JPH0650780B2 - Solar cell and manufacturing method thereof - Google Patents
Solar cell and manufacturing method thereofInfo
- Publication number
- JPH0650780B2 JPH0650780B2 JP63192013A JP19201388A JPH0650780B2 JP H0650780 B2 JPH0650780 B2 JP H0650780B2 JP 63192013 A JP63192013 A JP 63192013A JP 19201388 A JP19201388 A JP 19201388A JP H0650780 B2 JPH0650780 B2 JP H0650780B2
- Authority
- JP
- Japan
- Prior art keywords
- solar cell
- layer
- window
- film
- type
- 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.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910021424 microcrystalline silicon Inorganic materials 0.000 claims description 28
- 239000011521 glass Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 35
- 229910021417 amorphous silicon Inorganic materials 0.000 description 27
- 239000010409 thin film Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002294 plasma sputter deposition Methods 0.000 description 6
- 239000002826 coolant Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000013081 microcrystal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910010276 inorganic hydride Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/075—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0368—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including polycrystalline semiconductors
- H01L31/03682—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including polycrystalline semiconductors including only elements of Group IV of the Periodic Table
- H01L31/03685—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including polycrystalline semiconductors including only elements of Group IV of the Periodic Table including microcrystalline silicon, uc-Si
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
- Photovoltaic Devices (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ この発明は、シリコン系太陽電池とその製造方法に関
し、さらに詳しくは、pin型太陽電池の窓側層に用いた
微結晶シリコン薄膜の材質の改良と、その窓側層の製造
方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a silicon-based solar cell and a method for manufacturing the same, and more specifically, to an improvement in the material of a microcrystalline silicon thin film used for a window-side layer of a pin-type solar cell. And a method of manufacturing the window side layer.
［従来の技術］ 従来、シリコン系太陽電池は、アモルファスシリコン太
陽電池（以後a-Si太陽電池という）を主流として開発が
進められており、その特性上の概説として下記刊行物に
開示されたものがある。[Prior Art] Conventionally, silicon-based solar cells have been developed mainly in the form of amorphous silicon solar cells (hereinafter referred to as a-Si solar cells), and are disclosed in the following publications as an outline of their characteristics. There is.
電気学会：太陽電池調査専門委員会編；太陽電池ハンド
ブック；電気学会発行（昭和60年７月30日）．p96 とくに、a-Si太陽電池のpin構造において、ヘテロ接合
セルで形成される代表的な太陽電池の構成を以下説明す
る。The Institute of Electrical Engineers of Japan: Photovoltaic Cell Survey Special Committee Edition; Solar Cell Handbook; Published by The Institute of Electrical Engineers of Japan (July 30, 1985). p96 In particular, in the pin structure of an a-Si solar cell, the structure of a typical solar cell formed of heterojunction cells will be described below.
第３図はa-SiC：Ｈ（ｐ型）／a-Si：Ｈ（ｉ型）のヘテ
ロ接合セルを窓側層としたa-Si太陽電池の構造模式図で
ある。図において、１は光（ｈν）の窓を構成するガラ
ス基板で、２はガラス基板に形成されたITOで示される
透明導電膜、３はa-SiCからなるｐ型層（窓側層）、４
はa-Siで形成されるｉ型層、５はa-Siからなるｎ型層、
６はメタル（Me）で形成された電極である。この構成は
ガラス／ITO／pin／Meという符号で示されるもので、a-
SiC層３とa-Si層４とによってヘテロ接合を形成し、光
（ｈν）の変換効率の向上をはかっている。FIG. 3 is a structural schematic diagram of an a-Si solar cell having a window-side layer of a-SiC: H (p type) / a-Si: H (i type) heterojunction cell. In the figure, 1 is a glass substrate forming a window of light (hν), 2 is a transparent conductive film shown by ITO formed on the glass substrate, 3 is a p-type layer (window side layer) made of a-SiC, 4
Is an i-type layer made of a-Si, 5 is an n-type layer made of a-Si,
Reference numeral 6 is an electrode made of metal (Me). This structure is indicated by the code glass / ITO / pin / Me.
A heterojunction is formed by the SiC layer 3 and the a-Si layer 4 to improve the conversion efficiency of light (hν).
