TW201015731A - Photoelectric conversion device - Google Patents

Photoelectric conversion device Download PDF

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Publication number
TW201015731A
TW201015731A TW98130426A TW98130426A TW201015731A TW 201015731 A TW201015731 A TW 201015731A TW 98130426 A TW98130426 A TW 98130426A TW 98130426 A TW98130426 A TW 98130426A TW 201015731 A TW201015731 A TW 201015731A
Authority
TW
Taiwan
Prior art keywords
layer
semiconductor layer
photoelectric conversion
impurity
dielectric film
Prior art date
Application number
TW98130426A
Other languages
Chinese (zh)
Inventor
Kenji Kimoto
Original Assignee
Sharp Kk
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP2008235307A external-priority patent/JP4974183B2/en
Priority claimed from JP2008235360A external-priority patent/JP2010067921A/en
Application filed by Sharp Kk filed Critical Sharp Kk
Publication of TW201015731A publication Critical patent/TW201015731A/en

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    • 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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for 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
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for 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
    • H01L31/04—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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0475—PV cell arrays made by cells in a planar, e.g. repetitive, configuration on a single semiconductor substrate; PV cell microarrays
    • 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
    • H01L31/068—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 PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction 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
    • H01L31/04—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
    • H01L31/068—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 PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H01L31/0687—Multiple junction or tandem 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
    • H01L31/04—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
    • H01L31/04—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
    • H01L31/076—Multiple junction or tandem solar 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
    • Y02E10/544—Solar cells from Group III-V materials
    • 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
    • Y02E10/547—Monocrystalline 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

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  • Engineering & Computer Science (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Molecular Biology (AREA)
  • Health & Medical Sciences (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Disclosed is a photoelectric conversion device, wherein semiconductor layers (2, 2a, 2b, 2c, 12a, 12b, 101) and dielectric films (6, 6a, 6b, 6c, 26, 32, 34, 37, 39, 60, 105), which are arranged in contact with the surfaces of the semiconductor layers (2, 2a, 2b, 2c, 12a, 12b, 101), are included, and the dielectric films (6, 6a, 6b, 6c, 26, 32, 34, 37, 39, 60, 105) have impurities (5, 20, 21, 25, 50, 104) to be positive or negative fixed charges in the vicinity of interfaces between the dielectric films and the semiconductor layers (2, 2a, 2b, 2c, 12a, 12b, 101). Furthermore, the photoelectric conversion device includes semiconductor layers (2a, 2b, 2c), and dielectric films (6, 26, 32, 34, 37, 39), which are arranged in contact with the surfaces of the semiconductor layers (2a, 2b, 2c), and the dielectric films (6, 26, 32, 34, 37, 39) have the impurities (5, 25) to be positive or negative fixed charges in the vicinity of the interfaces between the dielectric films and the semiconductor layers (2a, 2b, 2c), and also have transparent conductive films (9, 33, 38) on the surfaces of the dielectric films (6, 26, 32, 34, 37, 39). Carriers transfer in the dielectric films (6, 26, 32, 34, 37, 39) by tunnel effects and the like and are taken out to the external from the transparent conductive films (9, 33, 38).

Description

201015731 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種光電轉換裝置，特別係關於一種具有 利用由固定電荷所誘發之反轉層之構成且特性優異之光電 轉換裝置。 又，本發明係關於-種光電轉換裝置，特別係關於一種 光電轉換效率等之特性優異之光電轉換裝置。 【先前技術】 例如，在專利文獻1(日本專利特開昭號公報） 中揭不有一種太陽電池，其具有如下構成：含有包含與 半導體表面直接相接之氧化矽之第—層、以及形成於該第 一層上且包含與第一層不同之絕緣材料之第二層，於第二 層内含有固定電荷。 於專利文獻1所揭示之太陽電池中，由於在第一層與第 一層之界面上設置有固定電荷，故會於半導體表面上誘發 反轉層。由誘發如此之反轉層而可預測’會具有相較摻雜 有雜質之通常之pn接合（p〇sitive_negative junction，正負 接合）時更高之紫外線感光度。 又’於專利文獻1中，揭示有當在第二層中使用氮化 石夕、進而在第二層中添加驗性離子（alkali i〇n)等之異種離 子時，可進一步提高固定電荷密度。 又’例如於專利文獻2(曰本專利特公昭63-48197號公報） 中揭示有一種光電動勢（photoelectromotive force)元件，其 係將多個單位晶胞（cell)積層而成之串聯結構，該單位晶 143168.doc 201015731 胞（cell)係由η型非晶梦（ain〇rphous silicon)層、i型非晶碎 層及p型非晶石夕層依此順序積層所得，該光電動勢元件之 構成為，於最下部包含導電性基板，並且於最上部包含透 明導電膜（例如’專利文獻i之第2圖、及第3頁左攔第7 行等）》 於該專利文獻2所揭示之光電動勢元件中，因光之照射 而產生之載體會自導電性基板及透明導電膜中分別被取 出。 先行技術文獻 專利文獻 專利文獻1:曰本專利特開昭55-59784號公報 專利文獻2 :日本專利特公昭63_48197號公報 【發明内容】 發明所欲解決之問題 然而，專利文獻1所揭示之太陽電池中，即使於包含氮 化石夕之第一層中添加有驗性離子等之異種離子之情形時， 半導體表面之反轉層中之載體密度亦不會變高，故而具有 無法獲得特性優異之太陽電池之問題。 又，專利文獻2所揭示之光電動勢元件中，短波長之光 會由最上部之p型非晶矽層所吸收，故而具有光電動勢元 件之短波長之光的光電轉換效率會變低之問題。 自降低由最上部之p型非晶矽層所吸收之短波長之光量 以提高光電動勢元件之轉換效率之觀點考慮，必需將最上 部之P型非晶矽層之厚度形成得較薄。 143168.doc 201015731 然而，於大面積之基板上均勻地形成例如1〇 nm以下之 薄度之p型非晶矽層非常困難。. 又，於非晶矽中，施體（donor)及受體（accept〇r)之活化 率較低，故而會將未活化之施體雜質、未活化之受體雜質 或者形成於其等周邊的懸鍵（dangling b〇nd)等作為再結合 中〜而發揮功能，因而具有在n型層及p型層中容易引起載 體再結合之問題。 因此，本發明之目的在於提供一種具有利用由固定電荷 所誘發之反轉層之構成且特性優異之光電轉換裝置。 又，本發明之目的在於提供一種光電轉換效率等之特性 優異之光電轉換裝置。 解決問題之技術手段 根據本發明之第1態樣，可提供一種光電轉換裝置，其 包含：半導體層、及以與半導體層之表面相接之方式而設 置的介電質膜’該介電質膜在與半導體層之界面附近，含 有成為正或負的固定電荷之雜質。 此處’於本發明之第1態樣之光電轉換裝置中，半導體 層亦可包含結晶矽（crystalline siiicon)、非晶矽或微晶 〇 又’於本發明之第1態樣之光電轉換裝置中，較好的是 介電質膜之帶隙（bandgap)為4.2 eV以上。 又’於本發明之第1態樣之光電轉換裝置中，介電質膜 亦可包含選自由氧化矽、氮氧化矽及氮化矽所組成之群中 之至少一種。 143168.doc 201015731 又’於本發明之第1態樣之光電轉換裝置中，成為正的 固定電荷之雜質亦可包含選自由鋰、鈉、鉀、鈿、絶、 鎂、鈣、锶、鋇、磷、砷及銻所組成之群中之至少一種。 又’於本發明之第丨態樣之光電轉換裝置中，成為負的 固疋電％之雜質亦可包含選自由蝴、銘、錁、銦、鈾、翁 化富勒烯（fluorofullerene)、氧化富勒烯、氟、氣、濞及碘 所組成之群中之至少一種。 又’本發明之第1態樣之光電轉換裝置較好的是，在與 介電質膜相接之半導體層之表面之區域的至少一部分上， 含有第1導電型或第2導電型之表面反轉層。 又，本發明之第1態樣之光電轉換裝置亦可包含雜質含 有層，其係於半導體層之表面之至少一部分上，含有與表 面反轉層為相同導電型之雜質，且更包含電極，其係與雜 質含有層相接。 又於本發明之第1態樣之光電轉換裝置中，電極亦可 匕3選自由金屬、金屬；^化物以及透明導電膜所組成之群 中之至少一種。 ^又，於本發明之第1態樣之光電轉換裝置中，較好的 疋’雜質存在最多之部位’係位於從半導體層與介電質膜 之界面起’在相對於界面而垂直之方向上朝著半導體層側 前進5⑽之區域、與朝著介電質膜側前進5 nm之區域之間 的區域。 又，於本發明之第1態樣之光電轉換裝i中，較好的是 於半導體層之表面形成有凹凸。 143168.doc 201015731 又’根據本發明之第2態樣，可提供一種光電轉換裝 置’其包含第1光電轉換層及第2光電轉換層，上述第以 電轉換層包a ·第1半導體層；表面介電質膜’其係以與 第1半導體層之表面相接之方式而設置，並且在與第^半導 體層之界面附近含有成為正或負的固定電荷之雜質；^ 導電型或第2導電型之表面反轉層，其係設置在與表面介 電質膜相接之第丨半導體層之表面之區域的至少一部分 上’及第1雜質含有層’其係設置於與第1半導體層之表面 為相反側之#面上’並且含有與表面反轉層為相反導電型 之第1雜質；上述第2光電轉換層包含：第2半導體層；第2 ❹ ❹ 雜質含有層，其係設置於第2半導體層之表面，並且含有 與表面反轉層為相反導電型之第2雜質；及第3雜質含有 層，其係設置於與第2半導體層之表面為相反側之背面 上，並且含有與第2雜質為相反導電型之第3雜質；且該光 電轉換裝置具有積層結構，其係將第！光電轉換層之第1雜 質含有層與第2光電轉換層之第2雜質含有層接合由第丄 光電轉換層與第2光電轉換層積層而成。 此處，於本發明之第2態樣之光電轉換裝置中，較好的 是第1半導體層之厚度較^半導體層内之載體擴散長度更 薄，第2半導體層之厚度較第2半導體層内之載體擴散長度 更薄。 又’於本發明之第2態樣之光電轉換裝置中，較好的是 靠近光入射側之第1半導體層之帶隙為遠離光入射側之第2 半導體層之帶隙以上。 143168.doc 201015731 又’於本發明之第2態樣之光電轉換裝置中，第1半導體 層及第2半導體層亦可包含結晶矽、非晶矽或微晶矽。 又’於本發明之第2態樣之光電轉換裝置中，較好的是 表面介電質膜之帶隙為4.2 eV以上。 又’於本發明之第2態樣之光電轉換裝置中，表面介電 質膜亦可包含選自由氧化矽、氮氧化矽及氮化矽所組成之 群中之至少一種。 又’於本發明之第2態樣之光電轉換裝置中，成為正的 固定電荷之雜質亦可包含選自由鋰、鈉、鉀、铷、铯、 鎂、鈣、鳃、鋇、磷、砷及銻所組成之群令之至少一種。 又，於本發明之第2態樣之光電轉換裝置中，成為負的 固定電荷之雜質亦可包含選自由硼、銘、鎵、銦、鉑、氟 化富勒烯、氧化富勒烯、氟、氣、溴及碘所組成之群中之 至少一種。 又，於本發明之第2態樣之光電轉換裝置中，亦可於第工 半導體層中進而包含電極。 又，於本發明之第2態樣之光電轉換裝置中，電極亦可 包含選自由金屬、金屬矽化物以及透明導電膜所組成之群 中之至少一種。 又，於本發明之第2態樣之光電轉換裝置中，較好的 疋於表面介電質膜中成為正或負的固定電荷之雜質存在 最多之。卩位，係位於從第丨半導體層與表面介電質膜之界 面起，在相對於界面而垂直之方向上朝著第丨半導體層侧 前進5 nm之區域、與朝著表面介電質膜側前進5 nm之區域 143168.doc 201015731 之間的區域。 又’本發明之第2態樣之光電轉換裝置亦可進而包含第3 光電轉換層，該第3光電轉換層包含：第3半導體層；背面 介電質膜，其係以與第3半導體層之背面相接之方式而設 置’並且在與第3半導體層之界面附近含有成為與表面介 電質膜所含之雜質為相反極性之固定電荷的雜質；背面反 轉層’其係設置在與背面介電質膜相接之第3半導體層之 表面之區域的至少一部分上，並具有與表面反轉層為相反 之導電型；及第4雜質含有層，其係設置於與第3半導體層 之背面為相反侧之表面上，並且含有與背面反轉層為相反 導電型之第4雜質；該光電轉換裝置具有積層結構，其係 將第3光電轉換層之第4雜質含有層、與第2光電轉換層之 第3雜質含有層接合，由第2光電轉換層與第3光電轉換層 積層而成。 又，於本發明之第2態樣之光電轉換裝置中，較好的 是，於背面介電質膜中雜質存在最多之部位，係位於從第 3半導體層與背面介電f膜之界面起，在相對於界面而垂 直之方向上朝著第3半導體層側前進5 nm之區域、與朝著 背面介電質膜側前進5 nm之區域之間的區域。 又，根據本發明之第3態樣，可提供一種光電轉換裝 置’其包含：半導體層；以與半導體層之表面上相接之方 式所設置的表面介電質膜；及以與半導體層之與表面為相 反側之背面相接之方式所設置的背面介電質膜；上述表面 介電質膜在與半導體層之界面附近，含有成為第ι極性之 143168.doc 201015731 固定電荷之雜質，上述背面介電質膜在與半導體層之界面 附近，含有成為與第1極性相反之第2極性之固定電荷的雜 質。 ^ 此處，於本發明之第3態樣之光電轉換裝置中，半導體 層亦可包含結晶石夕、非晶石夕或微晶石夕。 又，於本發明之第3態樣之光電轉換裝置中較好的是 表面介電質臈之帶隙為4.2 ev以上。 疋 人’於本發明之第3態樣之光電轉換裝置中，表面 質膜及背面介電質媒亦可包含選自由氧化石夕、氮氧切及 氮化石夕所組成之群中之至少一種。 又，於本發明之第3態樣之光電轉換裝置中 性之固定電荷的雜質亦可包含選自由鐘、納、鉀、1 鉋、鎖、約、銷、鎖、鱗、神及錄所組成之群中之至小一 為Γ極性之固定電荷的雜質亦可包含選自由娜、[Technical Field] The present invention relates to a photoelectric conversion device, and more particularly to a photoelectric conversion device having a configuration using an inversion layer induced by a fixed charge and having excellent characteristics. Further, the present invention relates to a photoelectric conversion device, and more particularly to a photoelectric conversion device having excellent characteristics such as photoelectric conversion efficiency. [Prior Art] For example, a solar cell is disclosed in Patent Document 1 (Japanese Patent Laid-Open Publication No.), which has a structure including a first layer containing ruthenium oxide directly in contact with a semiconductor surface, and a formation A second layer on the first layer and comprising a different insulating material than the first layer contains a fixed charge in the second layer. In the solar cell disclosed in Patent Document 1, since a fixed charge is provided at the interface between the first layer and the first layer, an inversion layer is induced on the surface of the semiconductor. By inducing such an inversion layer, it is predicted that it will have a higher ultraviolet sensitivity than a normal pn junction (positive and negative junction) doped with impurities. Further, in Patent Document 1, it is disclosed that when a heterogeneous ion such as an anion ion or the like is added to the second layer, the fixed charge density can be further increased. Further, a photoelectromotive force element which is a series structure in which a plurality of unit cells are laminated is disclosed in Japanese Laid-Open Patent Publication No. SHO63-48197. Unit crystal 143168.doc 201015731 The cell is obtained by laminating an η-type amorphous dream layer (ain〇rphous silicon layer), an i-type amorphous fragment layer, and a p-type amorphous slab layer in this order, and the photoelectromotive force element is The conductive substrate is included in the lowermost portion, and the transparent conductive film is included in the uppermost portion (for example, 'Patent Document i, Fig. 2, and Fig. 3, left bank, seventh line, etc.), which is disclosed in Patent Document 2 In the photoelectromotive force element, the carrier generated by the irradiation of light is taken out from the conductive substrate and the transparent conductive film, respectively. CITATION LIST Patent Literature Patent Literature 1: Japanese Laid-Open Patent Publication No. JP-A-63-59197 (Patent Document No. JP-A-63-48197) SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, the sun disclosed in Patent Document 1 In the case of a battery in which a heterogeneous ion such as an inspecting ion is added to the first layer containing the nitride, the carrier density in the inversion layer of the semiconductor surface does not become high, and thus the property is not excellent. The problem with solar cells. Further, in the photovoltaic cell disclosed in Patent Document 2, light of a short wavelength is absorbed by the uppermost p-type amorphous germanium layer, so that the photoelectric conversion efficiency of light having a short wavelength of the photovoltaic element becomes low. . From the viewpoint of reducing the amount of light of a short wavelength absorbed by the uppermost p-type amorphous germanium layer, it is necessary to make the thickness of the uppermost P-type amorphous germanium layer thinner from the viewpoint of improving the conversion efficiency of the photovoltaic element. 143168.doc 201015731 However, it is very difficult to uniformly form a p-type amorphous germanium layer having a thinness of, for example, 1 〇 nm or less on a large-area substrate. Moreover, in the amorphous germanium, the activation rate of the donor and the acceptor is low, so that the unactivated donor impurity, the unactivated acceptor impurity, or the like are formed around it. The dangling b〇nd or the like functions as a recombination medium, and thus has a problem that the carrier is recombined easily in the n-type layer and the p-type layer. Accordingly, it is an object of the present invention to provide a photoelectric conversion device having a configuration in which an inversion layer induced by a fixed charge is used and which is excellent in characteristics. Further, an object of the present invention is to provide a photoelectric conversion device which is excellent in characteristics such as photoelectric conversion efficiency. Means for Solving the Problem According to a first aspect of the present invention, a photoelectric conversion device comprising: a semiconductor layer; and a dielectric film provided in a manner of being in contact with a surface of the semiconductor layer The film contains an impurity which becomes a positive or negative fixed charge in the vicinity of the interface with the semiconductor layer. Here, in the photoelectric conversion device according to the first aspect of the present invention, the semiconductor layer may further include a crystalline siiicon, an amorphous germanium or a microcrystalline germanium, and a photoelectric conversion device according to the first aspect of the present invention. Preferably, the bandgap of the dielectric film is 4.2 eV or more. Further, in the photoelectric conversion device according to the first aspect of the invention, the dielectric film may include at least one selected from the group consisting of cerium oxide, cerium oxynitride, and cerium nitride. Further, in the photoelectric conversion device according to the first aspect of the present invention, the impurity which becomes a positive fixed charge may be selected from the group consisting of lithium, sodium, potassium, rubidium, magnesium, calcium, barium, strontium, At least one of a group consisting of phosphorus, arsenic and antimony. Further, in the photoelectric conversion device according to the third aspect of the invention, the impurity which becomes a negative solid-state electricity may also be selected from the group consisting of phosgene, cerium, indium, uranium, fluorofullerene, and oxidation. At least one of a group consisting of fullerenes, fluorine, gas, hydrazine, and iodine. Further, in the photoelectric conversion device according to the first aspect of the present invention, it is preferable that at least a part of a region of the surface of the semiconductor layer that is in contact with the dielectric film contains the surface of the first conductivity type or the second conductivity type. Reverse layer. Further, the photoelectric conversion device according to the first aspect of the present invention may further include an impurity-containing layer which is on at least a part of the surface of the semiconductor layer and contains impurities of the same conductivity type as the surface inversion layer, and further includes an electrode. It is in contact with the impurity-containing layer. Further, in the photoelectric conversion device according to the first aspect of the invention, the electrode may be at least one selected from the group consisting of a metal, a metal compound, and a transparent conductive film. Further, in the photoelectric conversion device according to the first aspect of the present invention, a preferred portion where the impurity is present most is located in a direction perpendicular to the interface from the interface between the semiconductor layer and the dielectric film. A region between the region of 5 (10) advancing toward the semiconductor layer side and the region advancing 5 nm toward the dielectric film side. Further, in the photoelectric conversion device i according to the first aspect of the invention, it is preferable that irregularities are formed on the surface of the semiconductor layer. Further, according to a second aspect of the present invention, a photoelectric conversion device includes a first photoelectric conversion layer and a second photoelectric conversion layer, and the first electrical conversion layer includes a first semiconductor layer; The surface dielectric film 'is disposed in contact with the surface of the first semiconductor layer, and contains an impurity which becomes a positive or negative fixed charge in the vicinity of the interface with the second semiconductor layer; ^ Conductive type or second a conductive surface inversion layer provided on at least a portion of a region of a surface of the second semiconductor layer that is in contact with the surface dielectric film, and a first impurity-containing layer that is disposed on the first semiconductor layer The surface is the #surface on the opposite side and includes a first impurity having a conductivity opposite to that of the surface inversion layer; the second photoelectric conversion layer includes: a second semiconductor layer; and a second impurity layer containing an impurity layer a second impurity having a conductivity opposite to the surface inversion layer; and a third impurity containing layer provided on the surface of the second semiconductor layer opposite to the surface of the second semiconductor layer, and Contains and 2nd Quality of opposite conductivity type third impurity; and the photoelectric conversion device having a stacked structure, which lines the first! The first impurity-containing layer of the photoelectric conversion layer is bonded to the second impurity-containing layer of the second photoelectric conversion layer by a second photoelectric conversion layer and a second photoelectric conversion layer. Here, in the photoelectric conversion device according to the second aspect of the present invention, it is preferable that the thickness of the first semiconductor layer is thinner than the diffusion length of the carrier in the semiconductor layer, and the thickness of the second semiconductor layer is smaller than that of the second semiconductor layer. The carrier within the diffusion length is thinner. Further, in the photoelectric conversion device according to the second aspect of the invention, it is preferable that the band gap of the first semiconductor layer close to the light incident side is equal to or larger than the band gap of the second semiconductor layer on the light incident side. Further, in the photoelectric conversion device according to the second aspect of the present invention, the first semiconductor layer and the second semiconductor layer may include crystalline germanium, amorphous germanium or microcrystalline germanium. Further, in the photoelectric conversion device according to the second aspect of the invention, it is preferable that the band gap of the surface dielectric film is 4.2 eV or more. Further, in the photoelectric conversion device according to the second aspect of the invention, the surface dielectric film may further comprise at least one selected from the group consisting of cerium oxide, cerium oxynitride, and cerium nitride. Further, in the photoelectric conversion device according to the second aspect of the present invention, the impurity which becomes a positive fixed charge may further include a substance selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, phosphorus, arsenic, and At least one of the group orders. Further, in the photoelectric conversion device according to the second aspect of the present invention, the impurity which becomes a negative fixed charge may further comprise a group selected from the group consisting of boron, indium, gallium, indium, platinum, fluorinated fullerene, oxidized fullerene, and fluorine. At least one of a group consisting of gas, bromine and iodine. Further, in the photoelectric conversion device according to the second aspect of the present invention, the electrode may be further included in the semiconductor layer. Further, in the photoelectric conversion device according to the second aspect of the invention, the electrode may include at least one selected from the group consisting of a metal, a metal halide, and a transparent conductive film. Further, in the photoelectric conversion device according to the second aspect of the present invention, it is preferable that the impurity which becomes a positive or negative fixed charge in the surface dielectric film is most present. The 卩 position is located in a region from the interface between the second semiconductor layer and the surface dielectric film, which is 5 nm toward the second semiconductor layer side in the direction perpendicular to the interface, and toward the surface dielectric film The side advances the area between the 5 nm area 143168.doc 201015731. Further, the photoelectric conversion device according to the second aspect of the present invention may further include a third photoelectric conversion layer including: a third semiconductor layer; a back surface dielectric film, and a third semiconductor layer The back surface is provided in contact with each other and contains an impurity which is a fixed charge having a polarity opposite to that of the impurity contained in the surface dielectric film in the vicinity of the interface with the third semiconductor layer; the back surface inversion layer is disposed in At least a part of a region of a surface of the third semiconductor layer to which the back dielectric film is in contact with a conductivity type opposite to the surface inversion layer; and a fourth impurity containing layer provided on the third semiconductor layer The back surface is on the opposite side surface and includes a fourth impurity which is opposite to the back surface inversion layer. The photoelectric conversion device has a laminated structure, and the fourth impurity-containing layer of the third photoelectric conversion layer is The third impurity-containing layer of the photoelectric conversion layer is bonded, and the second photoelectric conversion layer and the third photoelectric conversion layer are laminated. Further, in the photoelectric conversion device according to the second aspect of the present invention, it is preferable that the portion of the back surface dielectric film having the most impurities is located from the interface between the third semiconductor layer and the back dielectric film f. A region between a region that is 5 nm toward the third semiconductor layer side and a region that is 5 nm toward the back dielectric film side in a direction perpendicular to the interface. Further, according to a third aspect of the present invention, there is provided a photoelectric conversion device comprising: a semiconductor layer; a surface dielectric film provided in contact with a surface of the semiconductor layer; and a semiconductor layer a back surface dielectric film provided in contact with the back surface on the opposite side of the surface; the surface dielectric film contains an impurity which becomes a fixed charge of the first polarity of 143168.doc 201015731 in the vicinity of the interface with the semiconductor layer, The back surface dielectric film contains an impurity which is a fixed charge of a second polarity opposite to the first polarity in the vicinity of the interface with the semiconductor layer. Here, in the photoelectric conversion device according to the third aspect of the invention, the semiconductor layer may further comprise crystal slabs, amorphous slabs or microcrystalline slabs. Further, in the photoelectric conversion device according to the third aspect of the invention, it is preferable that the band gap of the surface dielectric material is 4.2 ev or more. In a photoelectric conversion device according to a third aspect of the present invention, the surface plasma film and the back dielectric medium may further comprise at least one selected from the group consisting of oxidized oxide, oxynitride, and nitride nitride. . Further, in the photoelectric conversion device according to the third aspect of the present invention, the neutral fixed charge impurity may further comprise a component selected from the group consisting of a clock, a nano, a potassium, a planer, a lock, a lock, a pin, a lock, a scale, a god, and a record. The impurity of the fixed charge in the group to the minor one may also be selected from the group consisting of

銘嫁姻、銘、盡/卜管治·》»丘 ML 氟化虽勒烯、氧化富勒烯、 及碘所組成之群十之至少一種。 、溴 ;本發明之第3態樣之光電轉換 性之固定電荷的雜質亦可包含選自由，二成為第1極 二說化富勒埽、氧化富勒烯、氣、 ：:：、 群中之至少1,成為第2極性之固定電所組成之 含選自-m、绝、，、：電:的：質亦可包 及銻所組成之群中之至少一種。 ‘鋇、磷、砷 於本發明之第3態樣之 於半導體層之表面形成有… 袭置中，較好的是 H3168.doc 201015731 又’於本發明之第3態樣之光電轉換裝置中，較好的是 在與表面介電質膜相接之半導體層之表面之區域的至少一 部分上，含有第1導電型或第2導電型之表面反轉層。 又’於本發明之第3態樣之光電轉換裝置中，較好的是 . 在與背面介電質膜相接之半導體層之背面之區域的至少一 - 部分上，含有與表面反轉層為相反導電型之背面反轉層。 又本發明之第3態樣之光電轉換裝置亦可包含雜質含 ❹ 有層，其係於半導體層之表面之至少一部分上，含有與表 ®反轉層為相同導電型之雜質’進而可包含電極，其係與 雜質含有層相接》 又，於本發明之第3態樣之光電轉換裝置中，電極亦可 包3選自由金屬、金屬矽化物以及透明導電膜所組成之群 中之至少一種。 又，於本發明之第3態樣之光電轉換裝置中，較好的 是，成為第1極性之固定電荷的雜質存在最多之部位係 ❹位於攸半導體層與表面介電質膜之界面起，在相對於界面 而垂直之方向上朝著半導體層側前進5 之區域、與朝著 表面介電質膜側前進5 nm之區域之間的區域。 又，於本發明之第3態樣之光電轉換裝置中較好的 疋’於背面介電質膜中第2極性之雜質存在最多之部位， 係位於從半導體層與背面介電質膜之界面起，在相對於界 而垂直之方向上朝著半導體層側前進5 nm之區域、與朝 著背面；I電質膜側前進5 nm之區域之間的區域。 進而，根據本發明之第4態樣，可提供一種光電轉換裴 143168.doc 201015731 置’其包含：第1半導體層；與第1半導體層之表面相接合 之第1介電質膜；與第i半導體層之背面相接合之第2介電 質膜，及與第2介電質膜之背面相接合之第2半導體層；上 述第1介電質膜在與第!半導體層之界面附近，含有成為第 1極性或第2極性之固定電荷的雜f，上述第2介電質膜在 與第1半導體層之界面附近、以及與第2半導體層之界面附 近’含有成為與帛W電質膜中所含之雜質為相反極性之 固定電荷的雜質。 又，於本發明之第4態樣之光電轉換裝置中，較好的 疋第1半導體層之厚度較第1半導體層内之載體擴散長度 更薄’第2半導體層之厚度㈣2半導體層内之載體擴散長 度更薄。 又，於本發明之第4態樣之光電轉換裝置中，較好的 是，靠近光入射侧之第i半導體層之帶隙為遠離光入射侧 之第2半導體層之帶隙以上。 又，於本發明之第4態樣之光電轉換裝置中，第丨半導體 層及第2半導體層亦可包含結晶矽、非晶矽或微晶矽。 又，於本發明之第4態樣之光電轉換装置中，較好的是 第1介電質膜及第2介電質膜之帶隙為4·2 eV以上。 又，於本發明之第4態樣之光電轉換裝置中，第丨介電質 膜及第2介電質膜亦可包含選自由氧化矽、氮氧化矽及氮 化矽所組成之群中之至少一種。 又，於本發明之第4態樣之光電轉換裝置中，成為第1極 性之固定電荷之雜質亦可包含選自由鋰、鈉、鉀、铷、 143168.doc •12- 201015731 铯、鎂、鈣、錦、铜 種，成為第2極性之固、銻所組成之群，之至少- 紹、鎵、銦、銘一 1 雜質亦可包含選自由棚、 亂化畐勒烯、氧化富勒稀、氟、臭 及填所組成之群中之至少—種。 ^ ^ ^ 比之計7明之第4態樣之光電轉換裝置中，成為第1極 性之固定電荷之雜質亦可包含選自由蝴、紹、錄、姻、 = 稀、氧化富勒稀、&、氣、漠及韻組成之铭嫁婚,铭,尽/卜治治·》»丘 ML Fluorine, at least one of the group consisting of olefins, oxidized fullerenes, and iodine. And bromine; the photoelectrically convertible fixed-charge impurity of the third aspect of the present invention may also be selected from the group consisting of, the second, the first, the second, the fullerene, the oxidized fullerene, the gas, the :::, the group. At least one of the group consisting of a fixed electric appliance having a second polarity and containing at least one selected from the group consisting of -m, absolute, and electric: a mass may also be included. '钡, phosphorus, and arsenic are formed on the surface of the semiconductor layer in the third aspect of the present invention. It is preferable to use H3168.doc 201015731 in the photoelectric conversion device of the third aspect of the present invention. Preferably, at least a portion of a region of the surface of the semiconductor layer that is in contact with the surface dielectric film contains a surface inversion layer of a first conductivity type or a second conductivity type. Further, in the photoelectric conversion device of the third aspect of the invention, it is preferable that at least one portion of the region on the back surface of the semiconductor layer that is in contact with the back dielectric film contains the surface inversion layer It is the backside inversion layer of the opposite conductivity type. Further, the photoelectric conversion device according to the third aspect of the present invention may further comprise an impurity-containing layer which is bonded to at least a part of the surface of the semiconductor layer and contains an impurity of the same conductivity type as the surface of the surface layer, and may further comprise Further, in the photoelectric conversion device according to the third aspect of the present invention, the electrode may be selected from at least a group consisting of a metal, a metal halide, and a transparent conductive film. One. Further, in the photoelectric conversion device according to the third aspect of the present invention, it is preferable that the portion of the impurity having the fixed charge of the first polarity is located at the interface between the germanium semiconductor layer and the surface dielectric film. A region between a region advancing 5 toward the semiconductor layer side in a direction perpendicular to the interface and a region advancing 5 nm toward the surface dielectric film side. Further, in the photoelectric conversion device according to the third aspect of the present invention, it is preferable that the portion of the second polarity impurity in the back surface dielectric film is most present at the interface between the semiconductor layer and the back dielectric film. The region between the region of 5 nm toward the semiconductor layer side in the direction perpendicular to the boundary, and the region between the region facing the back surface and the surface of the I plasma film by 5 nm. Further, according to a fourth aspect of the present invention, a photoelectric conversion layer 143168.doc 201015731 can be provided which includes: a first semiconductor layer; a first dielectric film bonded to a surface of the first semiconductor layer; a second dielectric film joined to the back surface of the semiconductor layer; and a second semiconductor layer bonded to the back surface of the second dielectric film; and the first dielectric film is adjacent to the interface with the semiconductor layer; The impurity f containing a fixed charge of the first polarity or the second polarity, the second dielectric film is contained in the vicinity of the interface with the first semiconductor layer and in the vicinity of the interface with the second semiconductor layer. The impurities contained in the film are fixed charges of opposite polarity. Further, in the photoelectric conversion device according to the fourth aspect of the present invention, preferably, the thickness of the first semiconductor layer is thinner than the carrier diffusion length in the first semiconductor layer, and the thickness of the second semiconductor layer (four) is 2 in the semiconductor layer. The carrier diffusion length is thinner. Further, in the photoelectric conversion device according to the fourth aspect of the invention, it is preferable that the band gap of the i-th semiconductor layer close to the light incident side is equal to or larger than the band gap of the second semiconductor layer on the light incident side. Further, in the photoelectric conversion device according to the fourth aspect of the invention, the second semiconductor layer and the second semiconductor layer may contain crystalline germanium, amorphous germanium or microcrystalline germanium. Further, in the photoelectric conversion device according to the fourth aspect of the invention, it is preferable that the band gap of the first dielectric film and the second dielectric film is 4·2 eV or more. Further, in the photoelectric conversion device according to the fourth aspect of the present invention, the second dielectric film and the second dielectric film may further include a group selected from the group consisting of cerium oxide, cerium oxynitride, and cerium nitride. At least one. Further, in the photoelectric conversion device according to the fourth aspect of the present invention, the impurity which becomes the fixed charge of the first polarity may further include a substance selected from the group consisting of lithium, sodium, potassium, cesium, 143168.doc • 12-201015731 铯, magnesium, calcium. , brocade, copper species, become the group of the second polarity solid, 锑, at least - Shao, gallium, indium, Ming-1 impurities can also be selected from the shed, chaotic olefins, oxidized fullerene, At least one of the group consisting of fluorine, odor and filling. ^ ^ ^ In the photoelectric conversion device of the fourth aspect of the seventh aspect, the impurity which becomes the fixed charge of the first polarity may also be selected from the group consisting of: butterfly, shovel, sho, marry, = dilute, oxidized fullerene, & , gas, desert and rhyme

