scanning micrograph showing the cross-sectional state of the grain structure of the TCO layer (5), Fig. 15 is a scanning micrograph showing the grain structure from a direction with an inclination angle of 80 degrees, and Fig. 16 is a scanning micrograph showing the grain structure of the TCO layer (5). FIG. 6 is a reflection characteristic diagram when the TCO layer of the structure (5) is used as a light-receiving surface electrode of a photovoltaic device. The magnification of such scanning micrographs is the same in FIG. 14 as in FIGS. 5 and 7, and in FIG. 15 as in FIGS. 6 and 8. Also, the semiconductor photoactive layer (3) of a photovoltaic device whose reflection properties are measured.
Both the aluminum back electrode (4) and the aluminum back electrode (4) were formed at the same time as those in FIGS. 11 and 12. Therefore, even if the TCO layer (5) disclosed in this prior art is used as the light-receiving surface electrode of a photovoltaic device, the reflection of the photovoltaic device equipped with the unevenly processed light-receiving surface electrode (2) of the present invention is It is clear that the characteristics are particularly poor in the long wavelength band of 600 nm.
（ト） 発明の効果
本発明は以上の説明から明らかな如く、半導体光活性層
との界面側に高低差約１０００〜５０００Å、凸部と凸
部との間隔約２０００〜ｔｏｏｏｏ人の凹凸面を備えた
平均粒径約５００〜２０００人のＴＣＯからなる受光面
電極を用いたので、受光面電極と半導体光活性層との界
面に於ける入射光の反射損失と、比抵抗の増大、光透過
率の減少及び支持基板との密着力の低下を同時に解決す
ることができ、光電変換効率を総合的に上昇せしめ得る
。(G) Effects of the Invention As is clear from the above description, the present invention has an uneven surface on the interface side with the semiconductor photoactive layer with a height difference of about 1000 to 5000 Å and a distance between the convex parts of about 2000 to too much. Since we used a light-receiving surface electrode made of TCO with an average particle size of about 500 to 2,000 people, we could reduce the reflection loss of incident light at the interface between the light-receiving surface electrode and the semiconductor photoactive layer, increase in specific resistance, and light transmission. It is possible to simultaneously solve the problem of a decrease in conversion rate and a decrease in adhesion to a support substrate, and to increase the photoelectric conversion efficiency overall.
第１図は本発明光起電力装置の一実施例を示す模式的断
面図、第２図乃至第４図は本発明光起電力装置に用いら
れる受光面電極の凹凸化方法を説明するための状態別模
式的断面図、第５図及び第６図は凹凸化される前の透光
性導電酸化物の粒子構造の断面状態及び傾斜角８０度の
方向から臨んだ状態を示す走査顕微鏡写真、第７図及び
第８図は凹凸化された後の透光性導電酸化物の粒子構造
断面状態及び傾斜角８０度の方向から臨んだ状態を示す
走査顕微鏡写真、第９図及び第１０図は第３図に相当す
る凹凸加工の途中状態に於ける透光性導電酸化物の粒子
構造の断面状態及び傾斜角８０度の方向から臨んだ状態
の走査顕微鏡写真、第１１図は本発明光起電力装置の反
射特性図、第１２図は従来装置の反射特性図、第１３図
は本発明の比較例として用いられた透光性導電酸化物基
板の模式的断面図、第１４図及び第１５図は上記第１３
図に示した本発明比較例に於ける透光性導電酸化物の粒
子構造の断面状態及び傾斜角８０度の方向から臨んだ状
態を示す走査顕微鏡写真、第１６図は本発明比較例の反
射特性図、を夫々示している。
（１）・・・透光性支持基板、（２）・・・受光面電極
、（２ｔｅｘ）・・・凹凸面、（３）・・・半導体光活
性層、（４）・・・背面電極。FIG. 1 is a schematic cross-sectional view showing one embodiment of the photovoltaic device of the present invention, and FIGS. 2 to 4 are diagrams for explaining a method of making the light-receiving surface electrode uneven for use in the photovoltaic device of the present invention. Schematic cross-sectional views by state; FIGS. 5 and 6 are scanning micrographs showing the cross-sectional state of the particle structure of the transparent conductive oxide before it is roughened, and the state viewed from a direction with an inclination angle of 80 degrees; Figures 7 and 8 are scanning micrographs showing the cross-sectional state of the grain structure of the translucent conductive oxide after it has been made uneven, and the state viewed from an angle of inclination of 80 degrees, and Figures 9 and 10 are Fig. 3 shows a cross-sectional state of the particle structure of the translucent conductive oxide in the middle of roughening process, and a scanning micrograph of the state viewed from the direction of the inclination angle of 80 degrees, and Fig. 11 shows the photovoltaic material of the present invention 12 is a reflection characteristic diagram of a conventional device; FIG. 13 is a schematic cross-sectional view of a transparent conductive oxide substrate used as a comparative example of the present invention; FIGS. 14 and 15. The figure is number 13 above.