第４図はa-Siの微結晶化層を窓側層に用いたヘテロ接合
太陽電池の構成模式図である。なお、この微結晶化層は
a-Si中に微結晶Siが点在して含まれた層で、一般にμｃ
−Siといわれているものである。図において、１，２，
４及び第３図の従来例と同一又は相当部分の符号と同一
符号で示し、説明を省略する。FIG. 4 is a schematic configuration diagram of a heterojunction solar cell in which a microcrystalline layer of a-Si is used as a window side layer. The microcrystallized layer is
A layer containing microcrystalline Si scattered in a-Si, generally μc
-It is called Si. In the figure, 1, 2,
4 and FIG. 3 are shown by the same reference numerals as those of the conventional example of FIG. 4 and FIG.
７は窓側層を形成するｎ型の微結晶化シリコン層であ
り、以下ｎ（μｃ−Si）層と称する。そして、８はｐ型
のa-Si層であり、第４図の構成は、ガラス／ITO／ｎ
（μｃ−Si）ip／Meで表わされ、正確にはnip構造であ
る。この場合、ｎ（μｃ−Si）層７とｉ型のa-Si層４に
よってヘテロ接合を形成し、光電変換効率を向上してい
る。Reference numeral 7 denotes an n-type microcrystallized silicon layer forming a window side layer, which is hereinafter referred to as an n (μc-Si) layer. 8 is a p-type a-Si layer, and the structure of FIG. 4 is glass / ITO / n.
It is represented by (μc-Si) ip / Me, and is precisely a nip structure. In this case, the n (μc-Si) layer 7 and the i-type a-Si layer 4 form a heterojunction to improve the photoelectric conversion efficiency.
この光電変換効率の向上については、とくに第４図の従
来例に示したヘテロ接合太陽電池においては、通常のa-
Si太陽電池に比べて開放電圧及び光電変換効率が大幅に
改善されるということが報告されている、このｎ（μｃ
−Si）膜、すなわちｎ型の微結晶化a-Si膜は一般のa-S
i：Ｈ膜に比べて吸収係数が小さく、光電導電率が高い
ことに起因するものと考えられている。Regarding the improvement of the photoelectric conversion efficiency, especially in the heterojunction solar cell shown in the conventional example of FIG.
It has been reported that the open-circuit voltage and photoelectric conversion efficiency are significantly improved compared to Si solar cells.
-Si) film, that is, an n-type microcrystallized a-Si film is a general aS
It is considered that the absorption coefficient is smaller than that of the i: H film and the photoelectric conductivity is high.
［発明が解決しようとする課題］ しかしながら、上記のような従来のヘテロ接合型a-Si太
陽電池、とくに従来法によって作成されたμｃ−Si膜
は、a-Si膜中に微結晶が点在するにすぎない形態を有す
るものであるから、その光電変換効率は7.8％程度であ
り、上記文献にみられる他の方法による値（〜10％）に
比べて満足すべき値といえない。したがって、太陽電池
を形成するSi膜としてのとくにμｃ−Si膜の物性の向上
が要望されていた。[Problems to be Solved by the Invention] However, in the conventional heterojunction a-Si solar cell as described above, particularly in the μc-Si film formed by the conventional method, microcrystals are scattered in the a-Si film. The photoelectric conversion efficiency is about 7.8%, which is not a satisfactory value compared with the values (-10%) obtained by the other methods found in the above literature. Therefore, it has been demanded to improve the physical properties of the μc-Si film, especially as the Si film forming the solar cell.
この発明はこのような要請に応ずるためになされたもの
で、μｃ−Si膜の中の微結晶体の体積率を増大させると
いうように膜体の物性を制御して光電変換効率が向上す
る太陽電池の製造方法とその電池構成を提供することを
目的とするものである。The present invention has been made in response to such a demand, and a solar cell in which the photoelectric conversion efficiency is improved by controlling the physical properties of the film body such as increasing the volume ratio of the microcrystalline body in the μc-Si film. It is an object to provide a battery manufacturing method and a battery configuration thereof.