參 入、愛白/ 一種，&為第2極性之固定電荷之雜質亦可包 含選自由鋰、鈉、钿、i 从 鉀铷、鉋、鎂、鈣、鋇、鋇、磷、砷 及銻所組成之群中之至少—種。 又’於本發明之第4態樣之光電轉換裝置中，亦可在與 第1介電質膜接合之第1半導體層之表面之區域的至少一部 刀上’含有第1導電型或第2導電型之第m轉層在與第2 ”電質膜接合之第i半導體層之背面之區域的至少一部 分、以及與第2介電質膜接合之第2半導體層之表面之區域 的至少一部分上，分別含有與第1反轉層為相反導電型之 第2反轉層。 又，於本發明之第4態樣之光電轉換裝置中，亦可於積 層結構之一方之側面含有第丨導電型半導體層，於積層結 構之另一方之側面含有第2導電型半導體層。 根據本發明之第5態樣，可提供一種光電轉換裝置，其 匕3·半導體層；及以與半導體層之表面相接之方式而設 置的介電質膜，該介電質膜至少在與半導體層之界面附 近，含有成為正或負的固定電荷之雜質，於介電質膜之表 143168.doc .13- 201015731 面上含有透明導電膜’利用穿随效應（tunnel effect)等使裁 體通過介電質膜而自透明導電膜被取出至外部。 此處’於本發明之第5態樣之光電轉換裝置中，亦可於 透明導電膜之表面上包含透明基板。 又，於本發明之第5態樣之光電轉換裝置中，亦可在與 介電質膜相接之半導體層之表面之區域的至少一部分上， 含有第1導電型或第2導電型之表面反轉層。 又，於本發明之第5態樣之光電轉換裝置中，半導體層 亦可包含結晶矽、非晶矽或微晶矽。 又，於本發明之第5態樣之光電轉換裝置中，較好的是 半導體層之厚度較半導體層内之載體擴散長度更薄。 又，於本發明之第5態樣之光電轉換裝置中，較好的是 ;丨電質膜之帶隙為4.2 ev以上。 又，於本發明之第5態樣之光電轉換裝置中，介電質膜 亦可包含選自由碳切、氧化$、氮氧切及氮化石夕所組 成之群中之至少—種。 又，於本發明之第5態樣之光電轉換裝置中，較好的是 介電質膜之厚度為3nm以下。 疋 固本發明之第5態樣之光電轉換裝置中，成為正的 疋電荷之雜質亦可包含選自由鋰、鈉、鉀、铷、 錄鋇、碟、神及錄所組成之群中之至少—種。 固：：本發明之第5態樣之光電轉換裝置中，成為負的 化：電荷之雜質亦可包含選自由硼、鋁、鎵銦、鉑氟 勒烯、氧化富勒稀、氟、氣、漠及峨所組成之群中之 143l68.d〇c 201015731 至少一種。 又，於本發明之第5態樣之光電轉換裝置中，較好的 是，雜質存在最多之部位，係位於從半導體層與介電質膜 之界面起，在相對於界面而垂直之方向上朝著半導體層側 前進5 nm之區域、與朝著介電質膜側前進5 nm之區域之間 的區域。 又，根據本發明之第6態樣，可提供一種光電轉換裝 ❹ 置’其包含：第1半導體層；以與第1半導體層之表面相接 之方式而設置的表面介電質膜；形成於第1半導體層之背 面之第1導電型雜質含有層；設置於W半導體層之背面側 之第2半導體層；形成於第2半導體層之表面之第2導電型 雜質含有層；形成於第2半導體層之背面之第i導電型雜質 含有層，6又置於第2半導體層之背面側之第3半導體層丨形 成於第3半導體層之表面之第2導電型雜質含有層；以及形 成於第3半導體層之背面之第1導電型雜質含有層；將第! e 半導體層之背面之第1導電型雜質含有層、與第2半導體層 之表面之第2導電型雜質含有層加以接合，將第2半導體層 之背面之第i導電型雜質含有層、與形成於第3半導體層之 表面之第2導電型雜質含有層加以接合’表面介電質膜在 與第1半導體層之界面附近，含有成為正或負的固定電荷 之雜質，在與表面介電質膜相接之第1半導體層之表面之 區域的至少一部分上，形成有第2導電型之表面反轉層， 於表面介電質膜之表面上，含有透明導電膜，利用穿随效 應等使載體通過表面介電質媒而自透明導電膜被取出至外 143I68.doc 15 201015731 部。 此處，於本發明之第6態樣之光電轉換裝置中，較好的 是第1半導體層之帶隙為相較第！半導體層更遠離光入射側 之第2半導體層之帶隙以上，第2半導體層之帶隙為相較第 2半導體層更遠離光入射側之第3半導體層之帶隙以上。 又’於本發明之第6態樣之光電轉換裝置中，較好的0 第！半導趙層之厚度較第！半導體層内之載體摘散長度= 薄。 又，於本發明之第6態樣之光電轉換裝置中，較好 第2半導體層之厚度較第2半導體層内之載體擴散長^ 薄。 又’於本發明之第6態樣之光電轉換裝置中 第3半導體層之厚产妨篦3主道麻、疋 厚度較第3+導體層内之载體擴散長度更 缚0 又，於本發明之第6態樣之光電轉換裝置中 表面介電質膜之帶隙為4.2 eV以上。 、疋 又，於本發明之第6態樣之光電轉換裝置中 人 質膜亦可包含選自由碳切、氧切、氮氧化 I: 所組成之群中之至少一種。 氮化石夕 又，於本發明之第6態樣之光電轉換裝置中 表面介電質膜之厚度為3nm以下。 的疋 又，於本發明之第6態樣之光電轉換裝I中 固定電荷之雜質亦可包含選自由鐘、、：為正的 Λ-C . ' 敍1、絶、 、 、鋇、碟、砷及銻所組成之群中之 足少一種。 143168.doc 201015731 二電= 月之第6態樣之光電轉換裳置中，成為負的 電何之雜質亦可包含選自由硼、鋁、 化富勒烯、氧化富勒烯、氟、氯、漠 /銷、氟 至少—種。 i /吴及礙所組成之群中之 Ο 魯 又，於本發明之第6態樣之光電轉換裝置中，較好的 ^從^正或負的^電荷之雜質存在最多之部位，係位 +導體層與表面介電質膜之界面起，在相對於界 =而垂直之方向上朝著第^導體層側前進5 nm之區域、 ，、朝著表面介電質膜侧前進5nm之區域之間的區域。 又立根據本發明之第7態樣，可提供一種光電轉換裝 、包含.第1半導體層；以與第i半導體層之表面相接 之方式而設置的表面介電質膜；形成於第丨半導體層之背 面，第1導電型雜質含有層；設置於第1半導體層之背面側 之第2半導體層；形成於第2半導體層之表面之第2導電型 :質3有層，形成於第2半導體層之背面之第^導電型雜質 含有層；設置於第2半導體層之背面側之第3半導體層 '形 成於第3半導體層之表面之第2導電型雜質含有層；以及形 成於第3半導體層之背面之背面介電質膜；將第1半導體層 之背面之第1導電型雜質含有層、與第2半導體層之表面之 第2導電型雜質含有層加以接合’將第2半導體層之背面之 第1導電型雜質含有層、與形成於第3半導體層之表面之第 導電里雜質含有層加以接合，表面介電質膜在與第工半導 體層之界面附近，含有成為正或負的固定電荷之雜質，在 與表面介電質膜相接之第1半導體層之表面之區域的至少 143168.doc •17· 201015731 口 P刀上’形成有第2導電彻 等電1之表面反轉層，背面介電質 膜3有成為與表面介電質膜 —& # 所含之雜質為相反極性之固 疋電何的雜質，在歲香而人 與貪面介電質膜相接之第3半導體層之 背面之區域的至少一邱八 4刀上’形成有第1導電型之背面反 ;表面介電質膜之表面上，含有透明導電膜，於背 面”電質膜之背面上，含有背面電極利用穿隨效應等使 載體通過表面介電f骐及背面介電質膜，@自透明導電膜 及背面電極分別被取出至外部。 此處，於本發明之第7態樣之光電轉換裝置中，較好的 是第1半導體層之帶隙為相較第1半導體層更遠離光入射側 之第2半導體層之帶隙以上’第2半導趙層之帶隙為相較第 2半導體層更遠離光入射側之第3半導體層之帶隙以上。 又，於本發明之第7態樣之光電轉換裝置中，較好的是 第1半導體層之厚度為相較第i半導體層更遠離光入射侧之 第2半導體層之厚度以下’第2半導體層之厚度為相較第2 半導體層更遠離光入射側之第3半導體層之厚度以下。 又，於本發明之第7態樣之光電轉換裝置中，較好的是 第1半導體層之厚度較第〗半導體層内之載體擴散長度更 薄。 又，於本發明之第7態樣之光電轉換裝置中，較好的是 第2半導體層之厚度較第2半導體層内之載體擴散長度更 薄。 又，於本發明之第7態樣之光電轉換裝置中，較好的是 第3半導體層之厚度較第3半導體層内之載體擴散長度更 143168.doc -18- 201015731 薄。 又，於本發明之第7態樣之光電轉換裝置中，較好的是 表面介電質膜之帶隙為4 2 eV以上。 又，於本發明之第7態樣之光電轉換裝置中，表面介電 質膜及背面介電質膜亦可分別包含選自由碳化矽、氧化 矽、氮氧化矽及氮化矽所組成之群中之至少一種。 又，於本發明之第7態樣之光電轉換装I中，較好的是 表面介電質膜之厚度及背面介電質膜之厚度分別以 質膜所合右 態樣之光電轉換裝置中’表面介電 之成為正或負的固定電荷之雜質亦可包含選自 由鋰、鈉、鉀、-、鉋、鎂、鈣、鳃、鋇、磷、砷及銻所 組成之群中之至小 ，及銻所 電行之… 介電質膜所含有之成為固定 =之雜質亦可包含選自由哪、銘、鎵、銦、翻 勒烯、氧化富勒烯、、备、6 匕田 烯氟氣、溴及碘所組成之群中 一種。 夕 質二：ΐ發明之第7態樣之光電轉換裳置中，表面介電 質膜所3有之成為固定電 鋁、鎵、銦、，… f亦可包含選自由硼、 及二二 氟化富勒稀、氧化富勒稀、氟、氣、淳 八所、，且成之群中之至少— 、 為固定電荷之雜質…+電質膜所含有之成 鎮H 選自由鐘、納、卸，、绝、 、又二 鱗、神及錦所組成之群中之至少-種。 於本發明之第7態樣之光 是，表面介電質膜所含有 ：、巾’較好的 战馮固疋電何之雜質存在最多 143168.doc •19· 201015731 之部位，係位於從第i半導體層與表面介電質膜之界面 起’在相對於界面而垂直之方向上朝著第！半導體層側前 進5 nm之區域、與朝著表面介電質膜侧前進5 間的區域。 域之 又，於本發明之第7態樣之光電轉換裝置中，較好的 疋身面介電質膜所含有之成為固定電荷之雜質存在最多 之部位’係位於從第2半導體層與f面介電質膜之界面 起’在相對於界面而垂直之方向上朝著第2半導體層侧前 進5 nm之區域、與朝著背面介電質膜側前進$ 之區域之❿ 間的區域。 又’根據本發明之第8態樣，可提供一 置，其包含:第物層;以與第物層 之方式而設置的第丨表面介電質膜；以與第丨半導體層之背 面相接之方式而設置的第1背面介電質膜；設置於第【半導 體層之背面側之第2半導體層；以與第2半導體層之表面相 接之方式而設置的第2表面介電質膜；以與第2半導體層之 背面相接之方式而設置的第2背面介電質膜；設置於第2半參 導體層之背面側之第3半導體層；以與第3半導體層之表面 相接之方式而設置的第3表面介電質膜；及以與第3半導體 層之责面相接之方式而設置的第3背面介電質膜，第^半導 體層之背面之第1背面介電質膜、與第2半導體層之表面之 第2表面電質膜係經由第1中間透明導電膜而接合，第2 半導體層之背面之第2背面介電質膜、與第3半導體層之表 面之第3表面介電質膜係經由第2中間透明導電膜而接合， 143168.doc -20· 201015731 第1表面介電質臈在與第1半導體層之界面附近，含有成為 正或負的固定電荷之雜質’在與第1表面介電質膜相接之 第1半導體層之表面之區域的至少一部分上，形成有第1導 電型或第2導電型之第1表面反轉層，第2表面介電質膜在 與第2半導體層之界面附近，含有成為與第丨表面介電質膜 所含之雜質為相同極性之固定電荷的雜質，在與第2表面 介電質膜相接之第2半導體層之表面之區域的至少一部分 上，形成有與第丨表面反轉層為相同導電型之第2表面反轉 層，第3表面介電質膜在與第3半導體層之界面附近，含有 成為與第1表面介電質膜所含之雜質為相同極性之固定電 射的雜質，在與第3表面介電質膜相接之第3半導體層之表 面之區域的至少一部分上，形成有與第丨表面反轉層為相 同導電型之第3表面反轉層，第i背面介電質膜在與第丨半 導體層之界面附近，含有成為與第1表面介電質膜所含之 雜質為相反極性之固定電荷的雜質，在與^背面介電質 膜相接之第1半導體層之背面之區域的至少一部分上，形 成^有與第1表面反轉層為相反導電型之第1背面反轉層，第 2用面"電質膜在與第2半導體層之界面附近，含有成為 第1背面介電質膜所含之雜質為相同極性之固定電荷的雜 質’在與第2背面介電質膜相接之第2半導體層之背面之區 域的至少一部分上’形成有與第1背面反轉層為相同導電 型之第2背面反轉層，第3背面介電質膜在與第3半導體層 之界面附近’含有成為與第1面介電質膜所含之雜 相同極性之固定雷# & μ # ''' 固疋電何的雜質’在與第3背面介電質膜相接 143168.doc -21 · 201015731 之第3半導體層之背面之p·祕αχ #面之£域的至少一部分上，形成有與 第面反轉層為相同实曾刑#势。北 』等電型之第3背面反轉層，於第1表 面介電質膜之表面上，含右捸 含有透明導電膜，於第3背面介電 質膜之背面上，含右哲 有背面電極，利用穿隧效應等使載體通 過表面介電質膜及背面介 ^^ · 牙囬1丨電質膜，而自透明導電膜及背面 電極分別被取出至外部。 β此處’於本發明之第8態樣之光電轉換裝置中，較好的 是第1半導體層之帶隙為相較第1半導體層更遠離光入射侧 之第2半導體層之帶隙以上，第2半導體層之帶隙為相較第 2半導體層更遠離光人射側之第3半導趙層之帶隙以上。 又’於本發明之第8態樣之光電轉換裝置中較好的是 第1半導體層之厚度為相較第i半導體層更遠離光入射侧之 第2半導體層之厚度以下，第2半導體層之厚度為相較第2 半導體層更遠離光入射側之第3半導體層之厚度以下。 又，於本發明之第8態樣之光電轉換裝置中，較好的是 第1半導體層之厚度較第〖半導體層内之載體擴散長度更 薄。 又於本發明之第8態樣之光電轉換裝置中，較好的是 第2半導體層之厚度較第2半導體層内之載體擴散長度更 薄。 又’於本發明之第8態樣之光電轉換裝置中，較好的是 第3半導體層之厚度較第3半導體層内之載體擴散長度更 薄。 又’於本發明之第8態樣之光電轉換裝置中，較好的是 143168.doc •22· 201015731 第1表面介電質膜、第1背面介電質膜、第2表面介電質 膜、第2背面介電質膜、及第3表面介電質膜各自之帶隙為 4·2 eV以上。 又，於本發明之第8態樣之光電轉換裝置中，第丨表面介 電質膜、第1背面介電質膜、第2表面介電質膜、第2背面 介電質膜、第3表面介電質膜、及第3背面介電質膜亦可分 別包含選自由碳切、氧切、氮氧切及氮切所組成 之群中之至少一種。Incorporation, whitening/a kind, and the impurity of the fixed charge of the second polarity may also be selected from the group consisting of lithium, sodium, cesium, i, potassium, planer, magnesium, calcium, barium, strontium, phosphorus, arsenic and antimony. At least one of the group consisting of. Further, in the photoelectric conversion device according to the fourth aspect of the present invention, at least one of the knives in the region of the surface of the first semiconductor layer bonded to the first dielectric film may include the first conductivity type or the first a conductive type m-th transfer layer of at least a portion of a region of a back surface of the i-th semiconductor layer bonded to the second dielectric film and a region of a surface of the second semiconductor layer bonded to the second dielectric film In a part of the photoelectric conversion device according to the fourth aspect of the present invention, the second inversion layer may be provided on the side of one of the laminated structures. The conductive semiconductor layer includes a second conductive semiconductor layer on the other side of the laminated structure. According to a fifth aspect of the present invention, a photoelectric conversion device including a semiconductor layer and a semiconductor layer can be provided. a dielectric film provided in a surface-contacting manner, the dielectric film containing impurities which become positive or negative fixed charges at least in the vicinity of the interface with the semiconductor layer, on the surface of the dielectric film 143168.doc.13 - 201015731 The surface contains transparent conductive The film is taken out from the transparent conductive film to the outside through the dielectric film by a tunnel effect or the like. Here, the photoelectric conversion device according to the fifth aspect of the present invention may be transparent. The surface of the conductive film includes a transparent substrate. In the photoelectric conversion device according to the fifth aspect of the present invention, at least a part of the surface of the surface of the semiconductor layer that is in contact with the dielectric film may include the first Further, in the photoelectric conversion device according to the fifth aspect of the present invention, the semiconductor layer may include crystalline germanium, amorphous germanium or microcrystalline germanium. In the photoelectric conversion device of the fifth aspect, it is preferable that the thickness of the semiconductor layer is thinner than the diffusion length of the carrier in the semiconductor layer. Further, in the photoelectric conversion device of the fifth aspect of the invention, it is preferable that Further, in the photoelectric conversion device of the fifth aspect of the present invention, the dielectric film may further comprise a carbon dioxide, an oxidized $, a oxynitride, and a nitride nitride. At least one of the groups formed by the evening. In the photoelectric conversion device of the fifth aspect of the invention, it is preferable that the thickness of the dielectric film is 3 nm or less. In the photoelectric conversion device according to the fifth aspect of the invention, the impurity which becomes a positive erbium charge may include Select at least one of the group consisting of lithium, sodium, potassium, cesium, sputum, dish, god, and record. Solid: The photoelectric conversion device of the fifth aspect of the invention becomes negative: charge The impurity may further comprise at least one selected from the group consisting of boron, aluminum, gallium indium, platinum-fluorene, oxidized fullerene, fluorine, gas, and indene, and 143l68.d〇c 201015731. In the photoelectric conversion device according to the fifth aspect of the invention, it is preferable that the portion where the impurity is most present is located from the interface between the semiconductor layer and the dielectric film toward the semiconductor layer in a direction perpendicular to the interface. The area between the 5 nm region and the region 5 nm toward the dielectric film side. Further, according to a sixth aspect of the present invention, there is provided a photoelectric conversion device comprising: a first semiconductor layer; a surface dielectric film provided in contact with a surface of the first semiconductor layer; a first conductivity type impurity-containing layer on the back surface of the first semiconductor layer; a second semiconductor layer provided on the back side of the W semiconductor layer; and a second conductivity type impurity-containing layer formed on the surface of the second semiconductor layer; a second conductivity type impurity-containing layer on the back surface side of the second semiconductor layer, and a second conductivity type impurity-containing layer formed on the surface of the third semiconductor layer; a first conductivity type impurity-containing layer on the back surface of the third semiconductor layer; and a first conductivity type impurity-containing layer on the back surface of the (e)th semiconductor layer and a second conductivity type impurity-containing layer on the surface of the second semiconductor layer The ith conductivity type impurity-containing layer on the back surface of the second semiconductor layer is bonded to the second conductivity type impurity-containing layer formed on the surface of the third semiconductor layer. The interface between the surface dielectric film and the first semiconductor layer nearby An impurity containing a positive or negative fixed charge is formed on at least a portion of a surface of the surface of the first semiconductor layer that is in contact with the surface dielectric film, and a surface inversion layer of the second conductivity type is formed on the surface. The surface of the electric film contains a transparent conductive film, and the carrier is taken out from the transparent conductive film through the surface dielectric medium by a wear-through effect or the like to the outside of 143I68.doc 15 201015731. Here, in the photoelectric conversion device according to the sixth aspect of the present invention, it is preferable that the band gap of the first semiconductor layer is the same as that of the first semiconductor layer! The semiconductor layer is further apart from the band gap of the second semiconductor layer on the light incident side, and the band gap of the second semiconductor layer is equal to or larger than the band gap of the third semiconductor layer farther from the light incident side than the second semiconductor layer. Further, in the photoelectric conversion device of the sixth aspect of the present invention, a preferred 0 number! The thickness of the semi-guided layer is better than the first! Carrier removal length in the semiconductor layer = thin. Further, in the photoelectric conversion device according to the sixth aspect of the invention, it is preferable that the thickness of the second semiconductor layer is thinner than that of the carrier in the second semiconductor layer. Further, in the photoelectric conversion device according to the sixth aspect of the present invention, the third semiconductor layer is thicker, and the thickness of the main channel is larger than that of the carrier in the third +-conductor layer. In the photoelectric conversion device of the sixth aspect of the invention, the band gap of the surface dielectric film is 4.2 eV or more. Further, in the photoelectric conversion device according to the sixth aspect of the invention, the human plasma film may further comprise at least one selected from the group consisting of carbon cut, oxygen cut, and nitrogen oxide I:. Further, in the photoelectric conversion device of the sixth aspect of the invention, the thickness of the surface dielectric film is 3 nm or less. Further, the impurity of the fixed charge in the photoelectric conversion device I of the sixth aspect of the present invention may further comprise Λ-C selected from the group consisting of a clock, and a positive Λ-C. ' 叙 1, 绝, 、, 钡, 碟, There is one less group of arsenic and antimony. 143168.doc 201015731 Second electricity = the sixth aspect of the month of photoelectric conversion, the negative electricity can also contain impurities selected from the group consisting of boron, aluminum, fullerene, oxidized fullerenes, fluorine, chlorine, Desert / pin, fluorine at least - species. In the photoelectric conversion device of the sixth aspect of the present invention, in the photoelectric conversion device of the sixth aspect of the present invention, it is preferable that the impurity of the positive or negative charge has the most part, the position + the interface between the conductor layer and the surface dielectric film, 5 nm in the direction toward the boundary of the conductor layer in the direction perpendicular to the boundary =, and 5 nm in the direction toward the surface of the dielectric film The area between. According to a seventh aspect of the present invention, there is provided a photoelectric conversion device comprising: a first semiconductor layer; a surface dielectric film provided in contact with a surface of the i-th semiconductor layer; a first conductivity type impurity-containing layer on the back surface of the semiconductor layer, a second semiconductor layer provided on the back surface side of the first semiconductor layer, and a second conductivity type formed on the surface of the second semiconductor layer: a second conductivity type impurity-containing layer formed on the back surface side of the second semiconductor layer, a second conductivity type impurity-containing layer formed on the surface of the third semiconductor layer, and a second conductivity type impurity layer formed on the surface of the third semiconductor layer a back surface dielectric film on the back surface of the semiconductor layer; a first conductivity type impurity-containing layer on the back surface of the first semiconductor layer; and a second conductivity type impurity-containing layer on the surface of the second semiconductor layer; The first conductivity type impurity-containing layer on the back surface of the layer is bonded to the first conductive impurity-containing layer formed on the surface of the third semiconductor layer, and the surface dielectric film is positive or in the vicinity of the interface with the semiconductor layer. negative The impurity of the fixed charge is at least 143168.doc •17·201015731 on the surface of the first semiconductor layer that is in contact with the surface dielectric film. In the transfer layer, the back dielectric film 3 has an impurity which is opposite to the impurity contained in the surface dielectric film-&#, and is connected to the greedy dielectric film at the age of the fragrance. At least one of the regions on the back side of the third semiconductor layer is formed on the back side of the first conductivity type; the surface of the surface dielectric film contains a transparent conductive film on the back side of the back surface of the dielectric film In the above, the back surface electrode is passed through the surface dielectric layer and the back surface dielectric film by the wear-through effect, etc., and the self-transparent conductive film and the back surface electrode are respectively taken out to the outside. Here, the seventh aspect of the present invention In the photoelectric conversion device, it is preferable that the band gap of the first semiconductor layer is higher than the band gap of the second semiconductor layer farther from the light incident side than the first semiconductor layer. a band gap of the third semiconductor layer farther from the light incident side than the second semiconductor layer Further, in the photoelectric conversion device according to the seventh aspect of the present invention, it is preferable that the thickness of the first semiconductor layer is lower than the thickness of the second semiconductor layer farther from the light incident side than the i-th semiconductor layer. The thickness of the semiconductor layer is less than the thickness of the third semiconductor layer which is further away from the light incident side than the second semiconductor layer. Further, in the photoelectric conversion device of the seventh aspect of the invention, the first semiconductor layer is preferably used. Further, in the photoelectric conversion device according to the seventh aspect of the invention, it is preferable that the thickness of the second semiconductor layer is larger than that of the carrier in the second semiconductor layer. Further, in the photoelectric conversion device according to the seventh aspect of the invention, it is preferable that the thickness of the third semiconductor layer is thinner than the carrier diffusion length in the third semiconductor layer by 143168.doc -18 - 201015731. Further, in the photoelectric conversion device according to the seventh aspect of the invention, it is preferable that the band gap of the surface dielectric film is 4 2 eV or more. Further, in the photoelectric conversion device of the seventh aspect of the invention, the surface dielectric film and the back dielectric film may each comprise a group selected from the group consisting of tantalum carbide, tantalum oxide, niobium oxynitride, and tantalum nitride. At least one of them. Further, in the photoelectric conversion device 1 of the seventh aspect of the present invention, it is preferable that the thickness of the surface dielectric film and the thickness of the back dielectric film are respectively in the photoelectric conversion device in which the plasma film is combined with the right state. The impurity which becomes a positive or negative fixed charge on the surface may also comprise a small group selected from the group consisting of lithium, sodium, potassium, -, planer, magnesium, calcium, barium, strontium, phosphorus, arsenic and antimony. And the electric field of the dielectric film... The impurity contained in the dielectric film may be selected from the group consisting of gems, gems, gallium, indium, fulcene, oxidized fullerenes, and hexanene. One of a group consisting of gas, bromine and iodine.夕质二: In the photoelectric conversion of the seventh aspect of the invention, the surface dielectric film 3 has a fixed electrical aluminum, gallium, indium, ..., f can also be selected from the group consisting of boron, and difluoro Fullerene, oxidized, fuller, fluorinated, fluorinated, sulphuric, sulphuric, sulphuric, sulphide, sulphide, sulphide, sulphide, sulphide, sulphide, sulphide, sulphide, sulphide At least one of the group consisting of unloading, fascinating, and two scales, gods and brocades. The light of the seventh aspect of the present invention is that the surface dielectric film contains: a towel, which is a good part of the von Fenggu, which has a maximum of 143168.doc • 19· 201015731, which is located at the The interface between the i-semiconductor layer and the surface dielectric film is 'facing in the direction perpendicular to the interface! The semiconductor layer side advances to a region of 5 nm and a region that advances toward the surface dielectric film side by five. Further, in the photoelectric conversion device according to the seventh aspect of the present invention, it is preferable that the portion of the surface of the dielectric film containing the fixed charge is the most present in the second semiconductor layer and f. The interface of the surface dielectric film is a region between a region which is 5 nm toward the second semiconductor layer side in the direction perpendicular to the interface and a region which advances by $ toward the back dielectric film side. Further, according to an eighth aspect of the present invention, there is provided an apparatus comprising: a first layer; a second surface dielectric film disposed in a manner corresponding to the first layer; and a back surface of the second semiconductor layer a first back dielectric film provided in the first embodiment; a second semiconductor layer provided on the back side of the semiconductor layer; and a second surface dielectric provided in contact with the surface of the second semiconductor layer a film; a second back surface dielectric film provided to be in contact with the back surface of the second semiconductor layer; a third semiconductor layer provided on the back side of the second half-joint conductor layer; and a surface of the third semiconductor layer a third surface dielectric film provided in contact with the first surface dielectric film provided in contact with the surface of the third semiconductor layer, and a first back surface of the back surface of the second semiconductor layer The dielectric film and the second surface dielectric film on the surface of the second semiconductor layer are bonded via the first intermediate transparent conductive film, and the second back surface dielectric film and the third semiconductor layer on the back surface of the second semiconductor layer The third surface dielectric film on the surface is bonded via the second intermediate transparent conductive film, 1431 68.doc -20· 201015731 The first surface dielectric 臈 contains an impurity which becomes a positive or negative fixed charge near the interface with the first semiconductor layer, and the first semiconductor which is in contact with the first surface dielectric film The first surface inversion layer of the first conductivity type or the second conductivity type is formed on at least a part of the surface of the layer, and the second surface dielectric film is included in the vicinity of the interface with the second semiconductor layer. The impurity contained in the surface dielectric film is a fixed charge of the same polarity, and the surface of the second semiconductor layer is formed on at least a portion of the surface of the second semiconductor layer that is in contact with the second surface dielectric film. The inversion layer is a second surface inversion layer of the same conductivity type, and the third surface dielectric film contains the same polarity as the impurity contained in the first surface dielectric film in the vicinity of the interface with the third semiconductor layer. The fixed-electrode impurity is formed on at least a portion of a region of the surface of the third semiconductor layer that is in contact with the third surface dielectric film, and a third surface inversion is formed in the same conductivity type as the second surface inversion layer. Layer, the i-th back dielectric film is in semi-conducting with the third The vicinity of the interface of the bulk layer contains an impurity which is a fixed charge having a polarity opposite to that of the impurity contained in the first surface dielectric film, and at least a portion of the region on the back surface of the first semiconductor layer which is in contact with the back surface dielectric film. The first back surface inversion layer having the opposite conductivity type to the first surface inversion layer is formed, and the second surface " the electric film is included in the vicinity of the interface with the second semiconductor layer to be the first back dielectric The impurity contained in the plasma film is a fixed charge of the same polarity, and the first back surface inversion layer is formed on at least a part of a region on the back surface of the second semiconductor layer that is in contact with the second back surface dielectric film. In the second back surface inversion layer of the same conductivity type, the third back surface dielectric film contains a fixed-polarity of the same polarity as that of the first surface dielectric film in the vicinity of the interface with the third semiconductor layer. μ # ''' 杂质 何 何 杂质 在 与 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 On the upper side, the formation is the same as the first inversion layer. The third back surface inversion layer of the north-type isoelectric type includes a transparent conductive film on the surface of the first surface dielectric film, and a back surface of the third back dielectric film, including the right side of the back surface The electrode is passed through the surface dielectric film and the back surface of the electrode by a tunneling effect or the like, and the transparent conductive film and the back electrode are respectively taken out to the outside. In the photoelectric conversion device according to the eighth aspect of the present invention, it is preferable that the band gap of the first semiconductor layer is larger than the band gap of the second semiconductor layer farther from the light incident side than the first semiconductor layer. The band gap of the second semiconductor layer is equal to or larger than the band gap of the third semiconductor layer of the second semiconductor layer farther from the light-emitting side. Further, in the photoelectric conversion device according to the eighth aspect of the present invention, it is preferable that the thickness of the first semiconductor layer is lower than the thickness of the second semiconductor layer farther from the light incident side than the i-th semiconductor layer, and the second semiconductor layer The thickness is equal to or less than the thickness of the third semiconductor layer farther from the light incident side than the second semiconductor layer. Further, in the photoelectric conversion device of the eighth aspect of the invention, it is preferable that the thickness of the first semiconductor layer is thinner than the diffusion length of the carrier in the semiconductor layer. Further, in the photoelectric conversion device according to the eighth aspect of the invention, it is preferable that the thickness of the second semiconductor layer is thinner than the carrier diffusion length in the second semiconductor layer. Further, in the photoelectric conversion device according to the eighth aspect of the invention, it is preferable that the thickness of the third semiconductor layer is thinner than the diffusion length of the carrier in the third semiconductor layer. Further, in the photoelectric conversion device according to the eighth aspect of the present invention, it is preferable that the first surface dielectric film, the first back dielectric film, and the second surface dielectric film are 143168.doc •22·201015731. The band gap of each of the second back dielectric film and the third surface dielectric film is 4·2 eV or more. Further, in the photoelectric conversion device according to the eighth aspect of the present invention, the second surface dielectric film, the first back dielectric film, the second surface dielectric film, the second back dielectric film, and the third The surface dielectric film and the third back dielectric film may each include at least one selected from the group consisting of carbon cutting, oxygen cutting, oxynitriding, and nitrogen cutting.