Figure 16 is a scanning micrograph showing the cross-sectional state of the particle structure of the transparent conductive oxide in the comparative example of the present invention and the state viewed from a direction with an inclination angle of 80 degrees. Characteristic diagrams are shown respectively. (1)...Transparent support substrate, (2)...Light-receiving surface electrode, (2tex)...Uneven surface, (3)...Semiconductor photoactive layer, (4)...Back electrode .
Claims (1)
活性層及び背面電極をこの順序で積層した光起電力装置
であって、上記受光面電極は平均粒径約５００〜２００
０Åの透光性導電酸化物からなると共に、この受光面電
極は半導体活性層との界面側に高低差約１０００〜５０
００Å、凸部と凸部との間隔約２０００〜１００００Å
の凹凸面を備えたことを特徴とした光起電力装置。(1) A photovoltaic device in which a light-receiving surface electrode, a semiconductor photoactive layer, and a back electrode are laminated in this order on a flat surface of a light-transmitting support substrate, wherein the light-receiving surface electrode has an average particle size of approximately 500 to 200.
This light-receiving surface electrode is made of a transparent conductive oxide with a thickness of 0 Å, and has a height difference of about 1000 to 50 Å on the interface side with the semiconductor active layer.
00 Å, distance between protrusions approximately 2000 to 10000 Å
A photovoltaic device characterized by having an uneven surface.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60131285A JPS61288473A (en) | 1985-06-17 | 1985-06-17 | Photovoltaic device |
| US06/872,684 US4732621A (en) | 1985-06-17 | 1986-06-10 | Method for producing a transparent conductive oxide layer and a photovoltaic device including such a layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60131285A JPS61288473A (en) | 1985-06-17 | 1985-06-17 | Photovoltaic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61288473A true JPS61288473A (en) | 1986-12-18 |
| JPH0328073B2 JPH0328073B2 (en) | 1991-04-17 |
Family
ID=15054375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60131285A Granted JPS61288473A (en) | 1985-06-17 | 1985-06-17 | Photovoltaic device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61288473A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0399477A (en) * | 1989-09-12 | 1991-04-24 | Canon Inc | Solar cell |
| JP2862174B2 (en) * | 1987-05-22 | 1999-02-24 | グラステツク・ソーラー・インコーポレーテツド | Substrates for solar cells |
| US6362414B1 (en) | 1999-05-31 | 2002-03-26 | Kaneka Corporation | Transparent layered product and glass article using the same |
| US6444898B1 (en) | 1999-06-18 | 2002-09-03 | Nippon Sheet Glass Co., Ltd. | Transparent layered product and glass article using the same |
| JP2002352956A (en) * | 2001-03-23 | 2002-12-06 | Mitsubishi Chemicals Corp | Thin-film light emitting substance and manufacturing method therefor |
| US6498380B1 (en) | 1999-06-18 | 2002-12-24 | Nippon Sheet Glass Co., Ltd. | Substrate for photoelectric conversion device, and photoelectric conversion device using the same |
| US7179527B2 (en) | 2001-10-19 | 2007-02-20 | Asahi Glass Company, Limited | Substrate with transparent conductive oxide film, process for its production and photoelectric conversion element |
| JP2009531842A (en) * | 2006-03-30 | 2009-09-03 | ユニヴェルスィテ ドゥ ヌシャテル | Uneven transparent conductive layer and method for producing the same |