［課題を解決するための手段］ この発明に係るpin型太陽電池は、ｐ型層及びｎ型層の
うちのいずれか一つの層で構成する窓側層を実質的に平
均粒径が100Å以下の微結晶Siのみの薄膜とするもので
ある。[Means for Solving the Problems] In a pin-type solar cell according to the present invention, a window-side layer composed of any one of a p-type layer and an n-type layer has an average particle diameter of substantially 100 Å or less. It is a thin film of only microcrystalline Si.
また、この発明に係るpin型太陽電池の製造方法は、ｐ
型層及びｎ型層のうちのいずれか一つの層を実質的に平
均粒径が100Å以下の微結晶Siのみからなる微結晶Si薄
膜で構成された窓側層として形成するもので、窓を構成
するガラス基板上に透明導電膜を形成したのち、上記ガ
ラス基板の温度を０℃以下に保持しながら、水素プラズ
マによるSiのスパッタリングを行って透明導電膜上にSi
を堆積することにより、実質的に100％に近い体積率を
有する微結晶シリコンのみの薄膜からなる窓側層を形成
するものである。Further, the method for manufacturing a pin-type solar cell according to the present invention is
One of the n-type layer and the n-type layer is formed as a window-side layer composed of a microcrystalline Si thin film consisting essentially of microcrystalline Si having an average grain size of 100Å or less After forming the transparent conductive film on the glass substrate, the temperature of the glass substrate is maintained at 0 ° C. or lower, and the Si is sputtered by hydrogen plasma to form Si on the transparent conductive film.
Is deposited to form a window-side layer composed of a thin film of only microcrystalline silicon having a volume ratio substantially close to 100%.
なお、窓側層の極性を左右するドーピングは、スパッタ
リング中に無機水素化物を導入することで達成され、例
えばｎ型微結晶Si薄膜の形成にはｐＨ３（ホスフィ
ン）、ｐ型微結晶Si薄膜の形成にはＢ２Ｈ６（ジボラ
ン）を導入する。The doping that affects the polarity of the window-side layer is achieved by introducing an inorganic hydride during sputtering. For example, in forming an n-type microcrystalline Si thin film, pH 3 (phosphine), a p-type microcrystalline Si thin film are used. B 2 H 6 (diborane) is introduced for formation.
［作用］ この発明の太陽電池の製造方法においては、pin構造の
窓側層を形成する場合、ガラス基板上に形成された透明
導電膜上にガラス基板温度を０℃以下とし、水素プラズ
マのスパッタリングによりSiを堆積するから、平均粒径
が100Å以下で、かつ100％近くの体積率を有するSi微結
晶体からなるSiの微結晶膜が得られる。[Operation] In the method for manufacturing a solar cell of the present invention, when the window side layer having a pin structure is formed, the temperature of the glass substrate is set to 0 ° C. or lower on the transparent conductive film formed on the glass substrate, and hydrogen plasma sputtering is performed. Since Si is deposited, a Si microcrystalline film composed of a Si microcrystalline body having an average grain size of 100Å or less and a volume ratio of nearly 100% can be obtained.
そして、この発明の製造方法で得られた微結晶Si膜はと
くに平均結晶粒径が100Å以下のときはバンドギャップ
幅が2.0eV位に大きくなる。さらに、この微結晶Si薄膜
は微結晶体の内部はSiであり、外部はシリコン水素化物
となって形成されており、各微結晶体はファンデルワー
ルス力でつながっているため、強固な薄膜が形成され
る。The band gap width of the microcrystalline Si film obtained by the manufacturing method of the present invention becomes as large as 2.0 eV especially when the average crystal grain size is 100 Å or less. Furthermore, this microcrystalline Si thin film is formed with Si inside the microcrystalline body and silicon hydride outside, and since each microcrystalline body is connected by Van der Waals force, a strong thin film is formed. It is formed.
このような微結晶Si薄膜を窓側層として形成されたヘテ
ロ接合構造の太陽電池は大きな光電変換効率特性を有す
る。A solar cell having a heterojunction structure in which such a microcrystalline Si thin film is formed as a window side layer has large photoelectric conversion efficiency characteristics.