又，於本發明之第8態樣之光電轉換裝置中，較好的是 第1表面介電質膜、第i背面介電質膜、第2表面介電質 膜、第2背面介電質膜、第3表面介電質膜、及第3背面介 電質膜各自之厚度為3 nm以下。 又，於本發明之第8態樣之光電轉換裝置中，第丨表面介 電質膜、第2表面介電質膜、及第3表面介電質膜所含有之 成為固定電荷之雜質亦可分別包含選自由m 如m m、神及録所組成之群中之至 少-種’第i背面介電質膜、第2背面介電質膜、及第3背 面介電質膜所含有之成為㈣電荷之雜質亦可分別包含選 :由硼、銘、鎵、銦、翻、氟化富勒烯、氧化富勒烯、 氟、氯、溴及碘所組成之群中之至少—種。 又，於本發明之第8態樣之光電轉換裝置中，第i表面介 =膜、第2表面介電質膜、及第3表面介電質膜所含有之 成為固定電荷之雜質亦可分別包含選自由，、銘、嫁、 鋼、麵、敦化富勒稀、氧化富勒稀、氣、氣、漠及埃所組 143168.doc -23- 201015731 成之群中之至少—種，第1背面介電質膜、第2背面介電質 膜、及第3背面介電質膜所含有之成為固定電荷之雜質亦 可刀別包含選自由鋰、鈉、鉀、铷、鉋、鎂、鈣、锶、 鋇碟、坤及錄所組成之群中之至少—種。 0又，於本發明之第8態樣之光電轉換裝置中，較好的 疋第1表面介電質膜所含有之成為固定電荷之雜質存在 最多之部位’係位於從第i半導體層與第#面介電質膜之 界面起’在相對於界面而垂直之方向上朝著^半導體層 侧前進5⑽之區域、與朝著第1表面介電質膜側前進5 nm 之區域之間的區域。 又，於本發明之第8態樣之光電轉換裝置中，較好的 是，第2表面介電質膜所含有之成為固^電荷之雜質存在 最多之部位’係位於從第2半導體層與第2表面介電質膜之 界2起，在相對於界面而垂直之方向上朝著第2半導體層 側前進5 nm之區域、與朝著第2表面介電質膜側前進$⑽ 之區域之間的區域。 又，於本發明之第8態樣之光電轉換裝置中，較好的 是，第3表面介電質膜所含有之成為固定電荷之雜質存在 最多之部位，係位於從第3半導體層與第3表面介電質膜之 界面起，在相對於界面而垂直之方向上朝著第3半導體層 側前進5 nm之區域、與朝著第3表面介電質膜側前進$ 之區域之間的區域。 又，於本發明之第8態樣之光電轉換裝置中較好的 是’第1背面介電質膜所含有之成為固$電荷之雜質存在 143168.doc -24- 201015731 最多之部位，係位於從第丨半導體層與第if面介電質膜之 在相對於界面而垂直之方向上朝著第時導體層 側刖進5 nm之區域、與朝著第1背面介電質膜側前進5nm 之區域之間的區域。 又，於本發明之第8態樣之光電轉換裝置中，較好的 是:第2背面介電質膜所含有之成為固定電荷之雜質存在 最多之部位，係位於從第2半導體層與第2背面介電質膜之 =，在相對於界面而垂直之方向上朝著第2半導體層 前進5⑽之區域、與朝著第2背面介電質膜側前進5⑽ 之區域之間的區域。 曰又’於本發明之第8態樣之光電轉換裝置中，較好的 是，第3背面介電質膜所含有之成為固定電荷之 最多之部位’係位於從第3半導體層與第3背面介電質膜之 =’在相對於界面而垂直之方向上朝著第3半導體層 ⑴⑽之區域、與朝著第3背面介電質臈側前進5、m 之區域之間的區域。 明^於本發明之第8態樣之光電轉換裝置中，亦可於透 電膜之表面上包含透明基板。 又，於本發明之第8態樣之光電轉換裝置中，第丨半導體 ，第2半導體層、及第3半導體層亦可分別包含結晶石夕、 非日日矽或微晶矽。 發明之效果 2據本發明，可提供—種具有利用由固定電荷所誘發之 轉層之構成且特性優異之光電轉換裝置。 143l68.doc -25- 201015731 可知:供種光電轉換效率等之特性優 又’根據本發明， 異之光電轉換裝置。 【實施方式】 以下， 之圖式中者0 對本發明之實施形態進行說明。再者，於本發明 ’相同之參照符號係表示相同部分或相當部分 又，於本發明中，所謂反轉層’亦包含由介電質膜中之 成為固定電荷之雜質所誘發之？型半導體表面之電子載體 層' η型半導體層表面之電洞載體層、或者別本徵型）半 導體表面之電子載體層或電洞載體層之情況。 又，於本發明之實施形態中’藉由將雜質掺雜到與半導 體層相同之半導體材料中來形成η型層及ρ型層，但亦可使 用與半導體層不同之半導趙材料。例如，當使用非晶矽作 為半導體層時，亦可將摻雜有„型或ρ型雜質之非晶石夕錯、 或者非晶碳化矽等用作!!型層或ρ型層。 又，於本發明之實施形態中，以主要使用矽作為半導體 層之情況為中心進行說明’但作為半導體層，除了矽以 外，亦可使用氮㈣、碳化石夕、碲化编、砂化嫁、麟化 銦、Cu(In、Ga)Se2、石夕録、錯等。 &lt;實施形態1&gt; 圖1(a)中表示本發明之光電轉換裝置之一例的光入射侧 之表面之俯視示意圖。此處，於圖1(a)所示之構成之本實 施形態的光電轉換裝置之光入射側之表面，設置有作為介 電質膜之氧化矽膜6。又，於氧化矽膜6之下部形成有作為 143168.doc -26- 201015731 雜貝含有層之梳形狀之n+層3,且形成有帶狀之金屬電極8 作為與梳形狀之n+層3相接之表面電極。 圖1(b)中表示沿著圖1(a)2lb_lb的剖面示意圖，圖1(幻 中表示〜著圖1(a)之lc-lc之剖面示意圖。如圖〖（…及圖 1(c)所不，於本實施形態之光電轉換裝置中，於作為半導 體層之P型矽基板2之光入射側之表面上形成有上述“層 3。又，於p型矽基板2之與光入射側之表面成為相反側之 表面的背面上形成有，並以與吋層1之背面相接之方 式而形成有背面電極7。再者，对層1係含有較1)型矽基板2 為更高濃度之p型雜質的層。 進而，上述氧化矽膜6係以覆蓋p型矽基板2之光入射側 之表面的方式而形成。並且，氧化矽膜6在與p型矽基板2 之光入射側之表面之界面上，含有成為正的固定電荷之雜 質之铯5。 此處’铯5在與p型矽基板2之光入射側之表面之界面附 近經離子化而成為正的固定電荷，因此在與氧化矽膜6相 接之p型矽基板2之光入射側之表面的至少一部分區域上， 會誘發與n+層3同樣地發揮作為η型半導體之作用的表面反 轉層4。 再者’亦可使用本徵型矽基板來代替ρ型矽基板 以下’對圖1所示之構成之本實施形態的光電轉換裝置 之製造方法之一例進行說明。首先，於ρ型矽基板2之光入 射側之表面形成氧化矽膜6。此處，如為ρ型矽基板2包含 單晶矽之情形時，以例如8〇〇。〇~1200。(：之溫度、較好的是 143168.doc •27· 201015731 以900 C~1050°C之溫度進行熱氧化，藉此可於？型矽基板2 之光入射側之表面形成氧化矽膜6。再者，氧化矽膜6亦可 利用例如CVD(ChemiCal VaP〇r Deposition，化學氣相沈積） 法或ALD(At〇mic Layer Deposition，原子層沈積）法等而形 成。又，藉由使用電漿CVD法形成氧化矽膜6，能夠以於 例如400 C以下之低溫形成氧化;g夕膜6。 其次，於ρ型矽基板2之背面形成p+層i。此處，？+層 形成例如可藉由在p型矽基板2之背面使p型雜質擴散等而 進行。又，p型雜質之擴散例如可藉由使用BBr3(三溴化硼） 等之含有ρ型雜質（硼）之氣體的氣相擴散而進行。再者，作 為Ρ型雜質，除了硼以外，亦可使用例如鋁或銦等。又， Ρ+層1亦可藉由使用例如離子佈植法或離子摻雜法等，將ρ 型雜質導入至ρ型矽基板2之背面後進行退火（anneal)等而 形成。 其次，於ρ型矽基板2之光入射側之表面形成11+層3。此 處，n+層3之形成可藉由在p型矽基板2之光入射側之表面 使η型雜質擴散而進行。又，n型雜質之擴散例如可在與 層3之形成部位相對應之部位的氧化矽膜6之一部分設置開 口部，並自該開口部使用POCh(三氣氧磷）等之含有η型雜 質（磷）之氣體藉由氣相擴散而進行。再者，作為η型雜質， 除了磷以外，亦可使用例如砷或銻等。又，η+層3例如亦 可藉由使用離子佈植法或離子摻雜法等，將η型雜質導入 至Ρ型石夕基板2之表面後進行退火等而形成。 其次，使形成於ρ型矽基板2之光入射侧之表面上的氧化 143168.doc -28- 201015731 石夕膜6中含有鉋5。此處，關於铯5，例如可在形成於p型矽 基板2之光入射侧之表面上的氧化石夕膜6中將铯離子進行離 子佈植，藉以使氧化矽膜6中含有鉋5。 接下來，進行p型矽基板2之退火。此處，p型矽基板2之 退火例如可藉由對上述铯離子佈植後之p型矽基板2在例如 800°c〜1000°c之溫度下實施退火來進行。藉此，可使氧化 石夕膜6中之鉋5偏析到與P型矽基板2之光入射側之表面之界 面上。偏析到氧化矽膜6與1)型矽基板2之界面上之鉋5係藉 ® 由使電子向P型矽基板2釋放而帶正電從而離子化，故而會 在與氧化碎膜6相接之p型梦基板2之光入射側之表面上形 成表面反轉層4。 其次’於p型矽基板2之光入射侧之表面形成金屬電極 8。此處，金屬電極8可藉由如下方法形成：例如在與形成 有金屬電極8之部位相對應之氧化矽膜6的部位上設置開口 部’並使用遮罩（mask)等將金屬蒸鍍成特定之形狀等。 ❹ 其次’於P型♦基板2之p+層1之背面形成背面電極7。此 處’背面電極7可藉由例如在p型矽基板2之p+層1之背面上 蒸鑛金屬等而形成。 最後’於上述金屬電極8及背面電極7形成後進行p型石夕 基板2之退火，藉此製作具有上述構成之本實施形態之光 電轉換裝置的一例。此處，p型矽基板2之退火例如可藉由 使P型矽基板2暴露於350°C~50(TC之溫度之氫環境中來進 行。 於以上方式所製作之上述構成之本實施形態的光電轉換 143168.doc -29- 201015731 裝置中’氧化矽膜6與p型矽基板2之光入射側之表面相 接’藉由在氧化矽膜6與p型矽基板2之光入射側之表面之 界面上已離子化之鉋，而於p型矽基板2之光入射側之表面 上形成表面反轉層4。 因此，於上述構成之本實施形態之光電轉換裝置中，與 設置有含固定電荷之第二層、及在與半導體表面之間不含 固定電荷之第一層之構成的專利文獻丨所揭示之太陽電池 相比’更容易在表面反轉層4上高密度地誘發負電荷，使 作為η型半導體之功能得以提高，故可抑制p型梦基板2之 光入射側之表面上之載體的再結合等，藉此，光電轉換效 率等之光電轉換裝置之特性會得到提高。 又’在ρ型矽基板2之光入射側之表面上，設置作為η型 半導體而發揮功能之表面反轉層4來代替成為短波長光之 吸收源的η+層3，藉此，與η+層3相比，短波長光之吸收更 知到抑制，因此可使光電轉換效率等之光電轉換裝置之特 性得到進一步提高。 又，於上述構成之本實施形態之光電轉換裝置中，可根 據氧化矽膜6與ρ型石夕基板2之光入射側之表面之界面上的 鉋之偏析量，來控制表面反轉層4上所誘發之負電荷（電子） 之密度。 特別是如本實施形態般’當藉由在氧化矽膜6中之铯離 子佈植及退火而使鉋偏析到氧化矽膜6與ρ型矽基板2之界 面上時，表面反轉層4上之用以獲得最佳的負電荷密度之 绝離子佈植量之容限（margin)較廣，因此可提供一種品質 143168.doc -30- 201015731 穩定且特性高的光電轉換裝置。 又’於上述構成之本實施形態之光電轉換裝置中，使p 型矽基板2之光入射側之表面上的界面能階因表面反轉層4 上所誘發之負電荷而終止，藉此可抑制p型矽基板2之光入 射側之表面之界面能階上的載體之再結合，從而可使光電 轉換效率等之光電轉換裝置之特性得到進一步提高。 又，於以上所述中，使用P型矽基板2作為半導體層，但 i不限定於此，亦可使用例如結晶石夕、非晶石夕、微晶石夕或 者矽以外之其他種類之半導體等的半導體層◎再者，結晶 石夕中包含單晶碎、多晶石夕、或者單晶石夕與多晶石夕之混合體 等。 又，於以上所述中，對p型矽基板2中包含單晶矽之情況 進行了說明，但例如當使用包含非晶矽之半導體層代替P 夕基板2時，較好的是在形成含有鉋5之氧化石夕膜6之後 不進行尚溫製程而製作本實施形態之光電轉換裝置。 ❹ 又於以上所述中，使用氧化矽膜6作為介電質膜，但 當然並不限定於此，亦可使用例如選自由氧化石夕、氮氧化 矽及氮化矽所組成之群中之至少一種。 又，作為介電質膜，較好的是使用帶隙為4.2 eV以上之 介電質膜。例如太陽光之大部分係由具有300 nm以上之波 光所構成，故而當使用帶隙為4.2 ev以上之介電質膜 而使太陽光入射時，可抑制具有300 nm以上之波長之太陽 光被”電質膜所吸收，從而轉換損失（loss)變少，因此光 電轉換裝置之特性有進-步提高之傾向。 143168.doc 31 201015731 ^ ^ β丨、’’丨〜一丨f句取两止的固定電 荷之雜質的情況進行了說明，但並不限定於此，，亦可使用 例如包含選自由鋰、鈉、鉀、铷、铯、鎂、鈣、鳃、鋇、 坤及銻所組成之群中之至少一種者。 、 又於上述構成之本實施形態之光電轉換裝置中，亦 =換P型與η型之導電型。於此情形時，可使用成為負的^ 疋電荷之雜質代替如絶之成為正的固定電荷之雜質。作為 成為負的固定電荷之雜質，可使用例如包含選自由删^Further, in the photoelectric conversion device according to the eighth aspect of the present invention, the first surface dielectric film, the ith back dielectric film, the second surface dielectric film, and the second back dielectric are preferably used. The thickness of each of the film, the third surface dielectric film, and the third back dielectric film is 3 nm or less. Further, in the photoelectric conversion device according to the eighth aspect of the present invention, the second surface dielectric film, the second surface dielectric film, and the third surface dielectric film may be impurities which are fixed charges. Each of the at least one type of the 'i-th back dielectric film, the second back dielectric film, and the third back dielectric film selected from the group consisting of m, such as mm, and sacred, is contained in (4) The impurities of the charge may also include at least one selected from the group consisting of boron, indium, gallium, indium, fluorinated fullerene, oxidized fullerene, fluorine, chlorine, bromine and iodine. Further, in the photoelectric conversion device according to the eighth aspect of the present invention, the impurity which becomes a fixed charge contained in the i-th surface dielectric film, the second surface dielectric film, and the third surface dielectric film may be separately Containing at least one selected from the group consisting of:,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The surface of the back dielectric film, the second back dielectric film, and the third back dielectric film which are fixed charges may be selected from the group consisting of lithium, sodium, potassium, rubidium, planer, magnesium, and calcium. At least one of the group consisting of 锶, 锶, 钡, 坤, and recorded. Further, in the photoelectric conversion device according to the eighth aspect of the present invention, it is preferable that the portion of the first surface dielectric film which contains a fixed charge is the most present portion from the i-th semiconductor layer and the first The interface of the #面 dielectric film is the region between the region which is 5 (10) toward the semiconductor layer side in the direction perpendicular to the interface, and the region 5 nm toward the first surface dielectric film side. . Further, in the photoelectric conversion device according to the eighth aspect of the present invention, it is preferable that the portion of the second surface dielectric film that contains the most impurities in the charge is located in the second semiconductor layer. The boundary of the second surface dielectric film is 2, and the region which is 5 nm toward the second semiconductor layer side in the direction perpendicular to the interface and the region which advances toward the second surface dielectric film side by $(10) The area between. Further, in the photoelectric conversion device according to the eighth aspect of the present invention, it is preferable that the third surface dielectric film contains the most abundant impurities in the fixed charge, and is located in the third semiconductor layer and the third semiconductor layer. (3) The interface between the surface dielectric film and the region which is 5 nm toward the third semiconductor layer side in the direction perpendicular to the interface, and the region which advances toward the third surface dielectric film side by $. region. Further, in the photoelectric conversion device according to the eighth aspect of the present invention, it is preferable that the impurity which is contained in the first back dielectric film and which has a solid charge is 143168.doc -24 - 201015731, which is located at the most a region in which the second semiconductor layer and the first-if dielectric film are perpendicular to the interface in the direction perpendicular to the interface toward the first conductor layer and 5 nm toward the first back dielectric film side. The area between the areas. Further, in the photoelectric conversion device according to the eighth aspect of the present invention, it is preferable that the second semiconductor layer and the second semiconductor layer contain the most impurities which are fixed charges. (2) A region between the region of the back surface dielectric film that is 5 (10) toward the second semiconductor layer and the region 5 (10) toward the second back dielectric film side in the direction perpendicular to the interface. Further, in the photoelectric conversion device according to the eighth aspect of the present invention, it is preferable that the portion of the third back surface dielectric film which is the most fixed charge is located from the third semiconductor layer and the third layer. The back dielectric film = 'a region between the region facing the third semiconductor layer (1) (10) in the direction perpendicular to the interface and the region advancing toward the third back dielectric dielectric side by 5, m. In the photoelectric conversion device of the eighth aspect of the invention, a transparent substrate may be included on the surface of the transparent film. Further, in the photoelectric conversion device according to the eighth aspect of the present invention, the second semiconductor, the second semiconductor layer, and the third semiconductor layer may each include a crystal ray, a non-daily or a microcrystalline germanium. Advantageous Effects of Invention According to the present invention, it is possible to provide a photoelectric conversion device having a structure which utilizes a transition layer induced by a fixed charge and which is excellent in characteristics. 143l68.doc -25- 201015731 It is understood that the characteristics of the photoelectric conversion efficiency and the like are excellent, and the photoelectric conversion device according to the present invention is different. [Embodiment] Hereinafter, an embodiment of the present invention will be described with reference to 0 in the drawings. In the present invention, the same reference numerals are used to refer to the same or equivalent parts. In the present invention, the "inverted layer" also includes impurities which are fixed charges in the dielectric film. The electron carrier layer on the surface of the semiconductor layer is the case of the electron carrier layer or the hole carrier layer on the surface of the semiconductor layer of the n-type semiconductor layer or the intrinsic type. Further, in the embodiment of the present invention, the n-type layer and the p-type layer are formed by doping impurities into the same semiconductor material as the semiconductor layer, but a semiconductor material different from the semiconductor layer may be used. For example, when an amorphous germanium is used as the semiconductor layer, an amorphous crystal doped with a „type or a p-type impurity, or an amorphous tantalum carbide or the like may be used as the !! type layer or the p type layer. In the embodiment of the present invention, the case where ruthenium is mainly used as the semiconductor layer will be mainly described. However, as the semiconductor layer, in addition to ruthenium, nitrogen (four), carbonized stone, smelting, sanding, and lining may be used. Indium, Cu (In, Ga) Se2, Shi Xi Lu, Wrong, etc. <Embodiment 1> Fig. 1(a) is a plan view showing the surface on the light incident side of an example of the photoelectric conversion device of the present invention. The surface of the photoelectric conversion device of the present embodiment having the configuration shown in Fig. 1(a) is provided with a ruthenium oxide film 6 as a dielectric film, and further formed under the yttrium oxide film 6. There is a comb-shaped n+ layer 3 as a layer containing 143168.doc -26- 201015731, and a strip-shaped metal electrode 8 is formed as a surface electrode which is in contact with the comb-shaped n+ layer 3. Fig. 1(b) A cross-sectional view along 2lb_lb of Fig. 1(a) is shown, and Fig. 1 (the illusion shows a section of lc-lc of Fig. 1(a) In the photoelectric conversion device of the present embodiment, the above-mentioned "layer 3" is formed on the surface on the light incident side of the P-type germanium substrate 2 as the semiconductor layer, as shown in Fig. 1 (c). Further, a back surface electrode 7 is formed on the back surface of the surface of the p-type germanium substrate 2 opposite to the surface on the light incident side, and the back surface electrode 7 is formed in contact with the back surface of the germanium layer 1. Further, the layer is formed In the first embodiment, the ruthenium oxide film 6 is formed to cover the surface on the light incident side of the p-type ruthenium substrate 2. Further, the ruthenium oxide film 6 is formed to cover the surface on the light incident side of the p-type ruthenium substrate 2. The ruthenium film 6 contains 铯5 which is a positive fixed charge impurity at the interface with the surface on the light incident side of the p-type ruthenium substrate 2. Here, 铯5 is on the surface of the light incident side with the p-type ruthenium substrate 2. Since the vicinity of the interface is ionized and becomes a positive fixed charge, at least a part of the surface on the light incident side of the p-type germanium substrate 2 that is in contact with the hafnium oxide film 6 is induced to function in the same manner as the n+ layer 3 The surface inversion layer 4 functioning as an n-type semiconductor. An example of a method of manufacturing the photoelectric conversion device of the present embodiment having the configuration shown in Fig. 1 will be described below. First, oxidation is formed on the surface of the light incident side of the p-type germanium substrate 2. The ruthenium film 6. Here, in the case where the p-type ruthenium substrate 2 contains a single crystal ruthenium, for example, 8 〇〇 〇 1200 1200. (: temperature, preferably 143168.doc • 27· 201015731 to 900 The oxidized ruthenium film 6 is formed on the surface of the light-incident side of the ruthenium-based substrate 2 by thermal oxidation at a temperature of C to 1050 ° C. Further, the ruthenium oxide film 6 can also be etched by, for example, CVD (ChemiCal VaP〇r Deposition). , chemical vapor deposition) method or ALD (At〇mic Layer Deposition) method or the like. Further, by forming the hafnium oxide film 6 by the plasma CVD method, it is possible to form oxidation at a low temperature of, for example, 400 C or less; Next, a p+ layer i is formed on the back surface of the p-type germanium substrate 2. Here,? The formation of the + layer can be performed, for example, by diffusing a p-type impurity or the like on the back surface of the p-type germanium substrate 2. Further, the diffusion of the p-type impurity can be carried out, for example, by gas phase diffusion using a gas containing a p-type impurity (boron) such as BBr3 (boron tribromide). Further, as the cerium-type impurity, in addition to boron, for example, aluminum or indium may be used. Further, the Ρ+ layer 1 may be formed by introducing an p-type impurity onto the back surface of the p-type ruthenium substrate 2 by using an ion implantation method, an ion doping method, or the like, followed by annealing or the like. Next, 11+ layers 3 are formed on the surface on the light incident side of the p-type germanium substrate 2. Here, the formation of the n + layer 3 can be performed by diffusing n-type impurities on the surface on the light incident side of the p-type germanium substrate 2. Further, for example, an opening portion may be provided in a portion of the ruthenium oxide film 6 at a portion corresponding to a portion where the layer 3 is formed, and an η-type impurity such as POCh (triomoperoxide) may be used from the opening portion. The gas of (phosphorus) is carried out by gas phase diffusion. Further, as the n-type impurity, for example, arsenic or antimony may be used in addition to phosphorus. Further, the η+ layer 3 can be formed by, for example, introducing an n-type impurity onto the surface of the ruthenium-type substrate 2 by an ion implantation method, an ion doping method, or the like, followed by annealing or the like. Next, the oxidized 143168.doc -28- 201015731 formed on the surface of the light incident side of the p-type ruthenium substrate 2 contains the planer 5. Here, regarding the crucible 5, for example, the cerium ions may be ion-implanted in the oxidized oxide film 6 formed on the surface on the light incident side of the p-type ruthenium substrate 2, whereby the ruthenium oxide film 6 contains the planer 5. Next, annealing of the p-type germanium substrate 2 is performed. Here, the annealing of the p-type germanium substrate 2 can be performed, for example, by annealing the p-type germanium substrate 2 after the above-described germanium ion implantation at a temperature of, for example, 800 ° C to 1000 ° C. Thereby, the planer 5 in the oxidized stone film 6 can be segregated to the interface with the surface on the light incident side of the P-type ruthenium substrate 2. The planer 5 segregated to the interface between the yttrium oxide film 6 and the 1) type ruthenium substrate 2 is positively ionized by releasing electrons to the P-type ruthenium substrate 2, and thus is connected to the oxidized film 6 The surface inversion layer 4 is formed on the surface of the light incident side of the p-type dream substrate 2. Next, the metal electrode 8 is formed on the surface on the light incident side of the p-type germanium substrate 2. Here, the metal electrode 8 can be formed by, for example, providing an opening portion at a portion of the ruthenium oxide film 6 corresponding to a portion where the metal electrode 8 is formed, and vapor-depositing the metal using a mask or the like. Specific shape, etc. Next, the back surface electrode 7 is formed on the back surface of the p+ layer 1 of the P-type substrate 2. Here, the back electrode 7 can be formed by, for example, vaporizing a metal or the like on the back surface of the p+ layer 1 of the p-type germanium substrate 2. Finally, after the formation of the metal electrode 8 and the back electrode 7, the p-type etched substrate 2 is annealed, and an example of the photoelectric conversion device of the present embodiment having the above configuration is produced. Here, the annealing of the p-type germanium substrate 2 can be performed, for example, by exposing the P-type germanium substrate 2 to a hydrogen atmosphere at a temperature of 350 ° C to 50 (the temperature of TC.) The above-described configuration of the above configuration Photoelectric conversion 143168.doc -29- 201015731 In the apparatus, the 'yttrium oxide film 6 is in contact with the surface of the light incident side of the p-type germanium substrate 2' by the light incident side of the tantalum oxide film 6 and the p-type germanium substrate 2. The surface inversion layer 4 is formed on the surface on the light incident side of the p-type germanium substrate 2 at the interface of the surface. Therefore, in the photoelectric conversion device of the present embodiment configured as described above, The second layer of the fixed charge and the solar cell disclosed in the patent document 不含 having no fixed charge between the semiconductor surface are more likely to induce a negative density on the surface inversion layer 4 at a higher density. The electric charge improves the function of the n-type semiconductor, so that the recombination of the carrier on the surface on the light incident side of the p-type dream substrate 2 can be suppressed, whereby the characteristics of the photoelectric conversion device such as photoelectric conversion efficiency are improved. Also 'on the p-type 矽 substrate 2 On the surface on the light incident side, a surface inversion layer 4 functioning as an n-type semiconductor is provided instead of the n + layer 3 which is an absorption source of short-wavelength light, whereby short-wavelength light is compared with the n+ layer 3 Further, the absorption of the photoelectric conversion device can be further improved, and the photoelectric conversion device of the present embodiment can be further improved. The amount of segregation of the planer on the surface of the light incident side of the substrate 2 controls the density of negative charges (electrons) induced on the surface inversion layer 4. In particular, as in the present embodiment, When the ruthenium ion in the film 6 is implanted and annealed to segregate the planer to the interface between the yttrium oxide film 6 and the p-type ruthenium substrate 2, the ion-repellent cloth on the surface reversal layer 4 for obtaining an optimum negative charge density is used. Since the tolerance of the planting amount is wide, it is possible to provide a photoelectric conversion device having a stable quality and high characteristics of 143168.doc -30-201015731. Further, in the photoelectric conversion device of the present embodiment configured as described above, the p-type is made Light incident on the substrate 2 The interface energy level on the surface of the side is terminated by the negative charge induced on the surface inversion layer 4, whereby the recombination of the carrier on the interface level of the surface on the light incident side of the p-type germanium substrate 2 can be suppressed, thereby Further, the characteristics of the photoelectric conversion device such as photoelectric conversion efficiency can be further improved. Further, in the above description, the P-type germanium substrate 2 is used as the semiconductor layer, but i is not limited thereto, and for example, crystallized stone may be used. A semiconductor layer such as a semiconductor such as a crystal slab, a microcrystalline stone, or a cerium other than a cerium; in addition, a crystal slab contains a single crystal, a polycrystalline stone, or a mixture of a single crystal slab and a polycrystalline stone. Further, in the above description, the case where the single crystal germanium is contained in the p-type germanium substrate 2 has been described. However, for example, when a semiconductor layer containing amorphous germanium is used instead of the P substrate 2, it is preferable. The photoelectric conversion device of this embodiment was produced without performing a warm-up process after forming the oxidized stone film 6 containing the planer 5. Further, in the above, the ruthenium oxide film 6 is used as the dielectric film, but it is of course not limited thereto, and for example, it may be selected from the group consisting of oxidized cerium oxide, lanthanum oxynitride, and cerium nitride. At least one. Further, as the dielectric film, a dielectric film having a band gap of 4.2 eV or more is preferably used. For example, most of the sunlight is composed of a light having a wavelength of 300 nm or more. Therefore, when a solar film having a band gap of 4.2 ev or more is used to make sunlight incident, it is possible to suppress sunlight having a wavelength of 300 nm or more. The electric film is absorbed, so that the loss of conversion is reduced, so the characteristics of the photoelectric conversion device tend to increase step by step. 143168.doc 31 201015731 ^ ^ β丨, ''丨~一丨f sentence take two Although the case of the fixed charge impurity is described, it is not limited thereto, and for example, it may be composed of, for example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, strontium, and barium. In the photoelectric conversion device of the present embodiment configured as described above, the P-type and the n-type conductivity type are also changed. In this case, an impurity which becomes a negative charge can be used. Instead of an impurity that becomes a positive fixed charge, as an impurity that becomes a negative fixed charge, for example, the inclusion may be selected from

鋁、鎵、銦、鉑、氟化富勒烯、氧化富勒烯、氟、氣、漢 及碘所組成之群中之至少一種者。 ，、 再者，成為正的固定電荷之雜質及成為負的固定電荷之 雜質亦可分別以氧化物之狀態而含有。At least one of the group consisting of aluminum, gallium, indium, platinum, fluorinated fullerene, oxidized fullerene, fluorine, gas, han, and iodine. Further, impurities which become positive fixed charges and impurities which become negative fixed charges may be contained in the state of oxides, respectively.