| US7608294B2 (en) | 2003-11-18 | 2009-10-27 | Nippon Sheet Glass Company, Limited | Transparent substrate with transparent conductive film, method of manufacturing the same, and photoelectric conversion element including the substrate |
| WO2011161961A1 (en) | 2010-06-23 | 2011-12-29 | Ｊｘ日鉱日石エネルギー株式会社 | Photoelectric conversion element |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4229606B2 (en) * | 2000-11-21 | 2009-02-25 | 日本板硝子株式会社 | Base for photoelectric conversion device and photoelectric conversion device including the same |
| CN109346556B (en) * | 2018-09-21 | 2020-02-21 | 中国科学院半导体研究所 | Preparation method of optically rough and electrically flat transparent conductive substrate |
-
1985
- 1985-06-17 JP JP60131285A patent/JPS61288473A/en active Granted
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2862174B2 (en) * | 1987-05-22 | 1999-02-24 | グラステツク・ソーラー・インコーポレーテツド | Substrates for solar cells |
| JPH0399477A (en) * | 1989-09-12 | 1991-04-24 | Canon Inc | Solar cell |
| US6362414B1 (en) | 1999-05-31 | 2002-03-26 | Kaneka Corporation | Transparent layered product and glass article using the same |
| US6444898B1 (en) | 1999-06-18 | 2002-09-03 | Nippon Sheet Glass Co., Ltd. | Transparent layered product and glass article using the same |
| US6498380B1 (en) | 1999-06-18 | 2002-12-24 | Nippon Sheet Glass Co., Ltd. | Substrate for photoelectric conversion device, and photoelectric conversion device using the same |
| JP2002352956A (en) * | 2001-03-23 | 2002-12-06 | Mitsubishi Chemicals Corp | Thin-film light emitting substance and manufacturing method therefor |
| US7179527B2 (en) | 2001-10-19 | 2007-02-20 | Asahi Glass Company, Limited | Substrate with transparent conductive oxide film, process for its production and photoelectric conversion element |
| US7364808B2 (en) | 2001-10-19 | 2008-04-29 | Asahi Glass Company, Limited | Substrate with transparent conductive oxide film, process for its production and photoelectric conversion element |
| US7883789B2 (en) | 2001-10-19 | 2011-02-08 | Asahi Glass Company, Limited | Substrate with transparent conductive oxide film, process for its production and photoelectric conversion element |
| US7608294B2 (en) | 2003-11-18 | 2009-10-27 | Nippon Sheet Glass Company, Limited | Transparent substrate with transparent conductive film, method of manufacturing the same, and photoelectric conversion element including the substrate |
| US7846562B2 (en) | 2003-11-18 | 2010-12-07 | Nippon Sheet Glass Company, Limited | Transparent substrate with transparent conductive film, method of manufacturing the same, and photoelectric conversion element including the substrate |
| JP2009531842A (en) * | 2006-03-30 | 2009-09-03 | ユニヴェルスィテ ドゥ ヌシャテル | Uneven transparent conductive layer and method for producing the same |
| WO2011161961A1 (en) | 2010-06-23 | 2011-12-29 | Ｊｘ日鉱日石エネルギー株式会社 | Photoelectric conversion element |
| US8802971B2 (en) | 2010-06-23 | 2014-08-12 | Jx Nippon Oil & Energy Corporation | Photoelectric conversion element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0328073B2 (en) | 1991-04-17 |
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