［実施例］ 実施例１； 第１図はこの発明の一実施例を示すシリコン系太陽電池
の構造を説明する模式図である。Example 1 Example 1 FIG. 1 is a schematic view for explaining the structure of a silicon-based solar cell showing an example of the present invention.
図において、11は光（ｈν）の窓を構成するガラス基板
であり、12はガラス基板11の表面に形成されたITO/SnO2
の２層膜からなる透明導電膜で、窓側の電極を形成する
ものである。13は透明導電膜12上に形成され、100％に
近い体積率をもち、かつ平均粒径が100Å（オングスト
ローム）以下の微結晶Si粒子からなるｎ型微結晶Si薄膜
（ｎ型の窓側層）である。14はｉ型のa-Si：Ｈ薄膜（ｉ
型層）、15はｐ型のa-Si：Ｈ薄膜（ｐ型層）である。ｎ
型微結晶Si薄膜13，ｉ型a-Si：Ｈ薄膜14及びｐ型a-Si薄
膜15によってヘテロ接合型太陽電池のnip構造を構成
し、第１図の実施例に示す全体で太陽電池を形成してい
る。In the figure, 11 is a glass substrate forming a window of light (hν), and 12 is ITO / SnO 2 formed on the surface of the glass substrate 11.
The window-side electrode is formed of a transparent conductive film composed of the above two-layer film. 13 is an n-type microcrystalline Si thin film (n-type window side layer) formed on the transparent conductive film 12 and having a volume ratio close to 100% and an average grain size of 100Å (angstrom) or less Is. 14 is an i-type a-Si: H thin film (i
15) is a p-type a-Si: H thin film (p-type layer). n
Type microcrystalline Si thin film 13, i-type a-Si: H thin film 14 and p-type a-Si thin film 15 constitute a nip structure of a heterojunction solar cell, and the solar cell is formed as a whole in the embodiment shown in FIG. Is forming.
この太陽電池の動作については、従来のa-Si型太陽電池
の動作と同様であり、周知であるので説明は省略する。The operation of this solar cell is the same as the operation of a conventional a-Si solar cell, and is well known, so description thereof will be omitted.
第１図の実施例の太陽電池の性能を試験した結果、開放
電圧は0.95Ｖと高い値を示し、光電変換効率は13.0％と
大幅に増大し、ほぼ満足される結果が得られた。As a result of testing the performance of the solar cell of the example of FIG. 1, the open circuit voltage was as high as 0.95 V, and the photoelectric conversion efficiency was significantly increased to 13.0%, and almost satisfactory results were obtained.
実施例２； この発明による太陽電池の上記窓側層の形成はプラズマ
スパッタリング装置を用いて行い、その他の部分は通常
の方法によって行った。以下、はじめに、プラズマスパ
ッタリング装置の構成について説明し、ついで製造方法
について説明する。Example 2 The formation of the window side layer of the solar cell according to the present invention was performed using a plasma sputtering apparatus, and the other portions were performed by a usual method. Hereinafter, first, the configuration of the plasma sputtering apparatus will be described, and then the manufacturing method will be described.
第２図は第１図の実施例の太陽電池を例として、太陽電
池の窓側層13の製造方法に用いたプラズマスパッタリン
グ装置の模式断面図である。図において、21は真空容器
で、図示しない真空装置に連結された排気孔31と真空容
器21の雰囲気を調整するガス導入孔22が設けられてい
る。27,29はプラズマ放電用の電極で、電極27には永久
磁石26が組込まれ、電極27の上面に半導体材料（この場
合Si）からなるターゲット25が設置されており、電極29
には太陽電池のガラス基板28が設置される。電極29には
図示しない冷却装置に連結された冷却媒体の出入孔30が
設けられている。23は電極27,29に電源を供給する高周
波電源である。なお、24は形成された水素プラズマであ
る。FIG. 2 is a schematic cross-sectional view of the plasma sputtering apparatus used in the method for manufacturing the window-side layer 13 of the solar cell, taking the solar cell of the embodiment of FIG. 1 as an example. In the figure, reference numeral 21 denotes a vacuum container, which is provided with an exhaust hole 31 connected to a vacuum device (not shown) and a gas introduction hole 22 for adjusting the atmosphere of the vacuum container 21. Reference numerals 27 and 29 denote electrodes for plasma discharge. A permanent magnet 26 is incorporated in the electrode 27, and a target 25 made of a semiconductor material (Si in this case) is placed on the upper surface of the electrode 27.