於上述構成之本實施形態之光電轉換裝置+，較好 的疋上述雜質存在最多之部位係位於從作為半導體層之p 型石夕基板2與作為介電質膜之氧化石夕膜6之界面起在相對 於=界面而垂直之方向上朝著作為半導體層之p型石夕基板2 進5 nm之區域、與朝著作為介電質膜之氧化石夕膜6側 月J進5 nm之區域之間的區域上。於此情形時 成之本實施形態之光電轉換裝置之特性有進一步提高^ 向。 盥即’於本實施形態之光電轉換裝置中，只要介電質膜在 ’、半導體層之界面附近含有成為正或負的較電荷之雜質 二可且只要該雜f之至少_部分係存在於從半導體層與 1電質膜之界面起’在相對於該界面而垂直之方向上朝著 I43I68.doc -32· 201015731 半導體層側前進5 nm之區域、與朝著介電質膜側前進5 nm 之區域之間的區域上即可。 又’於以上所述中，當然可使P型矽基板2之光入射側之 氧化矽膜6作為抗反射膜而發揮功能，亦可於氧化矽膜6之 表面形成紋理（texture)結構及/或蛾眼（moth_eye)結構等。 又’如上所述’於上述構成之本實施形態之光電轉換裝 置中，亦可調換η型與p型之導電型。再者，當上述構成之 本實施形態之光電轉換裝置中已調換η型與ρ型之導電型之 ❹ 情形時，正與負的電荷極性亦會被調換。 又’於上述構成之本實施形態之光電轉換裝置中，亦可 不形成Ρ +層1。 &lt;實施形態2&gt; 圖2(a)中表示本發明之光電轉換裝置之另一例的光入射 側之表面之俯視示意圖。又，圖2(b)中表示沿著圖2(勾之 2b-2b的剖面示意圖，圖2(c)中表示沿著圖2(a)i2c2c之剖 ▲ 面示意圖。 參 此處’圖2(a)〜圖2(c)所示之構成之本實施形態之光電轉 換裳置的特徵在於：在？型矽基板2之光入射側之表面之整 個面上’形成有透明導電膜9作為與n+層3相接之電極。 由於形成為如本實施形態所述之構成，故可使光自 矽基板2之光入射側之表面之整個面進行入射，從而可進 一步加強因電極之低電阻化而引起的光電轉換裝置之光電 轉換效率等的特性之提高。又，由於無需電極之圖案化步 驟及電極之圖案化用之遮罩，故亦可降低製造成本及提高 143168.doc •33· 201015731 製造效率。 再者，作為透明導電膜9,可使用例如包含肋卿㈣ Μ㈤心，氧化銦錫）、Wdndium 〇xide，氧化銦）、 Win Oxide，氧化錫）或者2〇細〇仙，氧化辞）之層 之單層或複數層的積層體。 而且透明導電膜9可藉由如下方式等而形成：例如以 使n+層3之至少一部分露出之方式於氧化石夕膜“—部分上 設置開口部，並且XU0 # u φ ^ 亚且以自其上方覆蓋之方式來蒸鍍包含 IT0 10、TO或者z〇等之透明導電膜9。 本實施形態中之上述以外之說明與實施形態i相同因 而在此省略其說明。 &lt;實施形態3&gt; 圖3(a)中表示本發明之光電轉換裝覃之另一例的光入射 侧之表面之俯視示意圖。又’圖3(b)中表示沿著圖3(幻之 3b-3b之剖面示意圖’圖3(c)中表示沿著圖3(a)i3c3c之剖 面示意圖。 此處，圖3(a)〜圖3(c)所示之構成之本實施形態的光電轉 換裝置的特徵在於：在p型矽基板2之光入射側之表面上， 以梳形狀而形成有作為與n+層3相接之電極的透明導電膜 9 〇 由於形成為如本實施形態所述之構成，故可減少形成於 p型石夕基板2之光入射側之表面上的透明導電膜9之表面之 面積’故可抑制因透明導電膜9而引起的光之反射或吸 收《藉此，於本實施形態之光電轉換裝置中，與實施形態 143168.doc • 34· 201015731 2之構成之光電轉換裝置相比，可進一步加強光電轉換效 率等之特性之提高。 本實施形態中之上述以外之說明與實施形態1及實施形 態2相同，因而在此省略其說明。 &lt;實施形態4&gt; 圖4(a)中表示本發明之光電轉換裝置之另一例的光入射 側之表面之俯視示意圖。又，圖4(b)中表示沿著圖4(a)之 4b-4b的剖面示意圖，圖4(c)中表示沿著圖4(a)之4c-4c的剖 面示意圖。 此處’圖4(a)〜圖4(c)所示之構成之本實施形態的光電轉 換裝置的特徵在於：在p型矽基板2之光入射側之表面上， 形成有梳形狀之金屬石夕化物10作為與n+層3相接之電極。 由於形成為如本實施形態所述之構成，因而藉由使用一 直以來公知之自行對準&gt;6夕化物化（SALICIDE)製程而可於梳 形狀之n+層3之表面上形成梳形狀之金屬矽化物1〇，故無 而電極之圖案化步驟及電極之圖案化用之遮罩，從而可降 低製造成本及提高製造效率。 再者，作為金屬矽化物10，只要為包含至少一種任意金 屬與石夕之化合物者便可使用而並不特別限定，例如，可使 用鈦矽化物（TiSix(x与0.5〜2))、铒矽化物（ErSix(x_〇 5〜 2))、鏡矽化物（YbSix(x#0.5〜2))、銘矽化物（PtSix(x与〇 5〜 U)、錄矽化物（NixSi(x与0.5〜2))或者鈷矽化物（c〇xSi (X .0.5〜2))等。又，當如使用非晶;g夕等代替p型石夕基板2般 之需要低溫製程之情形時，亦可藉由使用NixSi(x%卜2)、 143168.doc •35· 201015731In the photoelectric conversion device + of the present embodiment having the above-described configuration, it is preferable that the portion where the impurities are most present is located at the interface between the p-type slab substrate 2 as the semiconductor layer and the oxidized oxide film 6 as the dielectric film. In the direction perpendicular to the interface and perpendicular to the interface, the p-type lithography substrate of the semiconductor layer is 2 nm 5 nm, and the oxidized stone film 6 is applied to the dielectric film. On the area between the areas. In this case, the characteristics of the photoelectric conversion device of the present embodiment are further improved. In the photoelectric conversion device of the present embodiment, as long as the dielectric film contains a positive or negative relatively charged impurity in the vicinity of the interface of the semiconductor layer, as long as at least a portion of the impurity f exists in From the interface between the semiconductor layer and the 1-electroless film, 'the direction perpendicular to the interface is 5 nm toward the semiconductor layer side of the I43I68.doc -32·201015731 and the direction toward the dielectric film side 5 The area between the areas of nm is sufficient. Further, in the above description, of course, the ruthenium oxide film 6 on the light incident side of the P-type ruthenium substrate 2 functions as an anti-reflection film, and a texture structure can be formed on the surface of the ruthenium oxide film 6 and/or Or moth eye (moth_eye) structure, etc. Further, as described above, in the photoelectric conversion device of the present embodiment configured as described above, the n-type and p-type conductivity types can be replaced. Further, in the case where the n-type and p-type conductivity types are replaced in the photoelectric conversion device of the above-described configuration, the positive and negative charge polarities are also exchanged. Further, in the photoelectric conversion device of the embodiment configured as described above, the Ρ + layer 1 may not be formed. &lt;Embodiment 2&gt; Fig. 2(a) is a plan view showing the surface on the light incident side of another example of the photoelectric conversion device of the present invention. 2(b) is a cross-sectional view taken along line 2b-2b of FIG. 2, and FIG. 2(c) is a cross-sectional view taken along line 2(a) and i2c2c of Fig. 2(a). The photoelectric conversion panel of the present embodiment having the configuration shown in (a) to (c) of FIG. 2 is characterized in that a transparent conductive film 9 is formed on the entire surface of the surface on the light incident side of the ?-type substrate 2 as The electrode which is in contact with the n+ layer 3 is formed as described in the embodiment, so that light can be incident from the entire surface of the surface on the light incident side of the substrate 2, thereby further enhancing the low resistance of the electrode. The characteristics of the photoelectric conversion efficiency and the like of the photoelectric conversion device are improved. Moreover, since the masking step of the electrode and the mask for patterning the electrode are not required, the manufacturing cost can be reduced and the 143168.doc • 33· 201015731 Manufacturing efficiency. Further, as the transparent conductive film 9, for example, it may be oxidized by using rib (4) Μ (5), indium tin oxide, Wdndium 〇xide, indium oxide, Win Oxide, tin oxide, or 2 〇 〇 , a layer of a single layer or a plurality of layers. Further, the transparent conductive film 9 can be formed by, for example, providing an opening portion in a portion of the oxidized stone film in such a manner that at least a part of the n+ layer 3 is exposed, and XU0 #u φ ^ The transparent conductive film 9 including IT0 10, TO or z〇 is deposited by the above method. The descriptions other than the above in the present embodiment are the same as those in the embodiment i, and thus the description thereof will be omitted. <Embodiment 3> 3(a) is a schematic plan view showing the surface of the light incident side of another example of the photoelectric conversion device of the present invention. Further, FIG. 3(b) shows a cross-sectional view along FIG. 3 (the 3b-3b of the magical figure). 3(c) is a schematic cross-sectional view taken along line 3(a) and i3c3c. Here, the photoelectric conversion device of the present embodiment having the configuration shown in Figs. 3(a) to 3(c) is characterized by: On the surface on the light incident side of the ruthenium substrate 2, the transparent conductive film 9 作为 which is an electrode which is in contact with the n+ layer 3 is formed in a comb shape, and is formed as described in the embodiment, so that it can be reduced in formation. The surface of the transparent conductive film 9 on the surface of the light incident side of the p-type substrate In the photoelectric conversion device of the present embodiment, the photoelectric conversion device of the embodiment 143168.doc • 34·201015731 2 can be suppressed in the photoelectric conversion device of the embodiment. The improvement of the characteristics of the photoelectric conversion efficiency and the like can be further enhanced. The descriptions other than the above in the present embodiment are the same as those in the first embodiment and the second embodiment, and thus the description thereof will be omitted. <Embodiment 4> Fig. 4 (a Fig. 4(b) is a schematic plan view showing the surface of the light incident side of another example of the photoelectric conversion device of the present invention. Fig. 4(b) is a cross-sectional view taken along line 4b-4b of Fig. 4(a), Fig. 4(c) The middle portion of the photoelectric conversion device of the present embodiment having the configuration shown in Fig. 4(a) to Fig. 4(c) is characterized in that: On the surface on the light incident side of the ruthenium substrate 2, a comb-shaped metal lithium 10 is formed as an electrode that is in contact with the n+ layer 3. Since it is formed as described in the embodiment, it is conventionally used. Known to align yourself &gt;6 夕化化化(SALICIDE) The comb-shaped metal bismuth compound 1 形成 can be formed on the surface of the n+ layer 3 of the comb shape, so that the patterning step of the electrode and the mask for patterning the electrode are eliminated, thereby reducing manufacturing cost and improving manufacturing efficiency. Further, the metal halide 10 is not particularly limited as long as it contains at least one compound of any of the metals and the compound of the shovel. For example, titanium telluride (TiSix (x and 0.5 to 2)) can be used. Telluride (ErSix (x_〇5~ 2)), mirror telluride (YbSix(x#0.5~2)), Ming telluride (PtSix (x and 〇5~ U), recorded telluride (NixSi(x And 0.5~2)) or cobalt telluride (c〇xSi (X.0.5~2)) and the like. Further, when a low temperature process is required as in the case of using amorphous, g, or the like instead of the p-type slab substrate 2, NixSi (x%b 2), 143168.doc • 35· 201015731 can also be used.

CoxSi(x与1〜2)而於例如400°C以下之低溫下形成金屬碎化 物10 〇 本實施形態中之上述以外之說明與實施形態1〜實施形態 3相同，因而在此省略其說明。 〈實施形態5&gt; 圖5中表示本發明之光電轉換裝置之另一例之剖面示意 圖。圖5所示之構成之本實施形態的光電轉換裝置具有自 光入射側起依序積層第1光電轉換層51、.第2光電轉換層 52、及第3光電轉換層53所成之積層結構。 此處’第1光電轉換層51包含作為第1半導體層之第1非 晶矽層2a、及作為表面介電質膜之氧化矽膜6,該表面介 電質膜係以與第1非晶石夕層2 a之光入射側之表面相接之方 式所設置的介電質膜。 又’氧化矽膜6在與第1非晶矽層2a之界面附近，含有作 為成為正的固定電荷之雜質之鉋此處，鉋5在與第1非 晶石夕層2a之光入射側之表面之界面附近經離子化而成為正 的固定電荷，因此在與氧化矽膜6相接之第1非晶矽層2&amp;之 光入射側之表面之至少一部分區域上，會誘發作為n型半 導體而發揮功能之表面反轉層4。 又’在第1非晶矽層2a之與光入射側之表面成為相反側 之表面的背面上，形成有作為第1雜質含有層的p+層1，其 含有與上述表面反轉層4為相反導電型之第1雜質（本實施 形態中為p型雜質）。 又’第2光電轉換層52含有作為第2半導體層之第2非晶 143168.doc 201015731 碎層2b。 此處，於第2非晶矽層2b之光入射側之表面上，形成有 作為第2雜質含有層的n+層3,其含有與上述第1雜質為相 反導電型之第2雜質（本實施形態中為n型雜質 又，在第2非晶矽層2b之與光入射侧之表面成為相反侧 之表面的背面上，形成有作為第3雜質含有層的？+層1，其 含有與上述第2雜質為相反導電型之第3雜質（本實施形態 中為P型雜質）。 _ 又，第3光電轉換層53含有作為第3半導體層之第3非晶 碎層2c。 此處，於第3非晶矽層2c之光入射側之表面上，形成有 作為第4雜質含有層的n+層3,其含有與上述第3雜質為相 反導電型之第4雜質（本實施形態中為η型雜質）。 又，在第3非晶矽層2c之與光入射側之表面成為相反側 之表面的背面上，形成有作為第5雜質含有層的叶層1 ,其 ❹ 含有與上述第4雜質為相反導電型之第5雜質（本實施形態 中為P型雜質）。 並且’將在上述第1光電轉換層51之與光入射侧之表面 為相反侧之背面上所形成之P +層i、及在上述第2光電轉換 層52之光入射側之表面上所形成之n+層3加以接合。又， 將在上述第2光電轉換層52之與光入射側之表面為相反側 之背面上所形成之P+層1、及在上述第3光電轉換層53之光 入射側之表面上所形成之n+層3加以接合。藉由該等接合 而構成自光入射側起依序積層第1光電轉換層51、第2光電 143168.doc -37· 201015731 轉換層52及第3光電轉換層53所成之積層結構。 又，以與上述積層結構之第〗光電轉換層51之第〗非晶矽 層2a之光入射側的表面之一部分相接之方式而形成作為表 面電極之透明導電膜9 ’並且以與上述積層結構之第3光電 轉換層53之第3非晶矽層2。之背面的P+層1相接之方式而形 成j如匕含鋁等之背面電極7。此處，透明導電膜9係通過 形成於氧化矽膜6上之開口部而與第i非晶矽層。之光入射 側之表面相接。 再者，在透明導電膜9與第！非晶矽層23之大部分之接觸 #上，因肖特基能障（Schottky barrier)而難以實現導通， 從而難以取出光電轉換裝置令所生成之載體。然而，與第 1非明石夕層2a之光入射側之表面接觸的透明導電膜9之端部 即邊緣（edge)部11係與表面反轉層4接觸，於該邊緣部u 上’由於肖特基能障調變效應而使肖特基能障降低，接觸 電阻降低’從而可進行歐姆連接，因此可更容易地將光電 轉換裝置中所生成之載體取出至外部。 以下’對圖5所示之構成的本實施形態之光電轉換裝置 之製造方法之一例進行說明。首先，於背面電極7之表面 上形成第3光電轉換層53。此處，第3光電轉換層53可藉由 如下方式而形成：例如以CVD(Chemical Vapor Deposition) 法等’於背面電極7之表面上形成摻雜有p型雜質之p型非 晶石夕膜以形成p+層1之後，停止p型雜質之摻雜從而形成非 摻雜之非晶矽膜，以形成第3非晶矽層2c，進而形成摻雜 有η型雜質之n型非晶矽膜以形成n+層3。 143l68.do« •38· 201015731 又，由P型雜質之摻雜而形成p型非晶石夕膜係可藉由例如 在非晶石夕膜之原料氣體中混入有含口型雜質之搀雜氣體之 狀態下成膜非晶石夕膜來推γ $ 膘來進仃。再者，作為ρ型雜質，可使 用例如硼、銦或銘等。 又，由η型雜質之摻雜而形成η型非晶碎媒係可藉由例如 在非晶石夕膜之原料氣體中混人有^型雜質之摻雜氣體之 狀態下成膜非晶㈣來進行。再者，作為&quot;雜質，可使 用例如磷、砷或銻等。CoxSi (x and 1 to 2) is formed at a low temperature of, for example, 400 ° C or lower. The description of the present embodiment is the same as that of the first embodiment to the third embodiment, and thus the description thereof will be omitted. <Embodiment 5> Fig. 5 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention. The photoelectric conversion device of the present embodiment having the configuration shown in FIG. 5 has a laminated structure in which the first photoelectric conversion layer 51, the second photoelectric conversion layer 52, and the third photoelectric conversion layer 53 are sequentially laminated from the light incident side. . Here, the first photoelectric conversion layer 51 includes a first amorphous germanium layer 2a as a first semiconductor layer and a tantalum oxide film 6 as a surface dielectric film, which is first amorphous. The dielectric film provided in such a manner that the surface of the incident side of the light-emitting layer 2a is in contact with each other. Further, in the vicinity of the interface with the first amorphous germanium layer 2a, the tantalum oxide film 6 contains an impurity which is a positive fixed charge, and the planer 5 is on the light incident side with the first amorphous rock layer 2a. Since the interface near the surface is ionized and becomes a positive fixed charge, at least a part of the surface on the light incident side of the first amorphous germanium layer 2 & which is in contact with the tantalum oxide film 6 is induced as an n-type semiconductor. The surface inversion layer 4 functions as a function. Further, on the back surface of the surface on the opposite side to the surface on the light incident side of the first amorphous germanium layer 2a, a p+ layer 1 as a first impurity containing layer is formed, which is opposite to the surface inversion layer 4 The first impurity of the conductivity type (p-type impurity in the present embodiment). Further, the second photoelectric conversion layer 52 contains the second amorphous layer 143168.doc 201015731 as the second semiconductor layer. Here, on the surface on the light incident side of the second amorphous germanium layer 2b, an n+ layer 3 as a second impurity containing layer is formed, and the second impurity having a conductivity type opposite to that of the first impurity is formed (this embodiment) In the form of an n-type impurity, a ++ layer 1 as a third impurity-containing layer is formed on the back surface of the surface of the second amorphous germanium layer 2b opposite to the surface on the light incident side. The third impurity is a third impurity of the opposite conductivity type (P-type impurity in the present embodiment). Further, the third photoelectric conversion layer 53 contains the third amorphous fracture layer 2c as the third semiconductor layer. On the surface on the light incident side of the third amorphous germanium layer 2c, an n+ layer 3 as a fourth impurity-containing layer is formed, and a fourth impurity having a conductivity opposite to that of the third impurity is included (in the present embodiment, η Further, on the back surface of the surface of the third amorphous germanium layer 2c opposite to the surface on the light incident side, a leaf layer 1 as a fifth impurity-containing layer is formed, and the fourth layer and the fourth layer are formed. The impurity is the fifth impurity of the opposite conductivity type (P-type impurity in the present embodiment). And 'will be on The P + layer i formed on the back surface opposite to the surface on the light incident side of the first photoelectric conversion layer 51 and the n + layer 3 formed on the surface on the light incident side of the second photoelectric conversion layer 52 are applied. Further, the P+ layer 1 formed on the back surface opposite to the surface on the light incident side of the second photoelectric conversion layer 52 and the surface on the light incident side of the third photoelectric conversion layer 53 are placed. The formed n+ layer 3 is bonded, and the first photoelectric conversion layer 51, the second photoelectric 143168.doc-37·201015731 conversion layer 52, and the third photoelectric conversion layer 53 are sequentially formed from the light incident side by the bonding. Further, a transparent conductive film 9 as a surface electrode is formed so as to be in contact with one of the surfaces on the light incident side of the first amorphous germanium layer 2a of the photoelectric conversion layer 51 of the laminated structure. Further, a back electrode 7 such as yttrium-containing aluminum or the like is formed so as to be in contact with the P+ layer 1 on the back surface of the third amorphous germanium layer 2 of the third photoelectric conversion layer 53 of the above-mentioned laminated structure. Here, transparent The conductive film 9 passes through the opening formed on the yttrium oxide film 6 and the ith The surface of the wafer on the incident side of the wafer is in contact with each other. Further, in the contact # of the transparent conductive film 9 and the majority of the amorphous layer 23, it is difficult to realize due to the Schottky barrier. When it is turned on, it is difficult to take out the carrier formed by the photoelectric conversion device. However, the edge portion 11 of the transparent conductive film 9 which is in contact with the surface on the light incident side of the first non-Alum layer 2a is opposite to the surface. The transfer layer 4 contacts, on the edge portion u, the Schottky barrier is reduced due to the Schottky barrier modulation effect, and the contact resistance is lowered, thereby making an ohmic connection, so that the photoelectric conversion device can be more easily The generated vector was taken out to the outside. Hereinafter, an example of a method of manufacturing the photoelectric conversion device of the present embodiment having the configuration shown in Fig. 5 will be described. First, the third photoelectric conversion layer 53 is formed on the surface of the back surface electrode 7. Here, the third photoelectric conversion layer 53 can be formed by, for example, forming a p-type amorphous austenite film doped with a p-type impurity on the surface of the back surface electrode 7 by a CVD (Chemical Vapor Deposition) method or the like. After the p+ layer 1 is formed, doping of the p-type impurity is stopped to form an undoped amorphous germanium film to form a third amorphous germanium layer 2c, thereby forming an n-type amorphous germanium film doped with an n-type impurity. To form n+ layer 3. 143l68.do« •38· 201015731 Further, the formation of a p-type amorphous austenite film by doping with a P-type impurity can be carried out, for example, by mixing a impurity containing a smear-type impurity into a raw material gas of an amorphous stone film. In the state of gas, a film of amorphous austenite is formed to push γ $ 膘 to enter. Further, as the p-type impurity, for example, boron, indium or methane can be used. Further, the n-type amorphous dispersing agent formed by the doping of the n-type impurity can be formed into a film amorphous state by, for example, mixing a dopant gas of a type of impurity in a raw material gas of the amorphous stone film (4). Come on. Further, as the &quot;impurities, for example, phosphorus, arsenic or antimony can be used.

者，作為第3光電轉換層53，使用了 —結構之非晶 石夕，然而亦可使用於表面形成有以層之？型之單晶或多晶 矽。於此情形時，會進一步提高轉換效率。 其次，於第3光電轉換層53之表面上形成第2光電轉換層 =此處’第2光電轉換層52亦與第3光電轉換㈣同樣地 可藉由如下方式而形成：例如以CVD法等，於第3光電轉 換層53之表面上形成摻雜有p型雜f &amp;型非晶@膜以形成 P+層1之後，停止p型雜質之摻雜從而形成非摻雜之非晶矽 膜，以形成第2非晶矽層2b，進而形成摻雜有11型雜質之n 型非晶碎膜以形成η+層3。 接下來，於第2光電轉換層52之表面上形成第1光電轉換 層51。此處，第1光電轉換層51例如可藉由如下方式而形 成。首先，以CVD法等，於第2光電轉換層52之表面上形 成摻雜有ρ型雜質之ρ型非晶矽膜以形成p+層】之後，停止ρ 型雜質之摻雜從而形成非摻雜之非晶矽膜，以形成第i非 阳矽層2a。其後，於第1非晶矽層2a之表面上形成含有铯5 143168.doc •39- 201015731 之氧化矽膜6,藉此可形成第丨光電轉換層5ι。 此處’含有铯5之氧切膜6可藉由例如在cvd法中將絶 蒸氣等之含有铯之氣體與氧切之原料—同導人而形成。 又，關於绝5’例如可在形成於第】非晶石夕層h之光入射側 之表面上的氧化矽膜6中將绝離子進行離子佈植，藉以使 氧化石夕膜6中含有已離子化之铯5β又，在非晶石夕層h之表 面塗佈例如氣化铯水溶液或氫氧化鉋水溶液等之含有铯之 溶液並乾燥之後，例如以CVD法等而形成氧化矽膜6，藉 此可在非晶矽層2a與氧化矽膜6之界面附近配置铯5。 最後，在第1光電轉換層51之光入射側之表面上形成透 明導電膜9,藉此製作圖5所示之構成之本實施形態的光電 轉換裝置。此處，透明導電膜9可藉由如下方式等而形 成.例如以使第1非晶矽層2a之光入射侧之表面之至少一 邛刀露出之方式於氧化矽膜6之一部分上設置開口部並 且以自其上方覆蓋之方式來濺鍍或蒸艘包含IT〇、I〇、T〇 或者ZO等之透明導電膜9。 於由以上方式所製作之上述構成之本實施形態的光電轉 換裝置中，氧化矽膜6與第1非晶矽層2a之光入射側之表面 相接，藉由在氧化矽膜6與第1非晶矽層2a之光入射侧之表 面之界面上已離子化之鉋，而於第}#晶矽層2&amp;之光入射 側之表面上形成表面反轉層4。 因此，於上述構成之本實施形態之光電轉換裝置中，與 設置有含固定電荷之第二層、及在與半導體表面之間不含 固定電荷之第一層之構成的專利文獻丨所揭示之太陽電池 143168.doc -40- 201015731 相比’更容易在表面反轉層4上高密度地誘發負電荷，使 作為n型半導體之功能得以提高，故可抑制第1非晶石夕層2a 之光入射側之表面上之載體的再結合等，藉此，光電轉換 效率等之光電轉換裝置之特性會得到提高。 又’在第1非晶矽層2a之光入射側之表面上，代替成為 短波長光之吸收源的n+層而設置有作為η型半導體發揮功 能的表面反轉層4’藉此，與η+層相比，更可抑制短波長 之光的吸收，因此可使光電轉換效率等之光電轉換裝置之 特性得到進一步提高。 又’於上述構成之本實施形態之光電轉換裝置中，可根 據氧化石夕臈6與第1非晶石夕層2a之光入射側之表面之界面上 的铯之偏析量，來控制表面反轉層4上所誘發之負電荷之 密度。 又，於上述構成之本實施形態之光電轉換裝置中，使第 1非晶石夕層2a之光入射侧之表面上的界面能階因表面反轉 層4上所誘發之負電荷而終止’藉此可抑制於第1非晶石夕層 2a之光入射側之表面之界面能階上的載體之再結合，從而 可使光電轉換效率等之光電轉換裝置之特性得到進一步提 南。 又’如本實施形態之光電轉換裝置般，當在與表面電極 相接之半導體層中使用有非晶矽時，雜質之活化率會變 低’故而難以在與表面電極相接之半導體層上形成高濃度 之雜質掺雜層，但於上述構成之本實施形態之光電轉換裝 置中’藉由氧化矽膜6中之已離子化之铯而可於第1非晶矽 143168.doc •41· 201015731 層2a之表面上形成表面反轉層4,從而可使表面反轉層植 透明導電膜9接觸，因此無需形成高濃度之雜質摻雜層。 、於以上所述中，作為第1半導體層、第2半導體層、 及第3半導體層’分別使用了非晶矽，但並不限定於此， 作為第1半導體層、第2半導體層、及第3半導體層亦可 刀別使用例如結曰曰矽、非晶矽、微晶矽或者矽以外之其他 種類之半導體等的半導體層。再者結晶矽中包含單晶 夕夕曰曰石夕、或者單晶石夕與多晶矽之混合體等。 又，當第1半導體層、第2半導體層、及第3半導體層中 分別使用有結晶發時’第！光電轉換層51、第2光電轉換層 52、及第3光電轉換層53之積層結構例如可由以下方式而 製作。首先，製作兩塊矽基板（雙面摻雜矽基板），其係於 結晶矽之一方之表面上使p型雜質擴散而形成有p+層丄，且 於結晶矽之另一方之表面上使η型雜質擴散而形成者n+層 3，並且製作一塊矽基板（單面摻雜矽基板），其係僅於結晶 矽之一方之表面上使p型雜質擴散而形成有p +層工，且於結 B曰矽之另一方之表面上不使雜質擴散從而未形成n+層 3。繼而，使一塊雙面摻雜矽基板之n+層3黏合於單面摻雜 矽基板之p+層1，並且使另一塊雙面摻雜矽基板之11+層3黏 合於該雙面摻雜矽基板之p+層i，藉此可製作出上述積層 結構。 其後’於露出之單面摻雜矽基板之表面上配置鉋5之 後’例如以熱氧化法、CVD法、ALD法、RTO(Rapid Thermal Oxidation ’快速熱氧化）法、或者電漿氧化法等而於露出 143168.doc •42· 201015731 之單面摻雜矽基板之表面之一部分上形成氧化矽膜繼 而，利用例如濺鍍法、CVD法或溶膠凝膠法（s〇l_Gel method)等而形成包含IT〇、1〇、τ〇或者z〇等之透明導電 膜9，並與和該透明導電膜9為相反側之上述積層結構之背 面的P型層相接而形成背面電極7，藉此可製作本實施形態 之光電轉換裝置。再者，關於鉋5,亦可在形成氧化矽膜6 之後，於氧化矽膜6中將鉋離子進行離子佈植，其後進行 退火，藉此使其偏析到氧化矽膜6與單面摻雜矽基板之界 Φ 面上。 如此一來’當藉由氧化矽膜6之退火而使已離子化之铯5 偏析到氧化矽膜6與第1半導體層之界面附近時，表面反轉 層4上之用以獲得最佳的電子密度之鉋離子佈植量之容限 較廣，因此可提供一種品質穩定且特性高的光電轉換裝 置。又’亦可於形成相較所期望之膜厚更厚之氧化矽膜6 之後’於氧化矽膜6中將鉋離子進行離子佈植，繼而進行 藝退火，藉此使铯偏析到氧化矽膜6與單面換雜矽基板之界 面上，其後進行利用氫氟酸水溶液等之處理或者反應性離 子餘刻等’以使氧化石夕膜6變薄至所期望之膜厚為止。 又，於上述構成之本實施形態之光電轉換裝置中，較好 的是靠近光入射側之第1半導體層之帶隙為遠離光入射側 之第2半導體層之帶隙以上。又，更好的是靠近光入射侧 之第2半導體層之帶隙為遠離光入射侧之第3半導體層之帶 隙以上。進而，更好的是靠近光入射側之第1半導體層之 帶隙為遠離光入射側之第2半導體層之帶隙以上，且靠近 U3168.doc -43- 201015731 光入射側之第2半導體層之帶隙為遠離光入射側之第3半導 體層之帶隙以上（第3半導體層之帶隙$第2半導體層之帶 隙S第1半導體層之帶隙）。由於形成為如上所述之可自光 入射側起依序吸收短波長光至長波長光的積層結構，故而 入射至本實施形態之光電轉換裝置中之光的吸收量會變 大’因此光電轉換效率等之本實施形態之光電轉換裝置的 特性有提高之傾向。 再者，作為用以形成上述第3半導體層之帶隙$第2半導 體層之帶隙^第1半導體層之帶隙之關儀的半導體層之構 成，可舉出例如於第i半導體層中使用非晶碳化矽（Sic)、 於第2半導體層中使用非晶♦、絲第3半導體層中使用微 晶矽之構成。 又作為用以形成上述第3半導體層之帶隙$第2半導體 層之帶隙各第i半導體層之帶隙之關係的半導體層之其他 構成’可舉出例如於第4導體層中使用非晶碳化石夕、於 第2半導體層中使用非晶石夕、且於第3半導體層中使用非晶 矽鍺（SiGe)之構成。 又，較好的是第i半導體層之厚度較第lJf導體層内之載 體擴散長度更薄。於此情形時，可有效抑制^半導體層 内之載體之再結合，並且藉由如本實施形態般形成為積層 結構，亦可提高所入射之光被吸收之概率。 較好的是第2半導體層之厚度較第2半導體層 入 體擴散長度更薄。於此情形時，可古 ^ ^ 了有效抑制第2半導體層 内之載體之再結合，並且藉由如太奋 猎由如本實施形態般形成為積層 143I68.doc -44 - 201015731 結構，亦可提高所入射之光被吸收之概率。 又’較好的是第3半導體層之厚度較第3半導體層内之載 體擴散長度更薄。於此情形時’可有效抑制第3半導體層 内之載體之再結合，並且藉由如本實施形態般形成為積層 結構’亦可提高所入射之光被吸收之概率。As the third photoelectric conversion layer 53, a structure of amorphous quartz is used, but it can also be used for forming a layer on the surface. Type of single crystal or polycrystalline germanium. In this case, the conversion efficiency is further improved. Then, the second photoelectric conversion layer is formed on the surface of the third photoelectric conversion layer 53. Here, the second photoelectric conversion layer 52 can be formed similarly to the third photoelectric conversion layer (4), for example, by a CVD method or the like. After forming a p-type impurity f &amp; type amorphous @ film on the surface of the third photoelectric conversion layer 53 to form the P+ layer 1, the doping of the p-type impurity is stopped to form an undoped amorphous germanium film. To form the second amorphous germanium layer 2b, and further to form an n-type amorphous chip doped with a type 11 impurity to form the n+ layer 3. Next, the first photoelectric conversion layer 51 is formed on the surface of the second photoelectric conversion layer 52. Here, the first photoelectric conversion layer 51 can be formed, for example, as follows. First, a p-type amorphous germanium film doped with a p-type impurity is formed on the surface of the second photoelectric conversion layer 52 by a CVD method or the like to form a p+ layer], and then doping of the p-type impurity is stopped to form a non-doped layer. The amorphous ruthenium film forms the ith non-emergency layer 2a. Thereafter, a ruthenium oxide film 6 containing 铯5 143168.doc •39-201015731 is formed on the surface of the first amorphous germanium layer 2a, whereby the second photoelectric conversion layer 5ι can be formed. Here, the oxygen cut film 6 containing ruthenium 5 can be formed by, for example, introducing a gas containing ruthenium such as an absolute vapor and a raw material for oxygen cutting in a cvd method. Further, in the case of the ruthenium film 6, the ruthenium ion film 6 formed on the surface of the light incident side of the apex layer 11 can be ion-implanted, whereby the oxidized stone film 6 is contained. After the ionized ruthenium 5β is coated with a ruthenium-containing solution such as a vaporized hydrazine aqueous solution or a water-soluble argon aqueous solution, and dried, for example, a ruthenium oxide film 6 is formed by a CVD method or the like. Thereby, the crucible 5 can be disposed in the vicinity of the interface between the amorphous germanium layer 2a and the hafnium oxide film 6. Finally, a transparent conductive film 9 is formed on the surface on the light incident side of the first photoelectric conversion layer 51, whereby the photoelectric conversion device of the present embodiment having the configuration shown in Fig. 5 is produced. Here, the transparent conductive film 9 can be formed by, for example, providing an opening in a portion of the yttrium oxide film 6 such that at least one trowel of the surface on the light incident side of the first amorphous ruthenium layer 2a is exposed. The transparent conductive film 9 containing IT 〇, I 〇, T 〇 or ZO or the like is sputtered or vaporized in such a manner as to be covered from above. In the photoelectric conversion device of the present embodiment having the above-described configuration, the yttrium oxide film 6 is in contact with the surface on the light incident side of the first amorphous ruthenium layer 2a, and the ruthenium oxide film 6 is first. The surface of the surface of the amorphous germanium layer 2a on the light incident side is ionized, and the surface inversion layer 4 is formed on the surface of the light incident side of the first germanium layer 2&amp; Therefore, in the photoelectric conversion device of the present embodiment configured as described above, the patent document disclosed in the configuration of the second layer including the fixed charge and the first layer having no fixed charge between the semiconductor surface and the semiconductor surface is disclosed. Solar cell 143168.doc -40- 201015731 It is easier to induce a negative charge on the surface inversion layer 4 at a higher density, so that the function as an n-type semiconductor can be improved, so that the first amorphous layer 2a can be suppressed. The recombination of the carrier on the surface on the light incident side or the like, whereby the characteristics of the photoelectric conversion device such as photoelectric conversion efficiency are improved. Further, on the surface on the light incident side of the first amorphous germanium layer 2a, a surface inversion layer 4' functioning as an n-type semiconductor is provided instead of the n+ layer which is an absorption source of short-wavelength light, and η The absorption of short-wavelength light can be suppressed more than the + layer, so that the characteristics of the photoelectric conversion device such as photoelectric conversion efficiency can be further improved. Further, in the photoelectric conversion device of the present embodiment configured as described above, the surface reversal can be controlled based on the segregation amount of ruthenium at the interface between the surface of the oxide incident side and the surface of the first amorphous oliw layer 2a on the light incident side. The density of the negative charge induced on the transfer layer 4. Further, in the photoelectric conversion device of the present embodiment configured as described above, the interface energy level on the surface on the light incident side of the first amorphous layer 2a is terminated by the negative electric charge induced on the surface inversion layer 4. Thereby, recombination of the carrier at the interface level of the surface on the light incident side of the first amorphous oliw layer 2a can be suppressed, and the characteristics of the photoelectric conversion device such as photoelectric conversion efficiency can be further advanced. Further, as in the case of the photoelectric conversion device of the present embodiment, when an amorphous germanium is used in the semiconductor layer which is in contact with the surface electrode, the activation rate of the impurity becomes low, so that it is difficult to be on the semiconductor layer which is in contact with the surface electrode. A high-concentration impurity doped layer is formed, but in the photoelectric conversion device of the present embodiment configured as described above, the first amorphous germanium can be formed by the ionized germanium in the hafnium oxide film 6 143168.doc •41· The surface inversion layer 4 is formed on the surface of the layer 2a, so that the surface inversion layer is in contact with the transparent conductive film 9, so that it is not necessary to form a highly doped impurity doped layer. In the above, the amorphous semiconductor is used as the first semiconductor layer, the second semiconductor layer, and the third semiconductor layer ′. However, the first semiconductor layer, the second semiconductor layer, and the first semiconductor layer and the second semiconductor layer are not limited thereto. For the third semiconductor layer, a semiconductor layer such as a crucible, an amorphous germanium, a microcrystalline germanium, or another type of semiconductor other than germanium may be used. Further, the crystal ruthenium contains a single crystal, or a mixture of single crystal and polycrystalline germanium. Further, when crystallized light is used in each of the first semiconductor layer, the second semiconductor layer, and the third semiconductor layer, The laminated structure of the photoelectric conversion layer 51, the second photoelectric conversion layer 52, and the third photoelectric conversion layer 53 can be produced, for example, in the following manner. First, two ruthenium substrates (double-sided doped ruthenium substrates) are formed on the surface of one of the crystal ruthenium to diffuse p-type impurities to form p+ layer 丄, and η on the other surface of the crystallization 矽The type of impurity diffuses to form the n+ layer 3, and a tantalum substrate (single-sided doped germanium substrate) is formed, which diffuses the p-type impurity only on one surface of the crystalline germanium to form a p + layer, and The other side of the junction B曰矽 does not diffuse impurities so that the n+ layer 3 is not formed. Then, an n+ layer 3 of a double-sided doped germanium substrate is bonded to the p+ layer 1 of the single-sided doped germanium substrate, and another 11+ layer 3 of the double-sided doped germanium substrate is bonded to the double-sided doped germanium. The p+ layer i of the substrate can thereby produce the above laminated structure. Thereafter, after the planer 5 is disposed on the surface of the exposed single-sided doped germanium substrate, for example, by thermal oxidation, CVD, ALD, RTO (Rapid Thermal Oxidation), or plasma oxidation. A ruthenium oxide film is formed on a portion of the surface of the single-sided doped ruthenium substrate exposing 143168.doc • 42·201015731, and then formed by, for example, a sputtering method, a CVD method, or a sol gel method (s〇l_Gel method). a transparent conductive film 9 including IT〇, 1〇, τ〇 or z〇, and a P-type layer on the back surface of the laminated structure on the opposite side of the transparent conductive film 9 to form a back surface electrode 7 The photoelectric conversion device of this embodiment can be produced. Further, regarding the planer 5, after the yttrium oxide film 6 is formed, the shikonium ions are ion-implanted in the yttrium oxide film 6, and then annealed, thereby segregating the ruthenium oxide film 6 and the single-sided doping. The boundary of the hybrid substrate is on the Φ plane. In this way, when the ionized crucible 5 is segregated to the vicinity of the interface between the hafnium oxide film 6 and the first semiconductor layer by annealing of the hafnium oxide film 6, the surface inversion layer 4 is used for the best. The ion density of the electron density has a wide tolerance, so that a photoelectric conversion device with stable quality and high characteristics can be provided. In addition, it is also possible to ion-implant the cerium ions in the yttrium oxide film 6 after forming the yttrium oxide film 6 which is thicker than the desired film thickness, and then perform annealing, thereby segregating cerium into the yttrium oxide film. 6 and the interface of the single-sided mixed tantalum substrate, followed by treatment with a hydrofluoric acid aqueous solution or the like or reactive ion remnant or the like to thin the oxide oxide film 6 to a desired film thickness. Further, in the photoelectric conversion device of the present embodiment configured as described above, it is preferable that the band gap of the first semiconductor layer close to the light incident side is equal to or larger than the band gap of the second semiconductor layer on the light incident side. Further, it is more preferable that the band gap of the second semiconductor layer close to the light incident side is equal to or larger than the band gap of the third semiconductor layer on the light incident side. Further, it is more preferable that the band gap of the first semiconductor layer close to the light incident side is equal to or larger than the band gap of the second semiconductor layer on the light incident side, and is close to the second semiconductor layer on the light incident side of U3168.doc -43 - 201015731 The band gap is not less than the band gap of the third semiconductor layer on the light incident side (the band gap of the third semiconductor layer, the band gap of the second semiconductor layer, and the band gap of the first semiconductor layer). Since the laminated structure of the short-wavelength light to the long-wavelength light can be sequentially absorbed from the light incident side as described above, the amount of light incident on the photoelectric conversion device of the present embodiment becomes large. The characteristics of the photoelectric conversion device of the present embodiment, such as efficiency, tend to be improved. Further, as a structure of a semiconductor layer for forming a band gap of the third semiconductor layer, a band gap of the second semiconductor layer, and a band gap of the first semiconductor layer, for example, in the i-th semiconductor layer The amorphous yttrium carbide (Sic) is used, the amorphous ♦ is used for the second semiconductor layer, and the microcrystalline ruthenium is used for the third semiconductor layer. Further, as another configuration of the semiconductor layer for forming the band gap of the third semiconductor layer, the band gap of each of the i-th semiconductor layers of the second semiconductor layer, the second conductor layer may be used, for example, in the fourth conductor layer. In the case of a crystalline carbonaceous stone, an amorphous phase is used for the second semiconductor layer, and amorphous germanium (SiGe) is used for the third semiconductor layer. Further, it is preferable that the thickness of the i-th semiconductor layer is thinner than the carrier diffusion length in the first Jf conductor layer. In this case, the recombination of the carrier in the semiconductor layer can be effectively suppressed, and by forming the laminated structure as in the present embodiment, the probability that the incident light is absorbed can be improved. It is preferable that the thickness of the second semiconductor layer is thinner than the diffusion length of the second semiconductor layer. In this case, the recombination of the carrier in the second semiconductor layer can be effectively suppressed, and the structure can be formed as a laminate 143I68.doc -44 - 201015731 as in the present embodiment. Increase the probability that the incident light will be absorbed. Further, it is preferable that the thickness of the third semiconductor layer is thinner than the carrier diffusion length in the third semiconductor layer. In this case, the recombination of the carrier in the third semiconductor layer can be effectively suppressed, and by forming the laminated structure as in the present embodiment, the probability that the incident light is absorbed can be improved.

又’於以上所述中’使用氧化矽膜6作為表面介電質 膜，但當然並不限定於此，亦可使用例如選自由氧化矽、 氮氧化石夕及氮化石夕所組成之群中之至少一種。 又，作為表面介電質膜，較好的是使用帶隙為4 2 eV“ 上之介電質膜。例如太陽光之大部分係由具有3〇〇 nm以上 之波長之光所構成，故而當使用帶隙為42 eV以上之表面 介電質膜而使太陽光入射時，可抑制具有3〇〇⑽以上之波 長的太陽光被介電質膜所吸收，從而轉換損失變少，因此 光電轉換裝置之特性有進一步提高之傾向。 从又’於以上所述巾’對於使用铯5作為成為正的固定電 荷之雜質的情況進行了說明，但是並不限定於此，亦可使 用例如包含選自由鐘、納、鉀、麵、絶、鎖、每、錄、 頻磷、神及錄所組成之群中之至少一種者。 於上述構成之本實施形態之光電轉換裝置中，綃 之導電型亦可調換n㈣時， 固定電荷之雜皙符接吏用成為負的 Α ” #铯之成為正的固定電荷之雜質。作 銘、Μ伽 狀㈣，可使關如包含選自由蝴、 姑 鎵、銦、銘、1片 及起“ 氟化田勒烯、氧化富勒烯、氟、氯、溴 及碘所组成之群中之至少—種者。 軋溟 143168.doc -45- 201015731 雜=可：為正的固定電荷之雜質及成為負的固定電荷之 ’、’、0刀別以氧化物之狀態而含有。 :，於上述構成之本實施形態之光電轉換裝置中較好 層述雜質存在最多之部位係、位於從作為第1半導體 非晶石夕層2a與作為表面介電質膜之氧切膜6之界 面起’在相對於該界面而垂直之方向上朝著作為第^半導 體層之第1非晶⑦層2a側前進5 nm之區域、與朝著作為表 面介電質膜之氧化矽膜6侧前進5 nm之區域之間的區域 ;此It形時，上述構成之本實施形態之光電轉換裝置 之特性有提高之傾向。 即，於本發明之光電轉換裝置中，只要表面介電質膜在 與第1半導體層之界面附近含有成為正或負的固定電荷之 雜質即可，而該雜質之至少一部分只要係存在於從^半 導體層與表面介電質膜之界面起，在相對於該界面而垂直 之方向上朝著第1半導體層側前進5 nm之區域、與朝著表 面介電質膜側前進5 nm之區域之間的區域上即可。 又，於以上所述中，當然，可使第！非晶矽層2a之光入 射側之氧化妙膜6作為抗反射膜而的發揮功能，亦可於氧 化石夕膜6之表面形成紋理結構及/或蛾眼結構等。 又’已對上述構成之本實施形態之光電轉換裝置中，具 有將第1半導體層、第2半導體層、及第3半導體層之三層 進行積層所成之積層結構的情況進行了說明，但當然並不 限定於三層。 又，如上所述，於上述構成之本實施形態之光電轉換裝 143168.doc -46- 201015731 置中，亦可調換η型與p型之導電型。再者，當上述構成之 本實施形態之光電轉換裝置中已調換η型與p型之導電型之 情形時’正與負的電荷極性亦會被調換。Further, 'the yttrium oxide film 6 is used as the surface dielectric film in the above description, but it is of course not limited thereto, and for example, it may be selected from the group consisting of ruthenium oxide, oxynitride and nitrite. At least one of them. Further, as the surface dielectric film, it is preferable to use a dielectric film having a band gap of 4 2 eV. For example, most of sunlight is composed of light having a wavelength of 3 〇〇 nm or more, and thus When sunlight is incident on a surface dielectric film having a band gap of 42 eV or more, sunlight having a wavelength of 3 〇〇 (10) or more can be suppressed from being absorbed by the dielectric film, and conversion loss is reduced, so that photoelectricity is reduced. The characteristics of the conversion device are further improved. From the above description, the case where the crucible 5 is used as the impurity of the positive fixed charge has been described. However, the present invention is not limited thereto, and for example, the inclusion may be used. At least one of a group consisting of a free clock, a nanometer, a potassium, a surface, an absolute, a lock, a recording, a frequency, a phosphor, a god, and a recording. In the photoelectric conversion device of the embodiment configured as described above, the conductive type of the crucible When n (four) is also exchanged, the miscellaneous charge of the fixed charge is used as a negative Α ” ” 铯 becomes a positive fixed charge impurity. The implication and the sacral shape (4) can be used to contain a mixture selected from the group consisting of: butterfly, gallium, indium, ing, 1 piece and "fluorinated olefin, oxidized fullerene, fluorine, chlorine, bromine and iodine. At least one of the group. Rolling 溟 143168.doc -45- 201015731 Miscellaneous = can be: a positive fixed charge impurity and a negative fixed charge ', ', 0 knife is contained in the state of the oxide. In the photoelectric conversion device of the present embodiment, which is configured as described above, it is preferable that the portion where the impurity is most present is located, and the oxygen-cut film 6 which is the first semiconductor amorphous layer 2a and the surface dielectric film is located. The interface is 'in the direction perpendicular to the interface, the region is 5 nm forward toward the first amorphous 7 layer 2a side of the semiconductor layer, and the yttrium oxide film 6 side is the surface dielectric film. The region between the regions of 5 nm is advanced; in the case of the It, the characteristics of the photoelectric conversion device of the present embodiment configured as described above tend to be improved. That is, in the photoelectric conversion device of the present invention, as long as the surface dielectric film is Contains positive or negative fixation near the interface with the first semiconductor layer The impurity of the charge may be any, and at least a part of the impurity is present at a distance from the interface between the semiconductor layer and the surface dielectric film, and is 5 nm toward the first semiconductor layer side in a direction perpendicular to the interface. The region may be in a region between the region which is 5 nm toward the surface of the surface dielectric film. Further, in the above description, of course, the oxidation of the light incident side of the second amorphous germanium layer 2a may be performed. The membrane 6 functions as an antireflection film, and a texture structure and/or a moth eye structure can be formed on the surface of the oxidized stone film 6. Further, the photoelectric conversion device of the present embodiment having the above configuration has Although the laminated structure in which the three layers of the first semiconductor layer, the second semiconductor layer, and the third semiconductor layer are laminated is described, it is of course not limited to the three layers. In the photoelectric conversion device of the present embodiment, 143168.doc -46- 201015731, the n-type and p-type conductivity types may be exchanged. Further, in the photoelectric conversion device of the present embodiment configured as described above, the n-type and the n-type are replaced. P-type conductivity type -Shaped 'timing will also be replaced with the negative charge polarity.

又，如本實施形態之光電轉換裝置般，當於第丨半導體 層、第2半導體層、及第3半導體層中分別使用非晶矽時， 較好的是第1半導體層、第2半導體層、及第3半導體層分 別於光入射側之表面含有ρ +層。其係根據如下之理由：光 照射時之載體生成係在半導體層中亦會於光入射侧大量產 生’故在半導體層之光入射側之表面上設置叶層，藉此可 使較電子之壽命（life time)更短之電洞抵達ρ+層為止之移 動距離變小。因此，藉由抑制電洞之再結合而可提高轉換 效率。 於上述構成之本實施形態之光電轉換裝置中，作為透明 導電膜9，可使用例如包含ιτο、Ι〇、τ〇或者2〇之層的單 層或複數層之積層體。 再者，於上述構成之本實施形態之光電轉換裝置中，亦 可使用金屬電極代替透明導電膜9。然而，當使用金屬電 極作為與第丨半導體層相接之電極時，考慮到光入射情 況’較好的是僅形成於第1半導體層之表面之一部分上。 &lt;實施形態6&gt; 圖6中表示本發明之光電轉換裝置之另一例之剖面示意 圖。此處，圖6所示之構成之本實施形態之光電轉換裝置 的特徵在於：在第1光電轉換層51之作為第丨半導體層之第 1非晶石夕層2a之光入射侧的表面的一部分上，形成有+層 143168.doc -47- 201015731 3，並且以與n+層3相接的方式而形成透明導電膜9。 由於形成為如本實施形態所述之構成，故與實施形態5 之構成之光電轉換裝置相比，可降低透明導電膜9之接觸 電阻，因而可使光電轉換裝置之光電轉換效率等之特性得 以提高。Further, when an amorphous germanium is used for each of the second semiconductor layer, the second semiconductor layer, and the third semiconductor layer, the first semiconductor layer and the second semiconductor layer are preferably used as in the photoelectric conversion device of the present embodiment. And the third semiconductor layer respectively includes a ρ + layer on the surface on the light incident side. The reason for this is that the carrier generation in the case of light irradiation is also generated in a large amount on the light incident side in the semiconductor layer, so that a leaf layer is provided on the surface on the light incident side of the semiconductor layer, whereby the life of the electron can be made. (life time) The shorter the distance the hole reaches the ρ+ layer, the smaller the moving distance becomes. Therefore, the conversion efficiency can be improved by suppressing recombination of holes. In the photoelectric conversion device of the present embodiment having the above-described configuration, as the transparent conductive film 9, for example, a single layer or a plurality of layers including a layer of ιτο, Ι〇, τ〇 or 2〇 can be used. Further, in the photoelectric conversion device of the present embodiment configured as described above, a metal electrode can be used instead of the transparent conductive film 9. However, when a metal electrode is used as the electrode in contact with the second semiconductor layer, it is preferable to form only a part of the surface of the first semiconductor layer in consideration of the light incident condition. &lt;Embodiment 6&gt; Fig. 6 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention. Here, the photoelectric conversion device of the present embodiment having the configuration shown in FIG. 6 is characterized in that the first photoelectric conversion layer 51 is on the surface on the light incident side of the first amorphous layer 2a as the second semiconductor layer. On one of the portions, a + layer 143168.doc -47 - 201015731 3 is formed, and the transparent conductive film 9 is formed in contact with the n + layer 3. According to the configuration of the present embodiment, the contact resistance of the transparent conductive film 9 can be reduced as compared with the photoelectric conversion device having the configuration of the fifth embodiment, so that the photoelectric conversion efficiency of the photoelectric conversion device can be improved. improve.

又，於本實施形態之光電轉換裝置之氧化矽膜6中，成 為正的固定電荷之已離子化之鉋5係配置在與第!非晶矽層 2a之光入射側之表面之界面附近’因此在與氧切膜㈣ 接之層3之區域上會誘發負電荷而形成蓄積層13。藉由 該蓄積層13與透”電媒9之接㈣可降低透科電膜9之 接觸電阻。再者，當狭，_ 、 田，、於上述及下述之任一實施形態之 光電轉換裝置之構成中’誘發負電荷之反轉層與n+層之重 合區域、以及誘發正電荷之反轉層與P+層之重合區域之任 一者均能成為蓄積層。 又n+層3可藉由以下方式而形成：在作為第1半導體）Further, in the yttrium oxide film 6 of the photoelectric conversion device of the present embodiment, the ionized planer 5 which is a positive fixed charge is disposed in the vicinity of the interface with the surface on the light incident side of the second amorphous layer 2a. Therefore, a negative charge is induced in the region of the layer 3 connected to the oxygen-cut film (four) to form the accumulation layer 13. The contact resistance of the transparent electric film 9 can be reduced by the connection of the accumulation layer 13 and the "intermediate dielectric 9". Further, the photoelectric conversion of the embodiment of the invention can be reduced. In the configuration of the device, any one of the overlapping region of the negative charge inducing layer and the n+ layer, and the overlapping region of the inversion layer inducing the positive charge and the P+ layer can be an accumulation layer. Formed as follows: as the first semiconductor)

第非明梦層2a之光入射側的表面上，設置在與打+層^ 形成部位相對應之部位上含有開口部之遮罩之後，使n, =該開口部擴散。再者，㈣雜質之擴散可藉由m 又/〇C13專之含有11型雜質之氣體的氣相擴散來進行e :雜：二！可對上述開口部進行離子佈植或離子推㈣ 摻雜磷、坤或銻等之η型雜質以形成n+層3。 ㈣中之上述以外之說明與實施形態5相同，区 而在此省略其說明。 相丨j g &lt;實施形態7&gt; 143168.doc -48- 201015731 圖7中表示本發明之光電轉換裝置之另一例之剖面示意 圖此處，圖7所示之構成之本實施形態之光電轉換裝置 的特徵在於：於第1光電轉換層51之作為第1半導體層之第 1非阳矽層2a之光入射側的表面的一部分上，形成有金屬 矽化物10。 由於形成為如本實施形態所述之構成，故金屬矽化物1〇 為如金屬般之低電阻，因而可藉由金屬矽化物1〇而形成低 電阻之梳形狀之電極，並且可抑制因透明導電膜而引起之 光的吸收，因此與實施形態5之光電轉換裝置相比，可使 光電轉換裝置之光電轉換效率等之特性得以提高。 再者，金屬矽化物10可藉由使用例如一直以來公知之自 行對準石夕化物化（SALICIDE)製程來形成。由於使用 SALIC1DE製程，故無需電極加工用之遮罩，從而可容易 地形成電極。 又，作為金屬矽化物1〇，只要係包含至少一種任意金屬 與矽之化合物者便可使用而並無特別限定，作為與矽進行 化合之金屬，可舉出例如Ti、別、c〇、Er、Yb或Pt等。其 中，作為與矽進行化合之金屬，可使用能於低溫下形成之 鎳矽化物（NixSi(X与〇.5〜2))或者鈷矽化物（c〇xSi(xi?〇 5〜2)) 等。 又，於本實施形態之光電轉換裝置中，亦可使用與金屬 石夕化物10相接之透明導電膜等來形成配線層。 本實施形態中之上述以外之說明與實施形態5相同，因 而在此省略其說明。 143168.doc •49· 201015731 〈實施形態8&gt; 圖8申表示本發明之光電轉換裝置之另一例之剖面示意 圖。此處’圖8所示之構成之本實施形態之光電轉換裝置 的特徵在於：在第1光電轉換層51之作為第1半導體層之第 1非晶石夕層2a之光入射侧的表面的一部分上，形成有金屬 矽化物10，且在金屬矽化物10與第1非晶矽層2&amp;之間之區 域上形成有因n型雜質之偏析而形成之n+層3。 在如本實施形態所述之構成中’與實施形態7之構成之 光電轉換裝置相比，可改善金屬石夕化物1 〇與第1非晶石夕層 2a之間的整流特性，並且可降低金屬矽化物丨〇與表面反轉 層4之間的電阻，因此可使光電轉換裝置之光電轉換效率 等之特性得以提高。 又’由於形成為如本實施形態所述之構成，故與實施形 態7之構成之光電轉換裝置相比，可進一步降低透明導電 膜9之接觸電阻，因此可進一步提高光電轉換裝置之光電 轉換效率等之特性。 又’於本實施形態之光電轉換裝置中，亦可形成與金屬 石夕化物1 〇相接之透明導電膜。 本實施形態中之上述以外之說明與實施形態5〜7相同， 因而在此省略其說明。 &lt;實施形態9&gt; 圖9中表示本發明之光電轉換裝置之另一例之剖面示意 圖。此處’圖9所示之構成之本實施形態之光電轉換裝置 的特徵在於：以與第3光電轉換層53之第3非晶矽層2c之背 143168.doc 201015731 面相接的方式而形成作為背面介電質膜之氧切膜60,其 含有與表面介電質膜4所含之成為正的以電荷 相 反極性之成為負的固定電荷之雜質5〇。 為相 此處’背面介電質財所含之成為負的回定電荷之雜質 係在與第3非晶矽層2c之背面之界面附近經離子化等而成 為負的固定電荷，&amp;而在與背面介電質膜相接之第3非曰On the surface on the light incident side of the non-dream layer 2a, a mask having an opening portion at a portion corresponding to the formation portion of the layer + layer is provided, and then n, = the opening portion is diffused. Furthermore, (4) the diffusion of impurities can be carried out by gas phase diffusion of m//C13 specifically containing a type 11 impurity gas: m: impurity: two! The opening portion may be ion-implanted or ion-implanted (tetra) with an n-type impurity such as phosphorus, krypton or germanium to form an n+ layer 3. (4) The descriptions other than the above are the same as those in the fifth embodiment, and the description thereof is omitted here. [Embodiment 7] Embodiment 7&gt; 143168.doc -48- 201015731 FIG. 7 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention. Here, the photoelectric conversion device of the present embodiment having the configuration shown in FIG. The metal telluride 10 is formed on a part of the surface on the light incident side of the first non-emergency layer 2a as the first semiconductor layer of the first photoelectric conversion layer 51. Since it is formed in the configuration as described in the present embodiment, the metal telluride 1 is a metal-like low resistance, so that a low-resistance comb-shaped electrode can be formed by the metal telluride 1 ,, and transparency can be suppressed. Since the light is absorbed by the conductive film, the photoelectric conversion efficiency of the photoelectric conversion device can be improved as compared with the photoelectric conversion device of the fifth embodiment. Further, the metal halide 10 can be formed by using, for example, a conventionally known self-aligned SALICIDE process. Since the SALIC1DE process is used, a mask for electrode processing is not required, so that the electrode can be easily formed. Further, the metal halide compound is not particularly limited as long as it contains at least one compound of any of a metal and ruthenium, and examples of the metal compounded with ruthenium include Ti, other, c〇, and Er. , Yb or Pt, etc. Among them, as the metal to be combined with ruthenium, nickel ruthenium (NixSi (X and 〇. 5 〜 2)) or cobalt ruthenium (c 〇 x Si (xi 〇 5 2)) which can be formed at a low temperature can be used. Wait. Further, in the photoelectric conversion device of the present embodiment, a wiring layer can be formed by using a transparent conductive film or the like which is in contact with the metal ceramsite 10. The descriptions other than the above in the present embodiment are the same as those in the fifth embodiment, and thus the description thereof will be omitted. 143168.doc •49· 201015731 <Embodiment 8> Fig. 8 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention. In the photoelectric conversion device of the present embodiment, which is configured as shown in FIG. 8, the surface of the first photoelectric conversion layer 51 on the light incident side of the first amorphous layer 2a as the first semiconductor layer is characterized. A part of the metal halide 10 is formed, and an n+ layer 3 formed by segregation of an n-type impurity is formed in a region between the metal halide 10 and the first amorphous layer 2 &amp; In the configuration according to the present embodiment, the rectifying property between the metal lithium compound 1 〇 and the first amorphous olivine layer 2a can be improved and can be reduced as compared with the photoelectric conversion device having the configuration of the seventh embodiment. The electric resistance between the metal telluride and the surface inversion layer 4 can improve the characteristics of the photoelectric conversion efficiency and the like of the photoelectric conversion device. In addition, since the configuration as described in the present embodiment is formed, the contact resistance of the transparent conductive film 9 can be further reduced as compared with the photoelectric conversion device having the configuration of the seventh embodiment, so that the photoelectric conversion efficiency of the photoelectric conversion device can be further improved. Characteristics. Further, in the photoelectric conversion device of the present embodiment, a transparent conductive film which is in contact with the metal lithium compound 1 亦可 can be formed. The descriptions other than the above in the present embodiment are the same as those in the fifth to seventh embodiments, and thus the description thereof is omitted here. &lt;Embodiment 9&gt; Fig. 9 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention. Here, the photoelectric conversion device of the present embodiment having the configuration shown in FIG. 9 is formed so as to be in contact with the surface of the third amorphous germanium layer 2c of the third photoelectric conversion layer 53 on the back surface 143168.doc 201015731. The oxygen cut film 60 as the back surface dielectric film contains an impurity 5 与 which is a negative fixed charge which is positive in charge opposite to the charge contained in the surface dielectric film 4. The impurity which is a negative return charge contained in the back surface dielectric material is a fixed charge which becomes negative by ionization or the like in the vicinity of the interface with the back surface of the third amorphous germanium layer 2c. The third non-曰 connected to the back dielectric film