A glass substrate 28 of a solar cell is installed in the. The electrode 29 is provided with a cooling medium inlet / outlet hole 30 connected to a cooling device (not shown). Reference numeral 23 is a high frequency power supply for supplying power to the electrodes 27 and 29. In addition, 24 is the formed hydrogen plasma.
下表にこの実施例において上記窓側層13を形成したとき
の具体的な動作条件を挙げる。The following table shows specific operating conditions when the window side layer 13 is formed in this embodiment.
以下、第２図のプラズマスパッタリング装置による窓側
層13の形成方法を主として、この発明による太陽電池の
製造方法を説明する。 Hereinafter, the method of manufacturing the solar cell according to the present invention will be described, mainly about the method of forming the window side layer 13 by the plasma sputtering apparatus of FIG.
まず、ガラス基板11（第２図では28に相当）を真空容器
21内に設置する前に、ガラス基板11上にITO/SnO2（ITO
はInとTiの酸化物）の２層膜からなる透明導電膜12を形
成する。この状態のガラス基板をガラス基板28として電
極29上に設置し、ターゲット25と対向させる。First, place the glass substrate 11 (corresponding to 28 in FIG. 2) in a vacuum container.
Before installing in the 21, the ITO / SnO 2 (ITO
Forms a transparent conductive film 12 composed of a two-layer film of In and Ti oxide. The glass substrate in this state is set as the glass substrate 28 on the electrode 29 and is opposed to the target 25.
ついで、窓側層13を構成するｎ型微結晶Si膜を形成する
のであるが、その手順はガス導入孔22より水素（Ｈ２）
ガスと所定量のｐＨ３ガスを導入し、真空容器21内の雰
囲気として0.5Torrのガス圧を形成したのち、電極27,29
に高周波電源23からの電圧を印加する。このときプラズ
マ24が形成されプラズマ24中の水素イオンによりターゲ
ット25を構成するSiをスパッタリングし、液体窒素を冷
却媒体の出入口孔30からの導入により液体窒素温度に冷
却されたガラス基板28上にSiの薄膜を形成して窓側層13
を形成する。この場合、冷却媒体は０℃以下に冷却され
た水であってもよい。Next, an n-type microcrystalline Si film forming the window side layer 13 is formed. The procedure is as follows: hydrogen (H 2 )
After introducing a gas and a predetermined amount of pH 3 gas to form a gas pressure of 0.5 Torr as an atmosphere in the vacuum container 21, the electrodes 27, 29 are formed.
The voltage from the high frequency power supply 23 is applied to the. At this time, plasma 24 is formed and hydrogen ions in the plasma 24 sputter Si constituting the target 25, and liquid nitrogen is introduced onto the glass substrate 28 cooled to the liquid nitrogen temperature by introducing the cooling medium from the inlet / outlet hole 30 of the cooling medium. Window side layer 13
To form. In this case, the cooling medium may be water cooled to 0 ° C or lower.
形成されたSi薄膜、すなわち窓側層13を観測したとこ
ろ、平均粒径が100Å以下のSi微結晶がほぼ連続的に結
合して形成されていることがわかった。When the formed Si thin film, that is, the window-side layer 13 was observed, it was found that Si microcrystals having an average particle size of 100 Å or less were formed almost continuously.
ついで、この窓側層13上に通常の方法によりアモルファ
スのｉ型層であるｉ型a-Si：Ｈ膜14を形成し、さらにア
モルファスのｐ型層であるｐ型a-Si：Ｈ膜15を順次形成
してnip構造を形成した。Then, an i-type a-Si: H film 14 which is an amorphous i-type layer is formed on the window-side layer 13 by a usual method, and a p-type a-Si: H film 15 which is an amorphous p-type layer is further formed. The layers were sequentially formed to form a nip structure.