❹^背面之至少—部分區域上’會誘發作為p型半: 體而發揮功能之背面反轉層40。 於上述構成之本實施形態之光電轉換裝置中，當使用透 明導電膜等之透明電極作為f面電極7、且使光/僅自第工 光電轉換層51側而^亦自第3光電轉換層53側人射時，可 抑制因第3光電轉換層之州而產生之短波長之光的吸 收’故而可使光電轉換裝置之光電轉換效率等之特性得以 提高。 質臈，但當然並不 、氮氧化矽及氮化 再者’使用氧化矽膜60作為背面介電 限定於此，亦可使用例如選自由氧化石夕 石夕所組成之群中之至少一種。 又，於上述構成之本實施形態之光電轉換襞置中，較好 的是，作為背面介電質膜之氧化矽膜6〇中所含之雜質存 在最多之部位係位於從作為第3半導體層之第3非晶矽層= 與作為背面介電質膜之氧切⑽之界面起，^對於該C 界面而垂直之方向上朝著作為第3半導體層之第3非晶矽= 2c側前進5 nm之區域、與朝著作為背面介電質膜之氧化矽 膜60側前進5 nm之區域之間的區域上。於此情形時，上述 143168.doc •51 · 201015731 構成之本實施形態之光電轉換裝置之特性有進一步提高之 傾向。 即，於本發明之光電轉換裝置中，較好的是背面介電質 膜在與第3半導體層之界面附近，含有與表面介電質膜中 所含之成為正或負的固定電荷之雜質為相反極性之固定電 荷的雜質，但只要該雜質之至少一部分係存在於從第3半 導體層與背面介電質膜之界面起，在相對於該界面而垂直 之方向上朝著第3半導體層側前進5 nm之區域、與朝著背 面介電質膜側前進5 nm之區域之間的區域上即可。 本實施形態中之上述以外之說明與實施形態5相同，因 而在此省略其說明。 &lt;實施形態10&gt; 圖10中表示本發明之光電轉換裝置之另一例之立體示意 圖。此處，於圖1〇所示之構成之本實施形態的光電轉換裝 置之作為半導體層之P型矽基板2之光入射側的表面上，形 成有凹凸15，且於形成有凹凸15tp型矽基板2之光入射側 之表面上’設置有作為表面介電質膜之氧化矽膜6。又， 於作為半導體層之p型矽基板2之光入射側之表面之一部分 上，形成有n+層3。 又’氧化矽膜6在與p型矽基板2之光入射側之表面之界 面附近’含有成為正的固定電荷之雜質鉋（未圖示），絶係 在與P型矽基板2之光入射侧之表面之界面附近經離子化而 成為正的固定電荷，故而在與氧化矽膜6相接之p型矽基板 2之光入射側之表面的至少一部分區域上，會誘發與n+層3 143168.doc •52· 201015731 同樣地作為n型半導體而發揮功能之表面反轉層4。 又於Ρ型石夕基板2之與光入射側之表面成為相反侧之表 面㈣面之一部分上，形成有㈣！，並且於口型石夕基板2 之背面上叹置有氧化石夕膜26。又，於㈣碎基板^之背面上 經由氧切膜26而形成有背面電極7，背面電極7係以通過 形成於氧化矽膜26上之開口部並與扣層丨之背面之一部分 相接的方式而形成。 又，於Ρ型矽基板2之光入射側之表面上經由氧化矽膜6 而形成有作為表面電極之金屬電極8,金屬電極8係以通過 形成於氧化矽膜6上之開口部並與“層3之表面之一部分相 接的方式而形成。 以下，對圖10所示之構成的本實施形態之光電轉換裝置 之製造方法之一例進行說明。首先，於ρ型矽基板2之光入 射側之表面上形成凹凸15。此處，凹凸15之形成係可藉由 例如使用有氫氧化鉀水溶液或氫氧化鈉水溶液之濕式蝕刻 而於Ρ矽基板2之光入射側之表面形成紋理結構來進行。 又’凹凸15之形成亦可藉由例如雷射光之照射、 RIE(Reactive Ι〇η Etching，反應性離子蝕刻）或者電漿照射 等而去除卩型矽基板2之光入射侧之表面的一部分來進行。 其次，於ρ型矽基板2之光入射側之表面上形成氧化矽骐 6，並且於P型矽基板2之與光入射側之表面為相反側之背 面上形成氧化石夕膜26。此處，當？型石夕基板2包含單晶碎 時，例如在950°C以上之溫度下進行熱氧化，藉此可於ρ型 石夕基板2之光入射侧之表面形成氧化石夕膜6，並且於ρ型碎 143168.doc -53 · 201015731 基板2之背面形成氧化矽膜26。 其次，於p型矽基板2之背面形成p+層！。此處，叶層1之 形成可藉由如下方式而進行：例如於p型矽基板2之背面 上，設置有在與p+層1之形成部位相對應之部位上設有開 口部之遮罩，並使p型雜質自該開口部擴散等。又，p型雜 質之擴散可藉由例如使用有BBr3等之含有口型雜質之氣體 的氣相擴散來進行。 接下來，於p型矽基板2之光入射侧之表面形成11+層3。 此處，n+層3之形成可藉由在卩型矽基板2之光入射側之表 面使η型雜質擴散來進行。又，n型雜質之擴散可藉由例如 在與Μ層3之形成部位相對應之部位之氧化矽膜6的一部分 上設置開口部，並自該開口部以使用有？〇(：：13等之含有η型 雜質之氣體的氣相擴散而進行。 接下來，使形成於ρ型矽基板2之光入射側之表面上的氧 化矽膜6中含有铯5。此處，關於鉋5，例如可在形成於ρ型 矽基板2之光入射侧之表面上的氧化矽膜6中將鉋離子進行 離子佈植，藉以使氧化矽膜6中含有已離子化之铯5。 然後，進行ρ型矽基板2之退火。此處，ρ型矽基板2之退 火例如可藉由對上述鉋離子佈植後之？型矽基板2以例如 800°C〜1000°C之溫度進行退火來進行。藉此，可使氧化矽 膜6中已離子化之鏠5偏析到與{)型矽基板2之光入射側之表 面之界面上，因而會在與氧化矽膜6相接之ρ型矽基板2之 光入射側之表面上形成表面反轉層4。 然後，於ρ型矽基板2之光入射側之表面上形成金屬電極 143168.doc •54· 201015731 8。此處’金屬電極8可藉由如下方法等而形成：例如在使 與金屬電極8接觸之n+層3之表面露出之部位上，於氧化矽 膜6上設置開π部’並使㈣罩等將金屬驗成特定 狀。 其次，於p型矽基板2之背面上形成背面電極7。此處， 背面電極7可藉由如下方法等而形成：例如在使與背面電 極7接觸之p+層1之表面露出之部位上，於氧化矽膜6上設 置開口部’並使用遮罩等來蒸鍍金屬。 最後，進行在形成上述金屬電極8及背面電極7之後的p 型矽基板2之退火，藉此製作出具有上述構成的本實施形 態之光電轉換裝置之一例。此處，卩型矽基板2之退火可藉 由例如使p型矽基板2暴露於350〇c〜5〇(rc溫度之氫環境中 來進行。 在由以上方式所製作之上述構成之本實施形態的光電轉 換裝置中’氧化矽膜6與1)型矽基板2之光入射側之表面相 接’藉由在氧化矽膜6與p型矽基板2之光入射側之表面之 界面上已離子化之鉋，而於p型矽基板2之光入射側之表面 上形成有表面反轉層4。 因此’在上述構成之本實施形態之光電轉換裝置中，與 設置有含固定電荷之第二層、及在與半導體表面之間不含 固定電荷之第一層之構成的專利文獻1所揭示之太陽電池 相比’更容易在表面反轉層4上高密度地誘發負電荷，使 作為η型半導體之功能得以提高，故可抑制p型矽基板2之 光入射侧之表面上之載體的再結合等，藉此，光電轉換效 143168.doc •55- 201015731 率等之光電轉換裝置之特性會得到提高。 又’在P型石夕基板2之光入射側之表面上’代替成為短波 長光之吸收源的n+層3而設置有作為n型半導體發揮功能的 表面反轉層4來，藉此，與η+層3相比，更可抑制短波長之 光的吸收，因此可使光電轉換效率等之光電轉換 ^ 性得到進一步提高。 、、特 又，在氧化矽膜6中配置固定電荷，藉此，與形成11+層3 之情形相比，内建電位（built-in potential)更會增大，因此 P型矽基板2之内部電場變大。由於該較大的内部電場，使 鬱 得在載體傳導甲漂移（drift)成分相較擴散成分而成為支配 者，從而載體之移動速度增大’載體之再結合得到抑制。 藉此’可提高載體之收集效率。 又，於上述構成之本實施形態之光電轉換裝置中，根據 氧化矽膜6與p型矽基板2之光入射側之表面之界面上的铯 之偏析量，可控制表面反轉層4上所誘發之負電荷之密 度。 特別是如本實施形態般，當藉由在氧化矽膜6中之铯離 ® 子佈植及退火而使鉋偏析到氧化矽膜6與p型矽基板2之界 面上時，表面反轉層4上之用以獲得最佳的負電荷密度之 鉋離子佈植量之容限較廣，因此可提供一種品質穩定且特 性高的光電轉換裝置。 又’於上述構成之本實施形態之光電轉換裝置中，使p 型梦基板2之光入射側之表面上的界面能階因表面反轉層4 上所誘發之負電荷而終止，藉此可抑制p型石夕基板2之光入 143168.doc -56- 201015731 射側之表面之界面能階上的載體之再結合，從而可使光電 轉換效率等之光電轉換裝置之特性得到進一步提高。 進而，於上述構成之本實施形態之光電轉換裝置中，藉 由在p型妙基板2之光入射側之表面上所形成的凹凸15、以 及在p型碎基板2之與光入射側之表面為相反側之背面上所 形成的背面電極7，可獲得於p型矽基板2之内部之光封閉 效應。 本實施形態中之上述以外之說明與實施形態1相同，因 而在此省略其說明。 &lt;實施形態11&gt; 圖11中表示本發明之光電轉換裝置之另一例之立體示意 圖。此處，圖11所示之構成之本實施形態之光電轉換裝置 的特徵在於：於p型矽基板2之背面上，設置有作為背面介 電質膜之氧化矽膜60，氧化矽膜60係在與卩型矽基板2之背 面之界面附近，含有成為與氧化矽膜6中所含之绝為不同 ❹ 極性之負的固定電荷之雜質（未圖示），上述氧化矽膜6係作 為表面介電質膜而設置於p型矽基板2之光入射侧之表面 上。 此處’氧化矽膜60在與p型矽基板2之背面之界面附近， 含有成為負的固定電荷之雜質，成為負的固定電荷之雜質 係在與p型矽基板2之背面之界面附近經離子化等而成為負 的固定電荷，因此在與氧化矽膜6〇相接之p型矽基板2之背 面之至少一部分區域上，會誘發與叶層1同樣地作為p型半 導體而發揮功能之背面反轉層4〇。 I43168.doc •57· 201015731 於上述構成之本實施形態之光電轉換裝置_，不僅於p 型矽基板2之光入射側之表面上形成有表面反轉層4，而且 於P型矽基板2之與光入射側之表面為相反側之背面上形成 有背面反轉層40，從而可抑制在p型矽基板2之光入射側之 表面及其相反側之背面上分別進行載體之再結合，故而與 實施形態10之光電轉換裝置相比，可進一步提高光電轉換 效率等之光電轉換裝置之特性。並且，於上述構成之本實 施形態之光電轉換裝置中，與實施形態1〇之光電轉換裝置 相比，可抑制因P +層1而產生之光的吸收。 再者，使用氧化矽膜60作為背面介電質膜，但當然並不 限定於此’亦可使用例如氧化碎、氮氧化々及氮化石夕所組 成之群中之至少一種。 又，使作為背面介電質膜之氧化矽膜6〇中含有成為負的 固定電荷之雜質之方法，可使用與作為表面介電質膜之氧 化梦膜6相同之方法。 又於上述構成之本實施形態之光電轉換裝置中，較好 的作為背面介電質膜之氧化矽膜6〇中所含之雜質存在 最夕之。卩位係位於從作為半導體層之p型矽基板2與作為背 面&quot;電質膜之氧化石夕膜6〇之界面起，在相對於該界面而垂 方向上朝著P型矽基板2侧前進5 nm之區域、與朝著 者面&quot;電質膜之氧化石夕膜6〇側前進5 nm之區域之間的 區域上&amp;此情形時，上述構成之本實施形態之光電轉換 裝置之特性有進一步提高之傾向。 P於本發明之光電轉換裝置中，較好的是背面介電質 143168.doc 201015731 膜在與半導體層之界面附近，含有與表面介電質膜中所含 之成為正或負的固定電荷之雜質為相反極性之固定電荷的 雜質，但只要該雜質之至少一部分係存在於從半導體層與 背面介電質膜之界面起，在相對於該界面而垂直之方向上 朝著半導體層侧前進5 nm之區域、與朝著背面介電質膜侧 前進5 nm之區域之間的區域上即可。 本實施形態中之上述以外之說明與實施形態丨及實施形 態10相同，因而在此省略其說明。At least the partial area on the back surface of the ❹^ induces a backside inversion layer 40 that functions as a p-type half body. In the photoelectric conversion device of the present embodiment, the transparent electrode such as a transparent conductive film is used as the f-plane electrode 7, and the light/only from the photoelectric conversion layer 51 side is also used from the third photoelectric conversion layer. When the 53 side person is shot, the absorption of light of a short wavelength due to the state of the third photoelectric conversion layer can be suppressed. Therefore, the characteristics of the photoelectric conversion efficiency of the photoelectric conversion device can be improved. However, it is not limited to ruthenium oxynitride and nitridation. The use of the ruthenium oxide film 60 as the back surface dielectric is limited thereto, and at least one selected from the group consisting of oxidized stone shi Shi Xi may be used. Further, in the photoelectric conversion device of the present embodiment having the above-described configuration, it is preferable that the portion of the oxide film included in the ruthenium oxide film 6 背面 as the back surface dielectric film is most present as the third semiconductor layer. The third amorphous germanium layer = the interface with the oxygen cut (10) as the back surface dielectric film, and the third amorphous layer = 2c side of the third semiconductor layer is formed in the direction perpendicular to the C interface. The region of 5 nm is in a region between the region 5 nm advanced toward the side of the yttrium oxide film 60 which is the back surface dielectric film. In this case, the characteristics of the photoelectric conversion device of the present embodiment constituted by the above-mentioned 143168.doc • 51 · 201015731 tend to be further improved. That is, in the photoelectric conversion device of the present invention, it is preferred that the back surface dielectric film contains an impurity which is a positive or negative fixed charge contained in the surface dielectric film in the vicinity of the interface with the third semiconductor layer. a fixed charge impurity of opposite polarity, but as long as at least a part of the impurity exists in the direction perpendicular to the interface toward the third semiconductor layer from the interface between the third semiconductor layer and the back surface dielectric film It is sufficient to advance the region between 5 nm and the region 5 nm toward the back dielectric film side. The descriptions other than the above in the present embodiment are the same as those in the fifth embodiment, and thus the description thereof will be omitted. &lt;Embodiment 10&gt; Fig. 10 is a perspective view showing another example of the photoelectric conversion device of the present invention. Here, on the surface on the light incident side of the P-type germanium substrate 2 as the semiconductor layer of the photoelectric conversion device of the present embodiment shown in FIG. 1A, the unevenness 15 is formed, and the unevenness 15tp type is formed. A ruthenium oxide film 6 as a surface dielectric film is provided on the surface of the light incident side of the substrate 2. Further, an n + layer 3 is formed on a portion of the surface on the light incident side of the p-type germanium substrate 2 as the semiconductor layer. Further, the 'cerium oxide film 6' contains an impurity planer (not shown) which becomes a positive fixed charge in the vicinity of the interface with the surface on the light incident side of the p-type germanium substrate 2, and is incident on the light incident on the P-type germanium substrate 2. The vicinity of the interface on the side surface is ionized to become a positive fixed charge, so that at least a part of the surface of the light incident side of the p-type germanium substrate 2 that is in contact with the hafnium oxide film 6 is induced with the n+ layer 3 143168. .doc •52· 201015731 Similarly, the surface inversion layer 4 functions as an n-type semiconductor. Further, on one of the surfaces of the surface (four) which is opposite to the surface on the light incident side of the 石-type shixi substrate 2, (four) is formed! And an oxide oxide film 26 is slanted on the back surface of the mouth-shaped stone substrate 2. Further, a back surface electrode 7 is formed on the back surface of the (4) chip substrate via the oxygen cut film 26, and the back surface electrode 7 is formed to pass through an opening portion formed on the ruthenium oxide film 26 and is in contact with a portion of the back surface of the buckle layer. Formed by the way. Further, a metal electrode 8 as a surface electrode is formed on the surface on the light incident side of the 矽-type ruthenium substrate 2 via the ruthenium oxide film 6, and the metal electrode 8 is formed by the opening formed on the ruthenium oxide film 6 and An example of a method of manufacturing the photoelectric conversion device of the present embodiment having the configuration shown in Fig. 10 will be described below. First, on the light incident side of the p-type germanium substrate 2 The unevenness 15 is formed on the surface. Here, the unevenness 15 can be formed by forming a texture on the surface of the light incident side of the ruthenium substrate 2 by wet etching using, for example, an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution. Further, the formation of the unevenness 15 may be performed by, for example, irradiation of laser light, RIE (Reactive Et Etching), or plasma irradiation to remove the surface on the light incident side of the 矽-type ruthenium substrate 2. Next, yttrium oxide 6 is formed on the surface on the light incident side of the p-type ruthenium substrate 2, and oxidized olivine is formed on the back surface of the P-type ruthenium substrate 2 opposite to the surface on the light incident side. 26. Here, when the ?-type substrate 1 comprises a single crystal, for example, thermal oxidation is performed at a temperature of 950 ° C or higher, whereby an oxidized stone can be formed on the surface of the light incident side of the p-type substrate 2 The ruthenium film 6 is formed on the back surface of the substrate 2 on the back surface of the p-type ruthenium substrate 2. Next, a p+ layer is formed on the back surface of the p-type ruthenium substrate 2. Here, the formation of the leaf layer 1 can be performed. For example, on the back surface of the p-type germanium substrate 2, a mask having an opening portion at a portion corresponding to a portion where the p+ layer 1 is formed is provided, and p-type impurities are provided from the opening portion. Further, the diffusion of the p-type impurity can be performed by, for example, gas phase diffusion using a gas containing a lip-type impurity such as BBr3. Next, 11+ is formed on the surface of the light-incident side of the p-type germanium substrate 2. Layer 3. Here, the formation of the n+ layer 3 can be performed by diffusing an n-type impurity on the surface of the light-incident side of the germanium-type germanium substrate 2. Further, the diffusion of the n-type impurity can be performed, for example, by the germanium layer 3 An opening portion is formed in a portion of the cerium oxide film 6 at a portion corresponding to the formation portion, and is opened therefrom The portion is formed by gas phase diffusion using a gas containing an η-type impurity such as 〇 (: 13). Next, the yttrium oxide film 6 formed on the surface on the light incident side of the p-type ruthenium substrate 2 is contained.铯 5. Here, regarding the planer 5, for example, ionizing ions may be ion-implanted in the yttrium oxide film 6 formed on the surface on the light incident side of the p-type ruthenium substrate 2, whereby the yttrium oxide film 6 is contained therein. After ionization, the annealing of the p-type germanium substrate 2 is performed. Here, the annealing of the p-type germanium substrate 2 can be performed, for example, by 800 ° C for the ?-type substrate 2 after the above-mentioned planing ion implantation? Annealing is performed at a temperature of 1000 ° C. Thereby, the ionized crucible 5 in the hafnium oxide film 6 can be segregated to the interface with the surface of the light incident side of the {) type germanium substrate 2, and thus it is oxidized. The surface inversion layer 4 is formed on the surface on the light incident side of the p-type ruthenium substrate 2 to which the ruthenium film 6 is in contact. Then, a metal electrode 143168.doc •54· 201015731 8 is formed on the surface of the light incident side of the p-type ruthenium substrate 2. Here, the metal electrode 8 can be formed by, for example, providing a portion of the surface of the n+ layer 3 that is in contact with the metal electrode 8 with a π portion and a (four) mask. The metal is tested to a specific shape. Next, the back surface electrode 7 is formed on the back surface of the p-type germanium substrate 2. Here, the back surface electrode 7 can be formed by, for example, providing an opening portion ′ on the yttrium oxide film 6 at a portion where the surface of the p+ layer 1 that is in contact with the back surface electrode 7 is exposed, and using a mask or the like. Evaporation of metal. Finally, annealing of the p-type germanium substrate 2 after forming the metal electrode 8 and the back surface electrode 7 is performed, thereby producing an example of the photoelectric conversion device of the present embodiment having the above configuration. Here, the annealing of the ruthenium-type ruthenium substrate 2 can be performed by, for example, exposing the p-type ruthenium substrate 2 to a hydrogen atmosphere of 350 〇c to 5 〇 (the temperature of rc. The present embodiment of the above configuration produced by the above method) In the photoelectric conversion device of the form, the surface of the light incident side of the 'yttrium oxide film 6 and 1) type germanium substrate 2 is connected' by the interface between the surface of the light incident side of the tantalum oxide film 6 and the p-type germanium substrate 2 The ionized planer is formed with a surface inversion layer 4 on the surface on the light incident side of the p-type germanium substrate 2. Therefore, the photoelectric conversion device of the present embodiment configured as described above is disclosed in Patent Document 1 in which a second layer containing a fixed charge and a first layer having a fixed charge between the surface and the semiconductor surface are provided. The solar cell is more likely to induce a negative charge on the surface inversion layer 4 at a higher density, so that the function as an n-type semiconductor is improved, so that the carrier on the surface on the light incident side of the p-type germanium substrate 2 can be suppressed. By combining, etc., the characteristics of the photoelectric conversion device such as the photoelectric conversion effect 143168.doc • 55- 201015731 rate are improved. Further, 'on the surface on the light incident side of the P-type slab substrate 2', instead of the n+ layer 3 serving as an absorption source of short-wavelength light, a surface inversion layer 4 functioning as an n-type semiconductor is provided, thereby The η+ layer 3 can suppress the absorption of light of a short wavelength, and thus the photoelectric conversion efficiency such as photoelectric conversion efficiency can be further improved. Further, a fixed charge is disposed in the hafnium oxide film 6, whereby the built-in potential is increased more than in the case of forming the 11+ layer 3, and thus the P-type germanium substrate 2 is further increased. The internal electric field becomes larger. Due to this large internal electric field, the drift component of the carrier conduction is more dominant than the diffusion component, so that the moving speed of the carrier is increased, and the recombination of the carrier is suppressed. Thereby, the collection efficiency of the carrier can be improved. Further, in the photoelectric conversion device of the present embodiment having the above-described configuration, the surface inversion layer 4 can be controlled based on the segregation amount of ruthenium on the interface between the yttrium oxide film 6 and the surface on the light incident side of the p-type ruthenium substrate 2. The density of the induced negative charge. In particular, as in the present embodiment, when the planer is segregated to the interface between the yttrium oxide film 6 and the p-type ruthenium substrate 2 by the ruthenium separation and annealing in the ruthenium oxide film 6, the surface inversion layer The planer ion implantation amount for obtaining the optimum negative charge density has a wide tolerance, so that a photoelectric conversion device with stable quality and high characteristics can be provided. Further, in the photoelectric conversion device of the present embodiment configured as described above, the interface energy level on the surface on the light incident side of the p-type dream substrate 2 is terminated by the negative electric charge induced on the surface inversion layer 4, whereby The light of the p-type slab substrate 2 is suppressed from recombining the carrier on the interface level of the surface of the 143168.doc -56-201015731, so that the characteristics of the photoelectric conversion device such as photoelectric conversion efficiency can be further improved. Further, in the photoelectric conversion device of the present embodiment configured as described above, the unevenness 15 formed on the surface on the light incident side of the p-type substrate 2 and the surface on the light incident side of the p-type substrate 2 The back surface electrode 7 formed on the back side of the opposite side can obtain a light confinement effect inside the p-type germanium substrate 2. The description of the present embodiment other than the above is the same as that of the first embodiment, and thus the description thereof will be omitted. &lt;Embodiment 11&gt; Fig. 11 is a perspective view showing another example of the photoelectric conversion device of the present invention. Here, the photoelectric conversion device of the present embodiment having the configuration shown in FIG. 11 is characterized in that a ruthenium oxide film 60 as a back surface dielectric film and a ruthenium oxide film 60 are provided on the back surface of the p-type ruthenium substrate 2. In the vicinity of the interface with the back surface of the ruthenium-type ruthenium substrate 2, an impurity (not shown) which is a negative fixed charge which is a polarity different from that contained in the ruthenium oxide film 6 is contained, and the ruthenium oxide film 6 is used as a surface. The dielectric film is provided on the surface on the light incident side of the p-type germanium substrate 2. Here, the yttrium oxide film 60 contains an impurity which becomes a negative fixed charge in the vicinity of the interface with the back surface of the p-type ruthenium substrate 2, and an impurity which becomes a negative fixed charge is in the vicinity of the interface with the back surface of the p-type ruthenium substrate 2 Since ionization or the like becomes a negative fixed charge, at least a part of the back surface of the p-type germanium substrate 2 that is in contact with the yttrium oxide film 6 诱发 is induced to function as a p-type semiconductor similarly to the leaf layer 1 . The backside inversion layer is 4〇. In the photoelectric conversion device of the present embodiment configured as described above, the surface inversion layer 4 is formed not only on the surface on the light incident side of the p-type germanium substrate 2 but also on the P-type germanium substrate 2. The back surface inversion layer 40 is formed on the back surface opposite to the surface on the light incident side, thereby suppressing recombination of the carrier on the surface on the light incident side of the p-type germanium substrate 2 and the back side thereof. Compared with the photoelectric conversion device of the tenth embodiment, the characteristics of the photoelectric conversion device such as photoelectric conversion efficiency can be further improved. Further, in the photoelectric conversion device of the present embodiment configured as described above, the absorption of light due to the P + layer 1 can be suppressed as compared with the photoelectric conversion device of the first embodiment. Further, the ruthenium oxide film 60 is used as the back surface dielectric film, but it is of course not limited thereto. At least one of the group consisting of oxidized ash, bismuth oxynitride and cerium nitride may also be used. Further, a method of causing an impurity which is a negative fixed charge in the ruthenium oxide film 6 作为 as the back surface dielectric film can be the same as the method of oxidizing the dream film 6 as a surface dielectric film. Further, in the photoelectric conversion device of the present embodiment configured as described above, it is preferable that the impurities contained in the ruthenium oxide film 6 of the back surface dielectric film are present. The 卩 position is located from the interface between the p-type germanium substrate 2 as the semiconductor layer and the oxidized oxide film 6 作为 as the back surface of the electric film, and is oriented toward the P-type germanium substrate 2 in the vertical direction with respect to the interface. In the region between the region of 5 nm and the region where the surface of the oxidized stone of the plasma membrane is advanced by 5 nm, the photoelectric conversion device of the present embodiment configured as described above is The characteristics have a tendency to be further improved. In the photoelectric conversion device of the present invention, it is preferred that the back surface dielectric 143168.doc 201015731 film is in the vicinity of the interface with the semiconductor layer and contains a positive or negative fixed charge contained in the surface dielectric film. The impurity is a fixed charge impurity of opposite polarity, but as long as at least a part of the impurity exists from the interface between the semiconductor layer and the back surface dielectric film, and proceeds toward the semiconductor layer side in a direction perpendicular to the interface. The region between nm and the region extending 5 nm toward the back dielectric film side may be used. The descriptions other than the above in the present embodiment are the same as those in the embodiment and the embodiment 10, and thus the description thereof will be omitted.

&lt;實施形態12&gt; 圖12中表示本發明之光電轉換裝置之另一例之剖面示意 圖。圖12所示之構成之本實施形態之光電轉換裝置具有: 下構成：包含作為第i半導體層之薄膜碎層與薄媒矽 層12a之光入射側之表面相接合之作為第】介電質膜之氧化 石夕膜與薄膜碎層12a之與光入射側之表面為相反側之 背面相接合的料第2介電質膜之氧切賴；與氧化石夕 膜6b之背面相接合之作為第2半導體層之薄膜石夕層⑵的積 層結構° X ’亦可具有（包含正的固定電荷之氧切 膜)’(薄膜矽層)/(包含負的固定電荷之氧化矽膜)之週期結 構。 ，軋化矽膜6a在與薄膜矽層12a之界面附近含有成 :二固定電荷之雜質2〇。此處’於氧化矽膜“中，成為 !的固定電荷，雜質20係藉由離子化等而成為正的固定電 何因此在與氧化矽膜6a相接之薄膜矽思 按 寻膜矽層12a之光入射侧 表面的至卜部分區域上㈣發負電荷，從而誘發作為 143168.doc -59- 201015731 η型半導體而發揮功能之第1反轉層4a。 又，氧化石夕膜讣在與薄膜石夕層12a之界面附近及與薄膜 矽層12b之界面附近’含有成為負的固定電荷之雜質η。 此處’於氧化石夕膜6b中，成為負的固定電荷之雜質η係藉 由離子化等而成為負㈣定電荷，因此在與氧切膜帅 :之薄膜矽層12a之背面之至少一部分區域上會誘發正電 荷，從而誘發作為15型半導體而發揮功&amp;之第2反轉層4b’ 且在與氧切膜_目接之薄膜⑦層m之光人射側之表面 之至少-部分區域上會誘發正電荷從而誘發作為p型半 導體而發揮功能之第3反轉層4c。 進而’於薄膜矽層12b之背面上，接合有上述構成以外 之其他的積層結構，於該接合之積層結構之最外層上，在 與薄膜碎層12b之背面之界面附近，配置有含有成為正的 固定電荷之雜質20的氧切肢’於氧切膜&amp;中雜質2〇 成為正的固定電荷。藉此，於薄膜矽層12b之背面上會誘 負電荷從而誘發作為n型半導體而發揮功能之第4反轉 層4d。 因此於上述構成之本實施形態之光電轉換裝置中，藉 由在各半導體層與各半導體層之兩面上分別形成之反轉層 而形成有p-i-n結構之光電轉換層，從而成為由該光電轉換 層依序積層而成之構成。 再者，於以上所述中，正的固定電荷或者負的固定電荷 要至J存在於界面附近即可，因此亦可存在於氧化矽膜 中。 143168.doc 201015731 進而，於上述構成之積層結構之一方之側面上，設置有 作為第1導電型半導體層之n型半導體層17，於上述構成之 積層結構之另一方之側面上，設置有作為第2導電型半導 體層之Ρ型半導體層16，於η型半導體層1.7及ρ型半導體層 16上分別設置有未圖示之電極。 使光入射至上述構成之本實施形態之光電轉換裝置中， 藉此，於薄膜矽層12a上所生成之載體中，電子向含有成 為的固疋電荷之雜質20之氧化碎膜6a側移動，並且通過 氧化石夕膜6a及η型半導體層ρ而自設置於n型半導體層17上 之電極中取出。另一方面，於薄膜矽層12a上所生成之載 體中，電洞向含有成為負的固定電荷之雜質21之氧化矽膜 6b側移動，並且通過氧化矽膜讣及卩型半導體層16而自設 置於P型半導體層16上之電極中取出。 同樣地，使光入射至上述構成之本實施形態之光電轉換 裝置中，藉此，於薄膜矽層12b中所生成之載體中，電子 向含有成為正的固定電荷之雜質2〇之氧化矽膜&amp;側移動， 並且通過氧化矽膜6c及η型半導體層ρ而自設置於n型半導 體層17上之電極中取出。另一方面，於薄膜矽層12b中所 生成之載體中，電洞向含有成為負的固定電荷之雜質21之 氧化矽膜6b側移動，並且通過氧化矽膜讣及卩型半導體層 16而自权置於ρ型半導體層16上之電極中取出。 利用以上機構進行之載體之取出，可藉由在構成本實施 形態之光電轉換裝置之積層結構的各半導體層及各介電質 膜上進行而將載體自本實施形態之光電轉換裝置取出至外 143168.doc -61- 201015731 部。 以下，對圖12所千+诚L、 μ構成之本實施形態的光電轉換裝置 2=法之一例進行說明。首先，於基板之表面上形 、積層結構重複三個週期之積層結構體。 c=等積層結構體例如可藉由如下方法而形成：利用 m 麵基板等之特定基板之表面上，依序 積層3有成為負的固 層、含有… 雜質之氧化矽膜、薄膜矽 層。 ‘&quot;、的固定電荷之雜質之氧切膜以及薄膜發 再者’作為向氧化矽膜中導入成為 或者成為負的固定雷^“ 疋电仃之雜質 m- 質的方法，例如可藉由如下方 利用CVD法等形成薄膜石夕層之後， 為正的固定電荷之雜質 战 質之離μ。 #之離子或者成為負的固定電荷之雜 X ’可在薄膜#層上塗佈例如氫氧化铯水溶 二固定==!者氫氧化銘水溶液等之含有成為正或 參 形成氧其乾燥後，~ 固定電荷之雜質之氧等之成為正或負的 來形成，該薄媒梦層係利用二佈藉由黏合薄㈣層 右η…㈣利用離子佈植等而於表面形成有含 有成為正的以電荷之_之氧切膜者 =在軸板之表面形成氧切膜之後，利=; 佈植等將成為固定電荷之雜質導入至氧化石夕膜中並進行退 火。其次，亦可藉由智切（smart cut)法等來剝離單晶石夕基 板之表面從而依序積層於玻璃基板等上。 143168.doc -62- 201015731 接下來，去除上述積層結構體之一部分而使基板表面之 一部分露出。此處’上述積層結構體之去除可藉由例如蝕 刻等來進行。 接下來，例如圖13之剖面示意圖所示，使n型半導體層 17及ρ型半導體層16分別堆積於上述積層結構體之去除部 分上。此處，η型半導體層17及Ρ型半導體層16例如分別可 以CVD法等而堆積。 其後，例如圖13所示，於η型半導體層17之表面上形成η 型用電極18，並且於ρ型半導體層16之表面上形成層ρ型用 電極19。此處，η型用電極以及卩型用電極19分別可藉由例 如分別蒸鍍η型用電極18中所用之金屬及卩型用電極19中所 用之金屬等而形成。 最後，例如沿著圖13所示之虛線分別切斷η型半導體層 17及Ρ型半導體層16，藉此可製作圖12所示之構成之本實 施形態的光電轉換裝置。又，亦可不切斷η型半導體層17 ρ 及ρ型半導體層16來適當形成配線。 於由以上方式所製作之上述構成之本實施形態的光電轉 換裝置中，氧化矽膜6a與薄膜矽層12a相接，氧化矽膜6b 與薄膜矽層12a及薄膜矽層12b之兩者相接。 因此，在上述構成之本實施形態之光電轉換裝置中，與 設=有含固定電荷之第二層、及在與半導體表面之間不含 固定電荷之第-層之構成的專利文⑴所揭示之太陽電池 相比更今易在第1反轉層4a、第2反轉層4b、第3反轉層 4c及第4反轉層4d等之反轉層上高密度地誘發正或負的電 143168.doc • 63 - 201015731 荷’使作為η型半導體或p型半導體之功能得以提高，故可 抑制各半導體層之表面上之載體的再結合等，藉此，光電 轉換效率等之光電轉換裝置之特性會得到提高。 又’於上述構成之本實施形態之光電轉換裝置中，於薄 膜矽層12a及薄膜矽層12b等之半導體層之光入射側之表面 上’設置有作為η型半導體或p型半導體而發揮功能之反轉 層來代替成為短波長光之吸收源的η+層或ρ +層，藉此，與 層或者ρ+層相比，更可抑制短波長之光的吸收，因此可 使光電轉換效率等之光電轉換裝置之特性得到進一步提 ❹ 高0 又，於上述構成之本實施形態之光電轉換裝置中，可根 據氧化矽膜等之介電質膜與薄膜矽層等之半導體層之界面 上的成為i或負_定電荷之雜質之偏析4，來控制反 層上所誘發之正電荷或負電荷之密度。&lt;Embodiment 12&gt; Fig. 12 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention. The photoelectric conversion device of the present embodiment having the configuration shown in Fig. 12 has a structure in which a film layer including the i-th semiconductor layer is bonded to the surface of the light incident side of the thin dielectric layer 12a as a dielectric. The oxygen etch of the second dielectric film of the oxide oxide film of the film and the back surface of the film fragment 12a on the opposite side to the surface on the light incident side; and the back surface of the oxidized stone film 6b The laminated structure of the thin film layer (2) of the second semiconductor layer ° X ' may also have a period (a thin film containing a positive fixed charge) '(film tantalum layer) / (a negatively charged fixed tantalum oxide film) structure. The rolled tantalum film 6a contains two impurities of a fixed charge in the vicinity of the interface with the thin film layer 12a. Here, in the 'yttrium oxide film', it becomes a fixed charge, and the impurity 20 is a positive fixed electricity by ionization or the like. Therefore, in the film which is in contact with the yttrium oxide film 6a, the film 12a is formed. On the inferior portion of the light incident side surface, (4) is negatively charged, thereby inducing the first inversion layer 4a functioning as a 143168.doc -59-201015731 n-type semiconductor. Further, the oxidized stone is in the film and the film The vicinity of the interface of the layer 12a and the vicinity of the interface with the thin film layer 12b 'containing an impurity η which becomes a negative fixed charge. Here, in the oxide oxide film 6b, the impurity η which becomes a negative fixed charge is ion-based. Since it becomes a negative (four) constant charge, a positive charge is induced in at least a part of the back surface of the thin film layer 12a of the oxygen film, and the second reversal of the work is induced as a type 15 semiconductor. The layer 4b' induces a positive charge on at least a partial region of the surface of the light-emitting side of the film 7 layer m of the oxygen film, thereby inducing the third inversion layer 4c functioning as a p-type semiconductor. Further on the back side of the film layer 12b The laminated structure other than the above-described configuration is joined, and an oxygen-cutting body containing the impurity 20 which becomes a positive fixed charge is disposed in the vicinity of the interface with the back surface of the film fragment 12b on the outermost layer of the bonded laminated structure. In the oxygen cut film &amp; the impurity 2〇 becomes a positive fixed charge. Thereby, a negative charge is induced on the back surface of the thin film germanium layer 12b, thereby inducing the fourth inversion layer 4d functioning as an n-type semiconductor. In the photoelectric conversion device according to the embodiment of the present invention, the photoelectric conversion layer having the pin structure is formed by the inversion layer formed on each of the semiconductor layer and each of the semiconductor layers, and the photoelectric conversion layer is formed by the photoelectric conversion layer. Further, in the above description, a positive fixed charge or a negative fixed charge may exist until J exists in the vicinity of the interface, and thus may also exist in the ruthenium oxide film. 143168.doc 201015731 Further On the side of one of the laminated structures having the above-described configuration, an n-type semiconductor layer 17 as a first conductive semiconductor layer is provided, and the other of the laminated structures of the above configuration is provided. On the side surface, a 半导体-type semiconductor layer 16 as a second-conductivity-type semiconductor layer is provided, and an electrode (not shown) is provided on each of the n-type semiconductor layer 1.7 and the p-type semiconductor layer 16. The light is incident on the above-described configuration. In the photoelectric conversion device of the form, in the carrier formed on the thin film layer 12a, electrons move toward the side of the oxidized particle 6a containing the impurity 20 which becomes a solid charge, and pass through the oxidized stone film 6a and η. The semiconductor layer ρ is taken out from the electrode provided on the n-type semiconductor layer 17. On the other hand, in the carrier formed on the thin film layer 12a, the hole is erbium oxide containing the impurity 21 which becomes a negative fixed charge. The film 6b side is moved, and is taken out from the electrode provided on the P-type semiconductor layer 16 by the yttrium oxide film and the ytterbium-type semiconductor layer 16. In the same manner, the light is incident on the photoelectric conversion device of the present embodiment configured as described above, whereby the electrons are supplied to the carrier formed in the thin film layer 12b, and the electrons are erbium oxide film containing an impurity which becomes a positive fixed charge. The &amp; side is moved and taken out from the electrode provided on the n-type semiconductor layer 17 by the yttrium oxide film 6c and the n-type semiconductor layer ρ. On the other hand, in the carrier formed in the thin film layer 12b, the hole moves toward the yttrium oxide film 6b side containing the impurity 21 which becomes a negative fixed charge, and passes through the yttrium oxide film and the ytterbium-type semiconductor layer 16 The weight is taken out of the electrode on the p-type semiconductor layer 16. By taking out the carrier by the above-described mechanism, the carrier can be taken out from the photoelectric conversion device of the present embodiment by performing on each of the semiconductor layers and the dielectric films constituting the laminated structure of the photoelectric conversion device of the present embodiment. 143168.doc -61- 201015731 Department. Hereinafter, an example of the photoelectric conversion device 2 = method of the present embodiment which is constituted by the thousands of +, L, and μ of Fig. 12 will be described. First, a three-cycle laminated structure is formed on the surface of the substrate and the laminated structure is repeated. The laminated structure of c = is formed by, for example, a surface of a specific substrate such as an m-plane substrate, and the ordered layer 3 has a negative solid layer, a hafnium oxide film containing an impurity, and a thin film layer. '&quot;, a fixed-charge impurity, an oxygen-cut film, and a thin film-derived method, as a method of introducing an impurity m-type which becomes or becomes a negative fixed-thickness to the yttrium oxide film, for example, by After the thin film layer is formed by the CVD method or the like below, the impurity of the positive fixed charge is separated from the impurity. The ion of # or the negative fixed charge X' can be coated on the film # layer, for example, oxidized.铯Water-soluble two fixed ==! The hydroxide aqueous solution or the like is formed into positive or ginseng-forming oxygen, and after drying, the oxygen of the fixed-charge impurity is positive or negative, and the thin-film dream layer is utilized. The cloth is bonded to the thin (four) layer right η... (4) by ion implantation or the like, and the surface is formed with a positively charged oxygen film; after forming an oxygen film on the surface of the shaft plate, An impurity such as a fixed charge is introduced into the oxidized oxide film and annealed. Secondly, the surface of the single crystal substrate may be peeled off by a smart cut method or the like, and sequentially laminated on a glass substrate or the like. On. 143168.doc -62- 201015731 To remove a portion of the laminated structure to expose a portion of the surface of the substrate. Here, the removal of the laminated structure may be performed by, for example, etching. Next, for example, as shown in the cross-sectional view of FIG. 13, the n-type is made. The semiconductor layer 17 and the p-type semiconductor layer 16 are respectively deposited on the removed portion of the laminated structure. Here, the n-type semiconductor layer 17 and the Ρ-type semiconductor layer 16 can be deposited by, for example, a CVD method, etc. Thereafter, for example, FIG. As shown, an n-type electrode 18 is formed on the surface of the n-type semiconductor layer 17, and a layer p-type electrode 19 is formed on the surface of the p-type semiconductor layer 16. Here, the n-type electrode and the 卩-type electrode 19 are formed. For example, the metal used in the n-type electrode 18 and the metal used in the ruthenium-type electrode 19 can be formed by, for example, respectively. Finally, the n-type semiconductor layer 17 is cut, for example, along the broken line shown in FIG. The 半导体-type semiconductor layer 16 can be used to fabricate the photoelectric conversion device of the embodiment shown in Fig. 12. Alternatively, the n-type semiconductor layer 17p and the p-type semiconductor layer 16 can be formed without being cut. In the photoelectric conversion device of the present embodiment having the above-described configuration, the yttrium oxide film 6a is in contact with the film ruthenium layer 12a, and the ruthenium oxide film 6b is in contact with both the film ruthenium layer 12a and the film ruthenium layer 12b. Therefore, in the photoelectric conversion device of the present embodiment configured as described above, the patent (1) of the configuration including the second layer having a fixed charge and the first layer having no fixed charge between the surface and the semiconductor surface is provided. The disclosed solar cell is more likely to induce positive or negative density on the inversion layers of the first inversion layer 4a, the second inversion layer 4b, the third inversion layer 4c, and the fourth inversion layer 4d, etc., compared with the solar cell disclosed. 143168.doc • 63 - 201015731 The function of the n-type semiconductor or the p-type semiconductor is improved, so that recombination of the carrier on the surface of each semiconductor layer can be suppressed, whereby photoelectricity such as photoelectric conversion efficiency can be suppressed. The characteristics of the conversion device will be improved. Further, in the photoelectric conversion device of the present embodiment, the surface of the semiconductor layer such as the thin film layer 12a and the thin film layer 12b is provided with an n-type semiconductor or a p-type semiconductor. The inversion layer is used instead of the η+ layer or the ρ + layer which is an absorption source of short-wavelength light, whereby the absorption of light of a short wavelength can be suppressed as compared with the layer or the ρ+ layer, thereby making photoelectric conversion efficiency Further, in the photoelectric conversion device of the present embodiment configured as described above, the photoelectric conversion device such as the ruthenium oxide film or the semiconductor layer such as the thin film layer can be used. The segregation 4 of the impurity of i or negative _ fixed charge controls the density of the positive or negative charge induced on the reverse layer.

又，於上述構成之本實施形態之光電轉換裝置中，使 膜夕層12a之光入射侧之表面上的界面能階因第!反轉層 上所誘發之負電荷而終止，藉此可抑制薄財層l2a之 人射侧之表面之界面能階上的載體之再結合，從而可使 電轉換效率等之光電轉換裝置之特性得到進—步提高。 又’於以上所述中，對於第1半導體層及第2半導體層， =用薄财層，但該薄膜Further, in the photoelectric conversion device of the present embodiment configured as described above, the interface energy level on the surface on the light incident side of the film layer 12a is terminated by the negative charge induced on the first inversion layer, thereby suppressing The recombination of the carriers on the interface level of the surface of the person on the side of the thin layer of the thin layer l2a enables the characteristics of the photoelectric conversion device such as the electric conversion efficiency to be further improved. Further, in the above description, for the first semiconductor layer and the second semiconductor layer, a thin layer is used, but the film is used.

矽或微晶矽中之住—土 日日7非E ^ , —者所構成，亦可由除矽以外之立他穿 類之半導體所構成之”他# 發、或者單晶”多曰=7”包含…、多』 ’丹夕晶矽之混合體等。 143168.doc -64 - 201015731 又，上述積層結構之各半導體層之材質可各不相同。例 如，亦可形成為自光入射側起依序含有非晶矽、多晶矽及 早晶梦之構成。 又，當各半導體層中分別使用有結晶矽時，上述積層結 構可藉由例如使形成有上述介電質膜之結晶矽彼此黏合等 來製作。 又，於上述構成之本實施形態之光電轉換裝置中，較好 的是，靠近光入射側之半導體層之帶隙為相較該半導體層 9 t遠離光入射側之半導體層之帶隙以上。由於形成為如上 所述之可自光入射侧起依序吸收短波長光至長波長光之半 導體層的積層結構，故而入射至本實施形態之光電轉換裝 置中之光的吸收量會變大，因此光電轉換效率等之本實施 形態之光電轉換裝置的特性有提高之傾向。 成為如上所述之帶隙之關係的半導體層之積層結構可舉 出例如：自光入射侧起積層有非晶碳化矽、非晶矽及微晶 .矽之結構、以及自光入射侧起積層有非晶碳化矽非晶矽 及非晶矽鍺之結構。 較好的是，構成上述積層結構之至少一層之半導體層之 厚度相較Μ導體層内之載體擴散長度更薄。於此情形 時，可有效抑財導體層内之載體之再結纟，並且藉由如 本實％形態般形成為積層結構，亦可提高所入射之光被吸 收之概率。 又，於以上所述中，對於第1介電質膜及第2介電質膜等 之構成上述積層結構之介電質膜，使用有氧化石夕膜， 143168.doc -65· 201015731 ’’’、並不限疋於此’亦可使用例如選自由氧化矽、氮氧化矽 及氮化矽所組成之群中之至少一種。 又’作為第1介電質膜及第2介電質膜等之構成上述積層 結構之介電質膜’較好的是使用帶隙為4 2 ev以上之介電The 矽 or the microcrystalline 矽 — 土 土 土 土 土 土 7 7 7 7 7 7 7 7 7 7 7 7 7 土 土 土 土 土 土 土 土 土 土 土 土 土 他 他 他 他 他 他 他 他 他 他 他 他 他In addition, the material of each of the semiconductor layers of the above-mentioned laminated structure may be different. For example, it may be formed from the light incident side. In the case where crystal ruthenium is used for each of the semiconductor layers, the layered structure can be produced by, for example, bonding the crystallization ruths in which the dielectric film is formed to each other. Further, in the photoelectric conversion device of the present embodiment configured as described above, it is preferable that a band gap of the semiconductor layer close to the light incident side is larger than a band gap of the semiconductor layer 9 t away from the light incident side. Since the laminated structure which sequentially absorbs the short-wavelength light to the semiconductor layer of the long-wavelength light from the light incident side as described above is formed, the amount of light incident on the photoelectric conversion device of the present embodiment becomes large. ,therefore The characteristics of the photoelectric conversion device of the present embodiment, such as the electrical conversion efficiency, tend to be improved. The laminated structure of the semiconductor layer having the relationship of the band gap as described above may be, for example, an amorphous carbonized carbide layer deposited from the light incident side. The structure of the amorphous germanium and the microcrystals, and the structure of the amorphous tantalum carbide and the amorphous germanium are laminated from the light incident side. Preferably, the semiconductor layer constituting at least one of the above laminated structures is formed. The thickness of the carrier is thinner than that of the carrier in the conductor layer. In this case, the re-crusting of the carrier in the conductor layer can be effectively suppressed, and can be formed into a laminated structure by the present embodiment. In addition, as described above, in the dielectric film which constitutes the laminated structure of the first dielectric film and the second dielectric film, the oxidized film is used. 143168.doc -65· 201015731 ''', and is not limited thereto, may also use, for example, at least one selected from the group consisting of cerium oxide, cerium oxynitride, and cerium nitride. Electrochemical film and second dielectric Etc. constituting the dielectric film of the laminated structure 'is preferably less than the band gap of the dielectric 4 2 ev

質膜。例如，太陽光之大部分係由具有3〇〇 nm以上之波長 之光民構成，故而當使用帶隙為4 2 eV 使太陽光入射時，可抑制具有一以上之波長 被’丨電質膜所吸收，從而轉換損失變少，因此光電轉換裝 置之特性有進一步提高之傾向。 又’於以上所述中，成為正的固定電荷之雜質可使用例 如包含選自由鋰、鈉'鉀、铷、鎚、鎂、鈣、勰、鋇、 磷、砷及銻所組成之群中之至少一種者。 成為負的固定電荷之雜質可使用例如包含選自由侧、 鋁、鎵、銦、鉑、氟化富勒烯、氧化富勒烯、氣、氣溴 及蛾所組成之群中之至少一種者。 又，於上述構成之本實施形態之光電轉換裝置中，亦可 調換P型與η型之導電型，並且調換固定電荷之極性。 又，於上述構成之本實施形態之光電轉換裝置中，較好 的疋，上述雜質存在最多之部位係位於從半導體層與介電 質膜之界面起在相對於该界面而垂直之方向上朝著半導 體層侧前進5 nm之區域、與朝著介電質膜側前進5⑽之區 域之間的區域上。於此情形時，上述構成之本實施形態之 光電轉換裝置之特性有進一步提高之傾向。 即〃要各介電質膜中之成為正或負的固定電荷之雜質 143168.doc •66- 201015731 之至少一部分係存在於從半導體層與介電質膜之界面起， 在相對於該界面而垂直之方向上朝著半導體層側前進5 之區域、與朝著介電質膜側前進5 nm之區域之間的區域上 即可。 又’於上述構成之本實施形態之光電轉換裝置中，者 田 然’既可使薄膜石夕層12a之光入射侧之氧化硬膜6a作為抗 反射膜而發揮功能’亦可於氧化矽膜6&amp;之表面形成紋理結 構及/或蛾眼結構等。 又 S然，上述構成之本實施形態之光電轉換裝置中的 半導體層之數量及介電質膜之數量並非係限定於上述構成 者。 又，如上所述，於上述構成之本實施形態之光電轉換裝 置中’亦可調換η型與p型之導電型。再者，當上述構成之 本實施形態之光電轉換裝置中已調換η型與ρ型之導電型之 情形時，正與負的電荷極性亦會被調換。 &lt;實施形態13&gt; 圖27中表示本發明之光電轉換裝置之另一例之剖面示意 圖。圖27所示之構成之本實施形態的光電轉換裝置具有自 光入射側起依序積層作為第i半導體層之第1非晶矽層2a、 作為第2半導體層之第2非晶矽層2b、及作為第3半導體層 之第3非晶碎層2c所成的積層結構。 此處’以與第1非晶矽層2a之光入射側之表面相接之方 式而設置有作為介電質膜即表面介電質膜之氧化石夕膜6, 且氧化硬膜6係在與第1非晶矽層2a之界面附近，含有成為 143168.doc -67- 201015731 正的固定電荷之雜質的已離子化之铯5。 又，铯5係在與第！非晶矽層以之光入射側之表面之界面 附近經離子化而成為正的固^電冑’故而在與氧化石夕膜6 相接之第1非晶矽層2a之光入射側之表面之至少一部分區 域上會誘發負電荷，從而誘發作為n型半導體而發揮功能 之表面反轉層4。 又，於氧化矽膜6之光入射側之表面上設置有透明導電 膜9，於透明導電膜9之光入射側之表面上設置有作為透明 基板之玻璃基板14。 進而，在第1非晶矽層2a之與光入射側之表面為相反側 之背面上形成有作為第1導電型雜質含有層之p型層ι〇9，p 型層109係作為p型半導體而發揮功能。 又，於第2非晶矽層2b之光入射側之表面上形成有作為 第2導電型雜質含有層之n型層11〇，在第2非晶矽層沘之與 光入射側之表面為相反側之背面上形成有作為第丨導電型 雜質含有層之p型層U1。此處，n型層11〇係作為n型半導 體而發揮功能，p型層111係作為p型半導體而發揮功能。 又，於第3非晶矽層2c之光入射側之表面上形成有作為 第2導電型雜質含有層之n型層112，於第2非晶矽層沘之與 光入射側之表面為相反側之背面上形成有作為第1導電型 雜質含有層之ρ型層113。此處，η型層U2係作為η型半導 體而發揮功能，ρ型層113係作為ρ型半導體而發揮功能。 進而，以與第3非晶矽層2c之背面之ρ型層113之背面相 接的方式而設置有背面電極7。 I43I68.doc • 68 - 201015731 並且，將第1非晶矽層2a之背面之口型層1〇9、與第2非晶 矽層2b之光入射側之表面之n型層11〇加以接合。又，將第 2非晶矽層2b之背面的ρ型層m、與第3非晶矽層以之光入 射側之表面之η型雜質含有層即n型層112加以接合。藉由 該等之接合而構成自光入射側起依序積層有第丨非晶矽層 2a、第2非晶矽層2b、及第3非晶矽層〜所成之積層結構。 藉由使光入射至如上所述之構成之本實施形態的光電轉 換裝置而產生之載體，係自光入射側之透明導電膜9及背 面側之背面電極7分別取出至外部，但於光入射側，載體 係利用穿隧效應等通過氧化石夕膜6中而自透明導電膜9被取 出。 以下，對圖27所示之構成的本實施形態之光電轉換裝置 之製造方法之一例進行說明。首先，於玻璃基板14之成為 與光入射側之表面為相反側之背面的表面上形成透明導電 膜9 ^此處，透明導電膜9之形成可藉由例如使用濺鍍法、 蒸鍍法或溶膠凝膠法等，於玻璃基板14之成為與光入射側 之表面為相反側之背面的表面上形成ITO(Indium Tin Oxide)、IO(Indium Oxide，氧化銦）、TO(Tin 〇xide，氧化 錫）或者ZO(Zinc Oxide ’氧化鋅）等來進行。 其次，於鉋5配置後的透明導電膜9之成為與光入射側之 表面為相反側之背面的表面上形成氧化碎膜6 ^此處，氧 化石夕膜6可藉由例如CVD(Chemical Vapor Deposition)法、 ALD(Atomic Layer Deposition)法或者暴露於含有氧之環境 中之方法等來形成。 143168.doc •69· 201015731 ^次，於^切模6之成為與光入射侧之表面為相反側 之背面的表面上配置成為正的固定電荷之雜質鉋5。此 處：鉋5可利用例如於氧化矽膜6上塗佈氣化鉋水溶液或者 $氧化鎚水溶液等之含有铯之溶液的方法、或者暴露於絶 蒸氣中之方法等而配置於氧化矽膜6上。 又，亦可代替將绝5配置於氧化石夕膜6上，而於形成氧化 矽膜6時，例如使在CVD法或⑽法等尹使用之氧 之原料氣體中含有绝，藉此使氧化矽膜6中含有铯。、 其次’於氧化矽膜6之成為與光入射侧之表面為相反側 之背面的表面上’依序積層第】非晶梦層2a&amp;型層⑽。 此處，該等之層例如可利用CVD法等形成非捧雜之非晶石夕 膜從而形成第1非晶發層23之後，形成摻雜有料之p型雜 質之P型非晶矽臈，藉此形成p型層1〇9而依序積層。 再者’由P型雜質之摻雜而形成p型非晶石夕膜係可藉由例 如在非晶麥膜之原料氣體中混入有含p型雜質之推雜氣體 (例如’二棚烧等）之狀態下成膜非晶石夕膜來進行。再者， 作為P型雜質，可使用例如硼、鋁、鎵或銦等。 其次，於P型層⑽之成為與光人射側之表面為相反側之 =的表面上’依序積層n型層⑽、第2非_層加 型層川。此處，該等之層例如可藉由如下方式而積層. ^用CVD法等’在非晶石夕膜之原料氣體中混入有含打型雜 質之摻雜氣艘(例如’膦或胂等)之狀態下成膜 以形成η型層Π。之後，停止n型雜質之換雜而形成非推： 之非晶矽膜，從而形成第2非晶矽層孔，進而，在非 143168.doc -70· 201015731 膜之原料氣體中混人有包含p型雜 硼烷等）之狀態下成膜非晶矽膜藉 .' 、（例如，二 柯Λ形成p型層n】笙 _ 者，作為η型雜質，可使用例如磷、砷或銻等 寺。再 其次，於ρ型層111之成為與光入 .b 】之表面為相反你丨夕 身面的表面上，依序積層n型層U2、笛Plasma membrane. For example, most of the sunlight is composed of lighters having a wavelength of 3 〇〇 nm or more. Therefore, when the solar band is incident with a band gap of 4 2 eV, it is possible to suppress the wavelength of more than one wavelength. Since the absorption is reduced, the conversion loss is reduced, and thus the characteristics of the photoelectric conversion device tend to be further improved. Further, in the above description, the impurity which becomes a positive fixed charge may be, for example, a group selected from the group consisting of lithium, sodium 'potassium, strontium, hammer, magnesium, calcium, strontium, barium, phosphorus, arsenic and antimony. At least one kind. The impurity which becomes a negative fixed charge can be, for example, at least one selected from the group consisting of a side, aluminum, gallium, indium, platinum, fluorinated fullerene, oxidized fullerene, gas, gas bromine and moth. Further, in the photoelectric conversion device of the present embodiment configured as described above, the P-type and n-type conductivity types can be exchanged, and the polarity of the fixed charges can be changed. Further, in the photoelectric conversion device of the present embodiment configured as described above, it is preferable that the most abundant portion of the impurity is located in a direction perpendicular to the interface from the interface between the semiconductor layer and the dielectric film. The region on the side of the semiconductor layer is advanced by 5 nm and the region between the region 5 (10) advancing toward the dielectric film side. In this case, the characteristics of the photoelectric conversion device of the present embodiment configured as described above tend to be further improved. That is, at least a part of the impurity 143168.doc • 66- 201015731 which is a positive or negative fixed charge in each dielectric film exists from the interface between the semiconductor layer and the dielectric film, and is opposite to the interface. The region between the region advancing 5 toward the semiconductor layer side in the vertical direction and the region advancing 5 nm toward the dielectric film side may be used. Further, in the photoelectric conversion device of the present embodiment, the oxidized hard film 6a on the light incident side of the thin film layer 12a functions as an antireflection film. The surface of 6&amp; forms a texture structure and/or a moth-eye structure. Further, the number of semiconductor layers and the number of dielectric films in the photoelectric conversion device of the present embodiment configured as described above are not limited to the above-described constitution. Further, as described above, in the photoelectric conversion device of the present embodiment configured as described above, the n-type and p-type conductivity types can be replaced. Further, in the case where the n-type and p-type conductivity types are replaced in the photoelectric conversion device of the above-described configuration, the positive and negative charge polarities are also exchanged. &lt;Embodiment 13&gt; Fig. 27 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention. In the photoelectric conversion device of the present embodiment, which is configured as shown in FIG. 27, the first amorphous germanium layer 2a as the i-th semiconductor layer and the second amorphous germanium layer 2b as the second semiconductor layer are sequentially stacked from the light incident side. And a laminated structure formed as the third amorphous fracture layer 2c of the third semiconductor layer. Here, 'the oxidized oxide film 6 which is a surface dielectric film which is a dielectric film is provided in contact with the surface on the light incident side of the first amorphous germanium layer 2a, and the oxidized hard film 6 is attached thereto. In the vicinity of the interface with the first amorphous germanium layer 2a, the ionized germanium 5 which is an impurity of 143168.doc -67 - 201015731 positive fixed charge is contained. Also, 铯5 is in the same line! The surface of the amorphous amorphous layer which is ionized by the vicinity of the interface on the light incident side is positively charged, so that the surface of the first amorphous germanium layer 2a which is in contact with the oxidized oxide film 6 is incident on the light incident side. A negative charge is induced in at least a portion of the region to induce the surface inversion layer 4 functioning as an n-type semiconductor. Further, a transparent conductive film 9 is provided on the surface on the light incident side of the ruthenium oxide film 6, and a glass substrate 14 as a transparent substrate is provided on the surface on the light incident side of the transparent conductive film 9. Further, a p-type layer ι 9 as a first conductivity type impurity-containing layer is formed on the back surface of the first amorphous germanium layer 2a opposite to the surface on the light incident side, and the p-type layer 109 is used as a p-type semiconductor. And play the function. Further, an n-type layer 11 as a second conductivity type impurity-containing layer is formed on the surface on the light incident side of the second amorphous germanium layer 2b, and the surface of the second amorphous germanium layer on the light incident side is On the back side of the opposite side, a p-type layer U1 as a second-electrode-type impurity-containing layer is formed. Here, the n-type layer 11 functions as an n-type semiconductor, and the p-type layer 111 functions as a p-type semiconductor. Further, an n-type layer 112 as a second conductivity type impurity-containing layer is formed on the surface on the light incident side of the third amorphous germanium layer 2c, and is opposite to the surface on the light incident side of the second amorphous germanium layer A p-type layer 113 as a first conductivity type impurity-containing layer is formed on the back surface of the side. Here, the n-type layer U2 functions as an n-type semiconductor, and the p-type layer 113 functions as a p-type semiconductor. Further, the back surface electrode 7 is provided in contact with the back surface of the p-type layer 113 on the back surface of the third amorphous germanium layer 2c. I43I68.doc • 68 - 201015731 Further, the lip layer 1〇9 on the back surface of the first amorphous germanium layer 2a is bonded to the n-type layer 11 on the surface on the light incident side of the second amorphous germanium layer 2b. Further, the p-type layer m on the back surface of the second amorphous germanium layer 2b and the n-type layer 112 which is an n-type impurity containing layer on the surface on the light incident side of the third amorphous germanium layer are bonded. By these joining, a laminated structure in which the second amorphous germanium layer 2a, the second amorphous germanium layer 2b, and the third amorphous germanium layer are formed in this order from the light incident side is formed. The carrier generated by the photoelectric conversion device of the present embodiment configured as described above is taken out from the transparent conductive film 9 on the light incident side and the back electrode 7 on the back side, respectively, but is incident on the outside. On the side, the carrier is taken out from the transparent conductive film 9 through the oxidized stone film 6 by a tunneling effect or the like. Hereinafter, an example of a method of manufacturing the photoelectric conversion device of the present embodiment having the configuration shown in Fig. 27 will be described. First, a transparent conductive film 9 is formed on the surface of the glass substrate 14 which is the back surface opposite to the surface on the light incident side. Here, the transparent conductive film 9 can be formed by, for example, sputtering, evaporation, or In the sol-gel method or the like, ITO (Indium Tin Oxide), IO (Indium Oxide), and TO (Tin 〇xide) are formed on the surface of the glass substrate 14 which is on the opposite side to the surface on the light incident side. Tin) or ZO (Zinc Oxide 'zinc oxide) or the like. Next, an oxide film 6 is formed on the surface of the transparent conductive film 9 disposed on the opposite side to the surface on the light incident side after the planer 5 is disposed. Here, the oxidized film 6 can be by, for example, CVD (Chemical Vapor) Deposition) method, ALD (Atomic Layer Deposition) method or a method of exposure to an environment containing oxygen, etc. are formed. 143168.doc •69· 201015731 ^, the impurity planer 5 which is a positive fixed charge is disposed on the surface of the back surface of the cutting die 6 which is opposite to the surface on the light incident side. Here, the planer 5 can be disposed on the yttrium oxide film 6 by, for example, a method of applying a vaporized planing aqueous solution or a solution containing cerium, such as a cerium oxide solution, or a method of exposing it to a vapor. on. Further, instead of disposing the anode 5 on the oxidized stone film 6, when the yttrium oxide film 6 is formed, for example, it is contained in the raw material gas of oxygen used in the CVD method or the (10) method, thereby oxidizing The ruthenium film 6 contains ruthenium. Then, the first amorphous layer 2a &amp; type layer (10) is sequentially laminated on the surface of the ruthenium oxide film 6 which is opposite to the surface on the light incident side. Here, the layers may be formed by forming a non-nosed amorphous film by a CVD method or the like to form a first amorphous layer 23, and then forming a P-type amorphous germanium doped with a p-type impurity. Thereby, the p-type layer 1〇9 is formed and sequentially laminated. Further, the formation of a p-type amorphous austenite film by doping with a P-type impurity can be carried out, for example, by mixing a dopant gas containing a p-type impurity into a material gas of an amorphous wheat film (for example, 'two sheds, etc. In the state of forming a film of amorphous austenite, it is carried out. Further, as the P-type impurity, for example, boron, aluminum, gallium or indium can be used. Next, on the surface of the P-type layer (10) which is opposite to the surface on the light-emitting side, the n-type layer (10) and the second non-layer-added layer are sequentially laminated. Here, the layers may be laminated, for example, by a CVD method or the like, in which a dopant gas containing a type impurity is mixed in a material gas of an amorphous stone film (for example, 'phosphine or ruthenium, etc. The film is formed in a state to form an n-type layer. Thereafter, the substitution of the n-type impurity is stopped to form a non-pushing amorphous germanium film, thereby forming a second amorphous germanium layer hole, and further, the raw material gas of the film is not included in the non-143168.doc-70·201015731 film. In the state of a p-type heteroborane or the like, a film-forming amorphous germanium film is formed by using, for example, a bis-type impurity, for example, phosphorus, arsenic or antimony. Temple. Secondly, on the surface of the p-type layer 111 which is opposite to the surface of the light into the .b], the n-type layer U2, the flute is sequentially laminated.

昂3非晶石夕層2c以》« 型層1U。此處，該等之層例如 及P 错由如下方式而積層.Ang 3 amorphous stone layer 2c with "« type layer 1U. Here, the layers such as P and P are laminated as follows.

利用咖法等，形成摻雜有η型雜質之㈣㈣膜而形成 心層U2之後，停止η型雜質之摻雜而形成非摻雜之非曰 石夕膜，從而形成第3非晶碎“，進而形成摻雜有ρ型㈣曰 之Ρ型非晶石夕膜以形成ρ型層113等。 其次，於ρ型層113之成為與光入射側之表面為相反側之 背面的表面上形成背面電極7。此處，背面電極7可藉由例 如在㈣層⑴之成為與光人射側之表面為相反側之背面的 表面上蒸銀銘等之金屬等而形成。 最後，例如亦可於200〜5〇〇t之氫環境中進行退火。藉 此，懸鍵因氫而終止，故難以產生載體之再結合，從而^ 提高光電轉換效率》 再者，本發明中，亦可於背面電極7上以與上述相反之 積層順序而積層非晶石夕膜等。 於由以上方式所製作之上述構成之本實施形態的光電轉 換裝置令’氧化矽膜6與第1非晶矽層2a之光入射側之表面 相接’藉由在氧化矽膜6之與第1非晶矽層2a之光入射側之 表面之界面上已離子化之鉋5，而於第1非晶矽層2a之光入 射側之表面上形成表面反轉層4。 143168.doc •71 _ 201015731 因此’上述構成之本實施形態之光電轉換裝置中，與如 先前之專利文獻1之光電轉換裝置般的於半導體層之積層 結構之最上部設置有包含摻雜有雜質之半導體層的表面雜 質層之光電轉換裝置相比，表面雜質層中之短波長光之吸 收得到抑制，故而可使光電轉換效率等之光電轉換裝置之 特性得到提高。 又 3有成為正的固定電荷之雜質之已離子化之铯5的 氧化矽膜6係以與第丨非晶矽層2a之光入射側之表面相接之 方式而設置，可使已離子化之铯5作為成為正的固定電荷⑩ 之雜質而配置在與第i非晶石夕層2a之界面附近。藉此，於 第1非晶矽層2a之光入射側之表面上會高密度地誘發電子 而形成作為η型半導體之功能較高的表面反轉層4，因此， 由於第1非晶石夕層2a之光入射側之表面上之界面能階、或 者η型或p型雜質之能階等而導致的載體之再結合得到抑制 等’藉此，光電轉才奐效率等之光電#換裝置之特性會得到 又，先岫之專利文1之光電動勢元件中， ，在透明導電膜After forming the core layer U2 by forming a (4) (four) film doped with an n-type impurity by a method such as a coffee method, the doping of the n-type impurity is stopped to form an undoped non-germanium film, thereby forming a third amorphous chip, Further, a ruthenium-type amorphous ruthenium film doped with p-type (tetra) iridium is formed to form a p-type layer 113, etc. Next, a back surface is formed on the surface of the p-type layer 113 which is opposite to the surface on the light incident side. In this case, the back surface electrode 7 can be formed, for example, by evaporating a metal such as silver or the like on the surface of the (four) layer (1) which is on the opposite side to the surface on the light-emitting side. Annealing in a hydrogen atmosphere of 200 to 5 Torr, whereby the dangling bond is terminated by hydrogen, so that it is difficult to recombine the carrier, thereby improving the photoelectric conversion efficiency. Further, in the present invention, the back electrode may be used. In the seventh embodiment, the above-described configuration of the photoelectric conversion device of the above-described configuration is such that the yttrium oxide film 6 and the first amorphous germanium layer 2a are laminated. The surface of the light incident side is connected by 'on the yttrium oxide film 6 The surface of the first amorphous germanium layer 2a on the light incident side is ionized by the planer 5, and the surface inversion layer 4 is formed on the light incident side of the first amorphous germanium layer 2a. 143168.doc • In the photoelectric conversion device of the present embodiment of the above-described configuration, the semiconductor layer containing the impurity-doped semiconductor layer is provided on the uppermost portion of the laminated structure of the semiconductor layer as in the photoelectric conversion device of the prior patent document 1. In the photoelectric conversion device of the surface impurity layer, absorption of short-wavelength light in the surface impurity layer is suppressed, so that the characteristics of the photoelectric conversion device such as photoelectric conversion efficiency can be improved. Further, there is an impurity which becomes a positive fixed charge. The yttrium oxide film 6 of the ionized crucible 5 is provided in contact with the surface on the light incident side of the second amorphous germanium layer 2a, so that the ionized germanium 5 can be made to be a positive fixed charge 10 The impurity is disposed in the vicinity of the interface with the i-th amorphous layer 2a. Thereby, electrons are induced at a high density on the surface on the light incident side of the first amorphous germanium layer 2a to form a function as an n-type semiconductor. High In the surface reversal layer 4, the recombination of the carrier due to the interface energy level on the surface on the light incident side of the first amorphous layer 2a or the energy level of the n-type or p-type impurity is suppressed. 'Through this, the characteristics of the photoelectric conversion device, such as the photoelectric conversion efficiency, will be obtained again. In the light electromotive force component of Patent 1, the transparent conductive film