最後に通常の真空蒸着法により金属（Me）を蒸着して電
極16を形成することにより、この発明による太陽電池の
作成を完了する。Finally, metal (Me) is vapor-deposited by an ordinary vacuum vapor deposition method to form the electrode 16, thereby completing the production of the solar cell according to the present invention.
なお、上記実施例１，２においては、太陽電池のSi層を
nip構造とし、ｎ型微結晶Si膜を窓側層とする場合につ
いて説明したが、太陽電池のSi層をpin構造とし、ｐ型
微結晶Si膜を窓側層とすることも太陽電池の構成上差支
えないものである。この場合、nip構造は一般に称され
るpin構造の中に含まれるものである。また、ガラス基
板の冷却媒体としては０℃以下であればよいが、実施例
の液体窒素のほかに低温下限は液体ヘリウム温度まで実
施可能であり、微結晶媒体の形成には低温ほどよいこと
が確認されている。In Examples 1 and 2 above, the Si layer of the solar cell was
Although the case where the nip structure is used and the n-type microcrystalline Si film is used as the window-side layer has been described, it is also a structural difference of the solar cell that the Si layer of the solar cell has the pin structure and the p-type microcrystalline Si film is the window-side layer. There is no such thing. In this case, the nip structure is included in the commonly called pin structure. Further, the cooling medium for the glass substrate may be 0 ° C. or lower, but in addition to the liquid nitrogen of the embodiment, the lower limit of the low temperature can be implemented up to the liquid helium temperature, and the lower temperature is better for forming the microcrystalline medium. It has been confirmed.
［発明の効果］ 以上説明したようにこの発明による太陽電池は、微結晶
Si膜を窓側層として有するので、通常の製法では作製さ
れた微結晶化a-Si膜（μｃ−Si）よりバンドギャップが
広くなり、アモルファスSi太陽電池の開放電圧が増大
し、かつ光電変換効率の高性能な太陽電池の開発が可能
である。[Effects of the Invention] As described above, the solar cell of the present invention is
Since it has a Si film as the window-side layer, it has a wider bandgap than the microcrystallized a-Si film (μc-Si) produced by the usual manufacturing method, increasing the open circuit voltage of the amorphous Si solar cell and increasing the photoelectric conversion efficiency. It is possible to develop high performance solar cells.
また、この発明による太陽電池の製造方法は、Si膜の窓
側層形成において、基板温度を０℃以下に保持した状態
で水素プラズマによるスパッタリングを行って、ガラス
基板上にSi膜を形成するので、窓側層として100％に近
いSi微結晶からなる微結晶Si膜が形成される。このため
上記のような高性能太陽電池の供給に対する寄与が大で
ある。Further, in the method for manufacturing a solar cell according to the present invention, in forming the window-side layer of the Si film, sputtering with hydrogen plasma is performed while the substrate temperature is kept at 0 ° C. or lower to form the Si film on the glass substrate. As the window side layer, a microcrystalline Si film made of Si microcrystals close to 100% is formed. For this reason, it greatly contributes to the supply of the high-performance solar cell as described above.
第１図はこの発明の一実施例を示す太陽電池の構造模式
図、第２図はこの発明の太陽電池の製造工程中に用いた
プラズマスパッタリング装置の模式断面図、第３図は従
来のa-Si太陽電池のヘテロ接合セルの模式図、第４図は
従来のa-Si太陽電池に微結晶化Si膜を用いたヘテロ接合
セルの模式図である。 図において、11はガラス基板、12は透明導電膜、13はｎ
型微結晶Si膜、14はｉ型のa-Si膜、15はｐ型のa-Si膜、
16は電極、21は真空容器、22はガス導入孔、23は高周波
電源、24は水素プラズマ、25はターゲット、26は永久磁
石、27は電極、28はガラス基板、29は電極、30は冷却媒
体の出入孔、31は排気孔である。FIG. 1 is a schematic view of the structure of a solar cell showing an embodiment of the present invention, FIG. 2 is a schematic sectional view of a plasma sputtering apparatus used during the manufacturing process of the solar cell of the present invention, and FIG. Fig. 4 is a schematic view of a heterojunction cell of a -Si solar cell, and Fig. 4 is a schematic view of a heterojunction cell using a microcrystallized Si film in a conventional a-Si solar cell. In the figure, 11 is a glass substrate, 12 is a transparent conductive film, and 13 is n.
-Type microcrystalline Si film, 14 is i-type a-Si film, 15 is p-type a-Si film,
16 is an electrode, 21 is a vacuum container, 22 is a gas introduction hole, 23 is a high frequency power supply, 24 is hydrogen plasma, 25 is a target, 26 is a permanent magnet, 27 is an electrode, 28 is a glass substrate, 29 is an electrode, 30 is cooling A medium inlet / outlet hole, and an exhaust hole 31.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−117687（ＪＰ，Ａ) 特開 昭61−67280（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-60-117687 (JP, A) JP-A-61-67280 (JP, A)
Claims (2)
する太陽電池において、 上記ｐ型層及びｎ型層のうちのいずれか１つの層を窓側
層とし、この窓側層が実質的に平均粒径100Å以下の微
結晶シリコンのみからなる微結晶シリコン膜であること
を特徴とする太陽電池。1. A solar cell having a pin structure of a p-type layer, an i-type layer and an n-type layer, wherein any one of the p-type layer and the n-type layer is a window side layer, and the window side layer is A solar cell, which is a microcrystalline silicon film consisting essentially of microcrystalline silicon having an average grain size of 100Å or less.
し、上記ｐ型層及びｎ型層のうちのいずれか１つの層を
実質的に平均粒径100Å以下の微結晶シリコンのみから
なる微結晶シリコン膜で構成された窓側層とする太陽電
池の製造方法において、 窓を構成するガラス基板上に透明導電膜を形成したの
ち、上記ガラス基板温度を０℃以下に保ち、水素プラズ
マによるスパッタリングを行って上記透明導電膜上にシ
リコンを堆積して上記窓側層を形成することを特徴とす
る太陽電池の製造方法。2. A pin structure of a p-type layer, an i-type layer and an n-type layer, wherein any one of the p-type layer and the n-type layer has a fine grain size of substantially 100 Å or less. In a method for manufacturing a solar cell having a window-side layer composed of a microcrystalline silicon film composed only of crystalline silicon, a transparent conductive film is formed on a glass substrate forming a window, and then the glass substrate temperature is kept at 0 ° C. or lower. A method of manufacturing a solar cell, comprising: forming a window-side layer by depositing silicon on the transparent conductive film by performing sputtering with hydrogen plasma.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63192013A JPH0650780B2 (en) | 1988-08-02 | 1988-08-02 | Solar cell and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63192013A JPH0650780B2 (en) | 1988-08-02 | 1988-08-02 | Solar cell and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0242765A JPH0242765A (en) | 1990-02-13 |
| JPH0650780B2 true JPH0650780B2 (en) | 1994-06-29 |
Family
ID=16284153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63192013A Expired - Lifetime JPH0650780B2 (en) | 1988-08-02 | 1988-08-02 | Solar cell and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0650780B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210050A (en) | 1990-10-15 | 1993-05-11 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing a semiconductor device comprising a semiconductor film |
| US6362097B1 (en) * | 1998-07-14 | 2002-03-26 | Applied Komatsu Technlology, Inc. | Collimated sputtering of semiconductor and other films |
| JP2004335733A (en) * | 2003-05-07 | 2004-11-25 | National Institute Of Advanced Industrial & Technology | Thin film solar cell |
| JP2004335734A (en) * | 2003-05-07 | 2004-11-25 | National Institute Of Advanced Industrial & Technology | Thin film solar cell |
| JP2004356163A (en) * | 2003-05-27 | 2004-12-16 | Toyota Central Res & Dev Lab Inc | Silicon-based thin film, method of manufacturing the same and photoelectric conversion element |
| JP2009076743A (en) * | 2007-09-21 | 2009-04-09 | Nissin Electric Co Ltd | Photovoltaic element, and manufacturing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57187971A (en) * | 1981-05-15 | 1982-11-18 | Agency Of Ind Science & Technol | Solar cell |
-
1988
- 1988-08-02 JP JP63192013A patent/JPH0650780B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0242765A (en) | 1990-02-13 |
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