勢°當各ρη接合部分進行與非晶矽層 以及全體光電動勢元件中流動有電流 143168.doc -72- 201015731 清形時’於pn接合部分上會施加有順偏壓電压，從而該 等成為與先前之專利文獻1之光電動勢元件之總電動勢為 相反方向。然而，於本發明中，不存在如先前之專利文獻 1之光電動勢元件的使光電轉換效率減少之主要原因，故 . 而光電轉換裝置之特性會得到提高。 • 又，於上述構成之本實施形態之光電轉換裝置中，根據 氧化矽膜6與第1非晶矽層2a之光入射侧之表面之界面上的 鉋5之偏析量，可控制表面反轉層4上所誘發之電子之密 ® 度。 特別是在使铯5偏析到氧化矽膜6與第丨非晶矽層2a之界 面附近時，用以獲得表面反轉層4上的最佳的電子密度之 鉋離子佈植量之容限較廣，故而可提供一種品質穩定且特 性高的光電轉換裝置》 又，於上述構成之本實施形態之光電轉換裝置中，使第 1非晶矽層2a之光入射侧之表面上的界面能階因表面反轉 ❹ 層4上所誘發之負電荷而終止，藉此可抑制於第晶矽層 2a之光入射側之表面之界面能階上的載體之再結合，從而 使光電轉換效率等之光電轉換裝置之特性得到進一步提 高。 又，當與光入射側之透明導電膜9相接之半導體層中使 用有非晶矽時，難以應用高溫製程，故而難以在與透明導 電膜9相接之半導體層上形成雜質活化率較高的高濃度雜 質摻雜層以降低透明導電獏9與半導體層之間的接觸電 阻。然而，於上述構成之本實施形態之光電轉換裝置中， 143168.doc -73- 201015731 2由氧切膜6中之已離子化之絶5而於第i非晶㈣^ 入射側之表面上形成表面反轉層4 ,從而表面反轉層4 與透明導該9可經由㈣的氧切膜6而接觸，該氧化石夕 =係載體㈣穿随效應等而可通過者，因此即使不利用 …皿製程形成间濃度之雜質摻雜層，亦可降低透明導電膜 9與第1非晶矽層2a之接觸電阻。 又，於以上所述中，作為第^導體層、第2半導體層、 及第3半導體層，分別使用有非晶石夕，但並不限定於此， 作為第1半導體層、第2半導體層、及第3半導體層，亦可 分別使用例如結晶發、非晶石夕、微晶石夕或切以外之其他 種類之半導體等的半導體層。再者，結晶梦中包含單晶 矽、多晶石夕、或者單晶石夕與多晶碎之混合體等。再者，第 1半導體層、第2半導體層、及第3半導體層可分別由相同 材質之半導體層所形成’亦可為第}半導體層、第2半導體 層及第3半導體層中之至少一種係由不 層所形成。 胃之+導體 又’當第1半導體層、第2半導體層、及第3半導體層中 分別使用有結晶矽時’第!半導體層、第2半導體層、及第 3半導體層之積層結構例如可由以下方式而製作。首先， 製作兩塊矽基板（雙面摻雜矽基板），其係於結晶矽之一方 之表面上使p型雜質擴散而形成有p型層，且於結晶矽之另 一方之表面上使η型雜質擴散而形成有n型層，並且製作一 塊矽基板（單面摻雜矽基板），其係僅於結晶矽之一 之表 面上使Ρ型雜質擴散而形成有ρ型層，且於結晶矽之另—方 143168.doc • 74- 201015731 之表面上不使&quot;雜質擴散從而未形成η型層。繼而，使一 塊雙面摻㈣基板之_層黏合於單面摻雜％基板之ρ型 層，並且使另一塊雙面摻雜矽基板之η型層黏合於該雙面 換雜矽基板之ρ型層，藉此可製作出上述積層結構。 其後，於露出之單面摻雜矽基板之表面上配置鉋5之 後’例如以 CVD 法、ALD 法、RT〇(Rapid Th_al 11陕速熱氧化）法、或者電漿氧化法等而於露出 《早面摻雜⑦基板之表面之-部分上形成氧化梦膜6。繼 @利用例如濺鍍法、CVD法或溶膠凝膠法等而形成包含 ΠΌ ' 1〇、τ〇或者2〇等之透明導電膜&amp;，並與和該透明導 2膜9為相反側之上述積層結構之背面的ρ型層相接而形成 背面電極7,藉此可製作本實施形態之光電轉換裝置。再 者，關於鉋5，亦可在形成氧化矽膜6之後，於氧化矽膜6 中將绝離子進行離子佈植，其後進行退火，藉此使其偏析 到氧化石夕膜6與單面摻雜矽基板之界面上。 藝 如此來，當藉由氧化矽膜6之退火而使已離子化之鉋5 偏析到氧化矽膜6與第丨半導體層之界面附近時，表面反轉 層4上之用以獲得最佳的電子密度之铯離子佈植量之容限 較廣’因此可提供一種品質穩定且特性高的光電轉換裝 置。又’亦可於形成相較所期望之膜厚更厚之氧化矽膜6 之後’於氧化矽膜6中將鉋離子進行離子佈植，繼而進行 退火，藉此使鉋偏析到氧化矽膜6與單面摻雜矽基板之界 面上’其後進行利用氫氟酸水溶液等之處理或者反應性離 子姓刻等，以使氧化矽膜6變薄至所期望之膜厚為止。 143168.doc -75- 201015731 又，第1半導體層、第2半導體層、及第3半導體層之積 層結構例如亦可由以下之方式而製作。 首先，於單晶矽基板或多晶矽基板等矽基板之表面上形 成η型層。η型層係可藉由例如將磷、砷或銻等之n型雜質 於上述矽基板之表面進行離子佈植之後實施活化退火而形 成又，η型層亦可藉由在上述碎基板之表面上成膜推雜 有上述η型雜質型非晶矽膜而形成。 其次，於η型層上，例如使用CVD法等，依序堆積ρ型微 晶矽膜、非摻雜微晶矽膜、n型微晶矽膜、p型非晶矽膜以鬱 及非摻雜非晶矽膜。 其-人，於非摻雜非晶矽膜上，塗佈例如氫氧化鉋水溶液 或者氣化鉋水溶液等含有铯之溶液並使其乾燥藉此於非 摻雜非晶石夕膜之表面上配置鉋。 繼而，例如以CVD法或電漿氧化法等而形成氧化矽膜。 其後，於氧化石夕膜上形成透明導電膜。又，透明導電膜只 要利用例如濺鍍法、蒸鍍法或溶膠凝膠法等而形成IT〇、 ΙΟ、το或者ζο中之任一者即可。 @ 繼而，於上述矽基板之背面，形成背面電極。此處，背 面電極之形成例如可藉由利用滅鑛法或蒸鍍法等形成銘等 之金屬而進行。 最後，亦可於含有氫之環境中，實施300〜500。〇之退 火。藉此，可使膜與膜之界面、結晶粒界或非晶石夕中所存 在之懸鍵因氫而終止，故可抑制載體之再結合從而可使 光電轉換裝置之轉換效率提高。 143168.doc •76· 201015731 又，於上述構成之本實施形態之光電轉換裝置中，較好 的是靠近光入射側之第1半導體層之帶隙為遠離光入射侧 之第2半導體層之|隙以上。並且，更好的是靠近光入射 側之第2半導體層之帶隙為遠離光入射側之第3半導體層之 帶隙以上。進而，更好的是靠近光入射側之第丨半導體層 之帶隙為比第1半導體層更遠離光入射側之第2半導體層之 帶隙以上，且靠近光入射側之第2半導體層之帶隙為比第2 半導體層更遠離光入射側之第3半導體層之帶隙以上（第3 半導體層之帶隙$第2半導體層之帶隙‘第丨半導體層之帶 隙）。由於形成為如上所述之可自光入射侧起依序吸收短 波長光至長波長光的積層結構，故而入射至本實施形態之 光電轉換裝置中之光的吸收量會變大，因此光電轉換效率 等之本實施形態之光電轉換裝置的特性有提高之傾向。 再者，作為用以形成為上述的第3半導體層之帶隙$第2 半導體層之帶隙S第1半導體層之帶隙之關係的半導體層 鬱 之構成，可舉出例如於第1半導體層中使用非晶碳化矽 (SiC)、於第2半導體層中使用非晶矽、且於第3半導體層中 使用微晶矽之構成。 又’作為形成為上述的第3半導體層之帶隙$第2半導體 層之帶隙S第1半導體層之帶隙之關係的半導體層之其他 的構成’可舉出例如於第1半導體層中使用非晶碳化矽、 於第2半導體層中使用非晶矽、且於第3半導體層 晶料(SiGe)之構成。 用非 又’作為用以形成為上述的第3半導體層之帶隙各第2半 143168.doc -77· 201015731 導體層之帶隙半導體層之帶隙之關係的半導體層之 構成’可舉出例如於第i半導體層中使用非晶碳化矽 ㈣、於第2半導體層中使用非晶石夕、且於第3半導 使用單晶或多晶石夕之構成。 又，作為用以形成為上述的第3半導體 導體層之帶隙，半導趙層之帶隙之關係的半;體第層2: 構成，可舉出例如於第1半導體層中使用非晶石夕、於第2半 導體層中使財m且於第3半導體層中使用單晶或多 晶矽之構成。 再者，例如，包含石夕之半導體材料之帶隙的大小關係 為：非晶碳化矽〉多晶碳化矽&gt;單晶碳化矽&gt;非晶矽&gt;微晶矽 &gt;多晶石夕&gt;單晶石夕&gt;非晶石夕鍺&gt;多晶矽鍺&gt;單晶石夕鍺因此只 要以使帶隙越大之材料越靠近光人射側之方式進行: 可〇 又，較好的是第1半導體層之厚度較第1半導體層内之載 體擴散長度更薄。於此情形時，可有效抑制第1半導體層 内之載體之再結合’並且藉由如本實施形態般形成為積層 結構’亦可提高所入射之光被吸收之概率。 又，較好的是第2半導體層之厚度較第2半導體層内之載 體擴散長度更薄。於此情形時，可有效抑制第2半導體層 内之載體之再結合，並且藉由如本實施形態般形成為積層 結構’亦可提高所入射之光被吸收之概率。 又’較好的是第3半導體層之厚度較第3半導體層内之載 體擴散長度更薄。於此情形時，可有效抑制第3半導體層 143168.doc 78· 201015731 内之载體之再結合，並且藉由如本實施形態般形成為積層 結構’亦可提高所入射之光被吸收之概率。 又，於以上所述_，作為表面介電質臈係使用氧化矽膜 6 ,但當然並不限定於此，亦可使用例如選自由碳化矽、 • 氧化矽、氮氧化矽及氮化矽所組成之群中之至少一種。 .又，作為表面介電質膜，較好的是使用帶隙為42 ev&amp; 上之介電質膜。例如，太陽光之大部分係由具有3〇〇 nm以 上之波長之光所構成，故而當使用帶隙為4.2 eV以上之表 面介電質膜而使太陽光入射時，具有3〇〇 nm以上之波長的 太陽光不會被吸收，從而轉換損失變少，因此光電轉換裝 置之特性有進一步提高之傾向。 又，自提高穿隧效應之觀點考慮，表面介電質膜之厚度 好的疋3 nm以下，更好的是1 nm以下。即，於本實施形 態之光電轉換裝置中，自提高穿隧效應之觀點考慮，作為 表面介電質膜的氧化矽膜6之厚度較好的是3 nm以下。此 ❹ 外，使氧化矽膜6之厚度為1 nm以下，從而使直接穿隧之 載體傳導成為支配，故可減小透明導電膜8與表面反轉層4 之間的電阻。 又，於以上所述中，已對使用鉋5作為成為正的固定電 何之雜質之情況進行了說明，但並不限定於此，亦可使用 例如包含選自由鋰、鈉、鉀、铷、鉋、鎂、鈣、鳃、鋇、 磷、砷及銻所組成之群中之至少一種者。 又，於上述構成之本實施形態之光電轉換裝置中，亦町 調換P型與η型之導電型。於此情形時，可使用成為負的固 143168.doc -79- 201015731 定電荷之雜質代替如铯之成為正的固定電荷之雜質◦作為 成為負的固定電荷之雜質，可使用例如包含選自由 鋁、鎵、銦、鉑、氟化富勒烯、氧化富勒烯、氟、氣、溴 及碘所組成之群中之至少一種者。 又，於上述構成之本實施形態之光電轉換裝置中，較好 的是，上述雜質存在最多之部位係位於從作為第丨半導體 層之第1非晶矽層2a與作為表面介電質膜之氧化矽膜6之界 面起，在相對於該界面而垂直之方向上朝著作為第丨半導 體層之第1非晶矽層2a侧前進5 nm之區域、與朝著作為表 面介電質膜之氧化矽膜6側前進5 nm之區域之間的區域 上。於此情形時，上述構成之本實施形態之光電轉換裝置 之特性有進一步提高之傾向。 即，於本發明之光電轉換裝置中，只要表面介電質膜在 與第1半導體層之界面附近含有成為正或負的固定電荷之 雜質即可，而該雜質之至少—部分只要係存在^從第】半 導體層與表面介電質骐之界面起，在相對於該界面而垂直 之方向上朝著第1半導體層側了前進5 nm之區域、與朝著 表面介電質膜側前進5 nm之區域之間的區域上即可。 又，於以上所述中，當然，可使第1非晶矽層2a之光入 射側之氧化矽膜6作為抗反射膜而發揮功能，亦可於氧化 矽膜6之表面形成紋理結構及/或蛾眼結構等。 已對上述構成之本實施形態之光電轉換裝置中具有 積層有第1半導體層、第2半導體層、及第3半導體層該三 之積層結構的情況進行了說明，但並不限定於此，只要 143168.doc 201015731 為包含第1半導體層之一層以上’則半導體層之積層數並 無限定。再者，較好的是半導體層之厚度共計為1〇〇 上。藉此，對於長波長光，亦有可進行有效的光電轉換之 傾向。 又，如上所述，於上述構成之本實施形態之光電轉換裝 置中，亦可調換η型與ρ型之導電型。再者，當於上述構成 之本實施形態之光電轉換裝置中已調換η型與ρ型之導電型 《情形時’正與負的電荷之極性、以及電子與電洞亦會被 ® 調換。 於上述構成之本實施形態之光電轉換裝置中，作為透明 導電膜9，可使用例如包含汀〇、1〇、τ〇或者2〇之層的單 層或複數層之積層體。 又，當如本實施形態之光電轉換裝置般於第丨半導體層 中使用有非晶石夕時，較好的是使用成為負的固定電荷之雜 質來作為表面介電質膜氧化矽膜6中所含之雜質，以使第1 ❹ 半導體層之光入射側之表面上誘發正的電荷而形成作為ρ 型半導體發揮功能之表面反轉層4。 &lt;實施形態14&gt; 圖28中表示本發明之光電轉換裝置之另一例之剖面示意 圖。此處，圖28所示之構成之本實施形態之光電轉換装置 的特徵在於··於作為第3半導體層之第3非晶矽層以之與光 入射側為相反側之背面上，設置有作為背面介電質膜之氧 化矽膜26。 此處，作為背面介電質膜之氧化矽膜26在與第3非晶矽 143168.doc -81 - 201015731 層2c之界面附近’含有與表面介電質膜氧化碎.中所含 之成為正的固$電荷之雜質铯5為相反極性之負的固定電 荷之雜質25。並且，由於存在成為負的固定電荷之雜質 25，故在與氧化矽膜26相接之第3非晶矽層以之背面之區 域的至少一部分上，會誘發正的電荷而形成作為p型半導 體發揮功能之背面反轉層24。 藉由使光入射至如上所述之構成之本實施形態的光電轉 換裝置而產生之載體’係、自光入射側之透明導電膜9及背When the respective ρη junction portions are subjected to current flow 143168.doc -72- 201015731 in the amorphous germanium layer and the entire photoelectromotive force element, a forward bias voltage is applied to the pn junction portion, so that It becomes the opposite direction to the total electromotive force of the photoelectromotive force element of the prior patent document 1. However, in the present invention, there is no main cause for reducing the photoelectric conversion efficiency of the photovoltaic device as in the prior patent document 1, and the characteristics of the photoelectric conversion device are improved. Further, in the photoelectric conversion device of the present embodiment configured as described above, the surface inversion can be controlled according to the segregation amount of the planer 5 at the interface between the surface of the yttrium oxide film 6 and the light incident side of the first amorphous germanium layer 2a. The density of electrons induced on layer 4. In particular, when the yttrium 5 is segregated to the vicinity of the interface between the yttrium oxide film 6 and the second ytterbium amorphous layer 2a, the tolerance of the planer ion implantation amount for obtaining the optimum electron density on the surface inversion layer 4 is higher. In addition, in the photoelectric conversion device of the present embodiment configured as described above, the interface energy level on the surface on the light incident side of the first amorphous germanium layer 2a is provided. The surface is reversed by the negative charge induced on the layer 4, whereby the recombination of the carrier on the interface level of the surface on the light incident side of the fourth layer 2a can be suppressed, thereby making the photoelectric conversion efficiency and the like The characteristics of the photoelectric conversion device are further improved. Further, when an amorphous germanium is used in the semiconductor layer which is in contact with the transparent conductive film 9 on the light incident side, it is difficult to apply a high-temperature process, so that it is difficult to form a high impurity activation rate on the semiconductor layer which is in contact with the transparent conductive film 9. The high concentration impurity doped layer reduces the contact resistance between the transparent conductive germanium 9 and the semiconductor layer. However, in the photoelectric conversion device of the present embodiment configured as described above, 143168.doc -73 - 201015731 2 is formed on the surface of the i-th amorphous (tetra) incident side by the ionized 5 in the oxygen cut film 6. The surface inversion layer 4 is such that the surface inversion layer 4 and the transparent guide 9 can be contacted via the oxygen film 6 of (4), which can pass through the effect or the like, so that even if it is not used... The impurity doping layer of the concentration between the formation processes can also reduce the contact resistance between the transparent conductive film 9 and the first amorphous germanium layer 2a. In the above, the amorphous layer is used as the second conductive layer, the second semiconductor layer, and the third semiconductor layer. However, the present invention is not limited thereto, and the first semiconductor layer and the second semiconductor layer are used. Further, for the third semiconductor layer, a semiconductor layer such as a crystal hair, an amorphous stone, a microcrystalline stone, or another type of semiconductor other than the tantalum may be used. Further, the crystal dream includes a single crystal ruthenium, a polycrystalline stone, or a mixture of single crystal and polycrystalline granules. Furthermore, the first semiconductor layer, the second semiconductor layer, and the third semiconductor layer may each be formed of a semiconductor layer of the same material, or may be at least one of the first semiconductor layer, the second semiconductor layer, and the third semiconductor layer. It is formed by no layers. When the crystal 矽 is used for each of the first semiconductor layer, the second semiconductor layer, and the third semiconductor layer, the laminated structure of the 'the semiconductor layer, the second semiconductor layer, and the third semiconductor layer can be Made in the following ways. First, two ruthenium substrates (double-sided doped ruthenium substrates) are formed on the surface of one of the crystal ruthenium to diffuse p-type impurities to form a p-type layer, and η on the other surface of the crystallization ruthenium The type impurity is diffused to form an n-type layer, and a tantalum substrate (single-sided doped germanium substrate) is formed which diffuses the germanium-type impurity on only one surface of the crystal germanium to form a p-type layer, and is crystallized.矽 另 — 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 Then, a layer of a double-sided doped (four) substrate is bonded to the p-type layer of the single-sided doped % substrate, and another n-type layer of the double-sided doped germanium substrate is bonded to the double-sided doped substrate. The layer can be formed by the above laminated structure. Thereafter, after the planer 5 is disposed on the surface of the exposed single-sided doped germanium substrate, the exposure is performed, for example, by a CVD method, an ALD method, an RT 〇 (Rapid Th_al 11 thermal oxidation) method, or a plasma oxidation method. The oxidized dream film 6 is formed on the portion of the surface of the early doped 7 substrate. Forming a transparent conductive film &amp; ΠΌ '1〇, τ〇 or 2〇, etc., by using, for example, a sputtering method, a CVD method, a sol-gel method, or the like, and on the opposite side to the transparent conductive film 9 The p-type layer on the back surface of the laminated structure is connected to each other to form the back surface electrode 7, whereby the photoelectric conversion device of the present embodiment can be produced. Further, regarding the planer 5, after the ruthenium oxide film 6 is formed, the ion ions may be ion-implanted in the ruthenium oxide film 6, and then annealed to thereby segregate the oxidized stone film 6 and one side. On the interface of the doped germanium substrate. In this way, when the ionized planer 5 is segregated to the vicinity of the interface between the tantalum oxide film 6 and the second semiconductor layer by annealing of the tantalum oxide film 6, the surface inversion layer 4 is used for the best. The electron density has a wide tolerance for the ion implantation amount, so that a photoelectric conversion device with stable quality and high characteristics can be provided. Further, the ionizing agent may be ion-implanted in the yttrium oxide film 6 after forming the yttrium oxide film 6 thicker than the desired film thickness, and then annealed, thereby segregating the planer to the yttrium oxide film 6 On the interface with the single-sided doped ruthenium substrate, the treatment with a hydrofluoric acid aqueous solution or the like or the reactive ion implantation is performed to thin the yttrium oxide film 6 to a desired film thickness. 143168.doc -75- 201015731 Further, the laminated structure of the first semiconductor layer, the second semiconductor layer, and the third semiconductor layer can be produced, for example, in the following manner. First, an n-type layer is formed on the surface of a germanium substrate such as a single crystal germanium substrate or a polycrystalline germanium substrate. The n-type layer may be formed by performing an activation annealing after ion implantation of an n-type impurity such as phosphorus, arsenic or antimony on the surface of the germanium substrate, and the n-type layer may also be on the surface of the fragmented substrate. The upper film formation is mixed with the above-described n-type impurity type amorphous germanium film. Next, on the n-type layer, for example, a p-type microcrystalline germanium film, an undoped microcrystalline germanium film, an n-type microcrystalline germanium film, a p-type amorphous germanium film, and a non-doped state are stacked by using a CVD method or the like. Amorphous amorphous ruthenium film. On the non-doped amorphous ruthenium film, a solution containing ruthenium or the like, such as a water-based planing aqueous solution or a gasified planing aqueous solution, is applied and dried to be disposed on the surface of the non-doped amorphous stone film. plane. Then, a ruthenium oxide film is formed, for example, by a CVD method, a plasma oxidation method, or the like. Thereafter, a transparent conductive film is formed on the oxidized stone film. Further, the transparent conductive film may be formed by any one of IT 〇, ΙΟ, το or ζο, for example, by a sputtering method, a vapor deposition method, a sol-gel method or the like. @ Then, a back surface electrode is formed on the back surface of the above-mentioned tantalum substrate. Here, the formation of the back electrode can be performed, for example, by forming a metal such as a metallurgical method or a vapor deposition method. Finally, it is also possible to carry out 300 to 500 in an environment containing hydrogen. The fire of the cockroach. Thereby, the dangling bonds existing in the interface between the film and the film, the crystal grain boundary or the amorphous rock can be terminated by hydrogen, so that recombination of the carrier can be suppressed, and the conversion efficiency of the photoelectric conversion device can be improved. Further, in the photoelectric conversion device of the present embodiment configured as described above, it is preferable that the band gap of the first semiconductor layer close to the light incident side is the second semiconductor layer far from the light incident side. Above the gap. Further, it is more preferable that the band gap of the second semiconductor layer close to the light incident side is equal to or larger than the band gap of the third semiconductor layer on the light incident side. Further, it is more preferable that the band gap of the second semiconductor layer close to the light incident side is equal to or larger than the band gap of the second semiconductor layer on the light incident side from the first semiconductor layer, and is closer to the second semiconductor layer on the light incident side. The band gap is larger than the band gap of the third semiconductor layer farther from the light incident side than the second semiconductor layer (the band gap of the third semiconductor layer, the band gap of the second semiconductor layer, and the band gap of the second semiconductor layer). Since the laminated structure of the short-wavelength light to the long-wavelength light can be sequentially absorbed from the light incident side as described above, the amount of light incident on the photoelectric conversion device of the present embodiment becomes large, and thus photoelectric conversion is performed. The characteristics of the photoelectric conversion device of the present embodiment, such as efficiency, tend to be improved. In addition, as a structure of the semiconductor layer formed in the band gap of the third semiconductor layer, the band gap of the second semiconductor layer, and the band gap of the first semiconductor layer, the first semiconductor is exemplified. Amorphous tantalum carbide (SiC) is used for the layer, amorphous germanium is used for the second semiconductor layer, and microcrystalline germanium is used for the third semiconductor layer. Further, the other structure of the semiconductor layer which is formed as the band gap of the third semiconductor layer, the band gap of the second semiconductor layer, and the band gap of the first semiconductor layer, as described above, may be, for example, in the first semiconductor layer. An amorphous tantalum carbide is used, and an amorphous germanium is used for the second semiconductor layer and a third semiconductor layer crystal (SiGe) is used. The configuration of the semiconductor layer which is a relationship between the band gaps of the band gap semiconductor layers of the conductor layer formed by the second half of the band gap of the third semiconductor layer described above can be exemplified. For example, amorphous zirconium carbide (IV) is used for the i-th semiconductor layer, amorphous stone is used for the second semiconductor layer, and single crystal or polycrystalline stone is used for the third semiconductor. Further, as a half band of the band gap of the third semiconductor conductor layer and the band gap of the semiconductor layer, the body layer 2: the structure is, for example, amorphous in the first semiconductor layer. In the second semiconductor layer, a single crystal or a polycrystalline silicon is used in the third semiconductor layer. Further, for example, the size relationship of the band gap of the semiconductor material including Shi Xi is: amorphous niobium carbide > polycrystalline niobium carbide > single crystal niobium carbide > amorphous niobium > microcrystalline crucible > polycrystalline stone &gt;Single crystal stone&gt; Amorphous stone 锗 锗 多 多 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶 单晶The thickness of the first semiconductor layer is thinner than the diffusion length of the carrier in the first semiconductor layer. In this case, the recombination of the carrier in the first semiconductor layer can be effectively suppressed, and by forming the layered structure as in the present embodiment, the probability that the incident light is absorbed can be improved. Further, it is preferable that the thickness of the second semiconductor layer is thinner than the carrier diffusion length in the second semiconductor layer. In this case, the recombination of the carrier in the second semiconductor layer can be effectively suppressed, and by forming the laminated structure as in the present embodiment, the probability that the incident light is absorbed can be improved. Further, it is preferable that the thickness of the third semiconductor layer is thinner than the carrier diffusion length in the third semiconductor layer. In this case, the recombination of the carrier in the third semiconductor layer 143168.doc 78· 201015731 can be effectively suppressed, and the formation of the laminated structure as in the present embodiment can also increase the probability that the incident light is absorbed. . Further, as described above, the ruthenium oxide film 6 is used as the surface dielectric lanthanum, but it is of course not limited thereto, and for example, it may be selected from the group consisting of ruthenium carbide, ruthenium oxide, ruthenium oxynitride, and tantalum nitride. At least one of the group consisting of. Further, as the surface dielectric film, it is preferred to use a dielectric film having a band gap of 42 ev& For example, most of sunlight is composed of light having a wavelength of 3 〇〇 nm or more. Therefore, when a surface dielectric film having a band gap of 4.2 eV or more is used to make sunlight incident, it has 3 〇〇 nm or more. Since the sunlight of the wavelength is not absorbed and the conversion loss is reduced, the characteristics of the photoelectric conversion device tend to be further improved. Further, from the viewpoint of improving the tunneling effect, the thickness of the surface dielectric film is preferably 疋3 nm or less, more preferably 1 nm or less. In other words, in the photoelectric conversion device of the present embodiment, the thickness of the ruthenium oxide film 6 as the surface dielectric film is preferably 3 nm or less from the viewpoint of enhancing the tunneling effect. Further, the thickness of the yttrium oxide film 6 is 1 nm or less, so that the conduction of the carrier by direct tunneling is dominant, so that the electric resistance between the transparent conductive film 8 and the surface inversion layer 4 can be reduced. Further, in the above description, the case where the planer 5 is used as the positive fixed electric source has been described. However, the present invention is not limited thereto, and for example, it may be selected from the group consisting of lithium, sodium, potassium, and cesium. At least one of a group consisting of planing, magnesium, calcium, barium, strontium, phosphorus, arsenic and antimony. Further, in the photoelectric conversion device of the present embodiment configured as described above, the P-type and n-type conductivity types are also exchanged. In this case, an impurity which becomes a negative solid 143168.doc -79 - 201015731 can be used instead of the impurity which becomes a positive fixed charge, such as ytterbium, as an impurity which becomes a negative fixed charge, and for example, it is selected from the group consisting of aluminum At least one of a group consisting of gallium, indium, platinum, fluorinated fullerenes, oxidized fullerenes, fluorine, gas, bromine, and iodine. Further, in the photoelectric conversion device of the present embodiment configured as described above, it is preferable that the portion where the impurities are most present is located from the first amorphous germanium layer 2a as the second semiconductor layer and the surface dielectric film. The interface of the yttrium oxide film 6 is a region which is 5 nm in the direction perpendicular to the interface toward the first amorphous germanium layer 2a of the second semiconductor layer, and is a surface dielectric film. The yttrium oxide film 6 side advances over a region between the regions of 5 nm. In this case, the characteristics of the photoelectric conversion device of the present embodiment configured as described above tend to be further improved. In other words, in the photoelectric conversion device of the present invention, the surface dielectric film may contain an impurity which is a positive or negative fixed charge in the vicinity of the interface with the first semiconductor layer, and at least a part of the impurity may be present. From the interface between the semiconductor layer and the surface dielectric layer, a region that advances toward the first semiconductor layer side by 5 nm in the direction perpendicular to the interface and advances toward the surface dielectric film side 5 The area between the areas of nm can be. Further, in the above description, of course, the ruthenium oxide film 6 on the light incident side of the first amorphous ruthenium layer 2a functions as an antireflection film, and a texture structure can be formed on the surface of the yttrium oxide film 6 and/or Or moth eye structure. In the photoelectric conversion device of the present embodiment configured as described above, the laminated structure in which the first semiconductor layer, the second semiconductor layer, and the third semiconductor layer are laminated is described. However, the present invention is not limited thereto. 143168.doc 201015731 The number of layers of the semiconductor layer is not limited to include one or more layers of the first semiconductor layer. Further, it is preferred that the thickness of the semiconductor layer is 1 共计 in total. Therefore, for long-wavelength light, there is a tendency to perform effective photoelectric conversion. Further, as described above, in the photoelectric conversion device of the present embodiment configured as described above, the n-type and p-type conductivity types can be exchanged. Further, in the photoelectric conversion device of the present embodiment configured as described above, the polarity of the positive and negative charges and the electrons and holes are also exchanged by the n-type and p-type conductivity types. In the photoelectric conversion device of the present embodiment having the above-described configuration, as the transparent conductive film 9, for example, a single layer or a plurality of layers including a layer of Ting, 1 〇, τ 〇 or 2 可 can be used. Further, when an amorphous phase is used in the second semiconductor layer as in the photoelectric conversion device of the present embodiment, it is preferable to use a negatively fixed impurity as the surface dielectric film yttrium oxide film 6. The impurities contained therein form a surface inversion layer 4 functioning as a p-type semiconductor by causing a positive charge on the surface on the light incident side of the first semiconductor layer. &lt;Embodiment 14&gt; Fig. 28 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention. In the photoelectric conversion device of the present embodiment, which is configured as shown in FIG. 28, the third amorphous germanium layer as the third semiconductor layer is provided on the back surface opposite to the light incident side. As the ruthenium oxide film 26 of the back surface dielectric film. Here, the yttrium oxide film 26 as the back surface dielectric film is positively contained in the vicinity of the interface with the third amorphous germanium 143168.doc -81 - 201015731 layer 2c and contains the surface dielectric film oxidized powder. The impurity 铯5 of the solid $charge is a negatively charged impurity 25 of opposite polarity. Further, since there is an impurity 25 which becomes a negative fixed charge, a positive charge is induced on at least a part of the region on the back surface of the third amorphous germanium layer which is in contact with the yttrium oxide film 26 to form a p-type semiconductor. The function of the backside inversion layer 24. The carrier which is generated by causing light to be incident on the photoelectric conversion device of the present embodiment configured as described above, the transparent conductive film 9 from the light incident side, and the back

面側之背面電極7分別取出至外部，但於光入射侧，載體 係利用穿隧效應等通過氧切膜6而自透明導電膜9被取 出’於背面侧，載體係利用穿隨效應等通過氧切膜辦 而自背面電極7被取出。The back surface electrode 7 on the front side is taken out to the outside, but on the light incident side, the carrier is taken out from the transparent conductive film 9 by the oxygen cut film 6 by a tunneling effect or the like, and the carrier is passed through the wear effect or the like. The oxygen cutting film is taken out from the back electrode 7.

由於形成為如本實施形態所述之構成，故當使用透明導 電膜等之透0月電極作為背面電極7而使光不僅自作為第1年 導體層之第1非晶矽層2“則而且自作為第3半導體層之第 非晶碎層2c側進行入射時，與在第3非晶石夕層以之背面上 子在有藉由使P型雜質擴散所形成之p型層之情形相比，可 抑制因P型層而產生之短波長之光的吸收故而可提高光 電轉換裝置之光電轉換效率等之特性。 曰又’由於形成為如本實施形態所述之構《，故使第㈣ 阳夕層之背面上之界面能階因背面反轉層μ上所誘發之 正電何而終止，藉此可抑制於第3非晶矽層2c之背面之界 面此階上的載體之再結合，從而可使光電轉換效率等之光 電轉換裝置之特性得到進一步提高。 143】 68.doc •82· 201015731 再者，當背面電極7包含透明導電膜等之透明電極時， 作為背面電極7,可使用例如包含玎〇、1〇、τ〇或者2〇之 層的單層或複數層之積層體。又’背面電極7亦可包含例 如鋁等之金屬電極。 又於上述構成之本實施形態之光電轉換裝置中，較好 的疋第1半導體層之厚度為第2半導體層之厚度以下，且第 2半導體層之厚度為第3半導體層之厚度以下。通常，關於 “有串列連接之半導體層之光電轉換裝置的光電轉換效 率，由於越靠近光入射側之半導體&amp;，會入射越廣光譜之 光，因此每單位厚度之產生電流亦有越靠近光入射側之半 導體層越變大之傾向。又，於包含有串列連接之半導體層 之光電轉換裝置中’產生電流量最小之半導體層之電流會 限制全體光電轉換裝置中流動之電流量，故而較好的是各 半導體層中產生之電流量相等。因此，使越遠離光入射側 之半導體層形成得越厚，藉此可使各半導體層中產生之電 © 流量大致一致，故而可提高光電轉換效率。 又，於上述構成之本實施形態之光電轉換裝置中，作為 背面介電質膜，使用有氧化矽膜26，但當然並不限定於 此，亦可使用例如選自由碳化石夕、氧化石夕、氮氧切及氮 化矽所組成之群中之至少一種。 又，於上述構成之本實施形態之光電轉換裝置中，較好 的疋，作為背面介電質膜之氧化矽膜26中所含之雜質25存 在最多之部位係位於從作為第3半導體層之第3非晶矽層。 與作為背面介電質膜之氧化矽膜26之界面起，在相對於該 143168.doc -83- 201015731 界面而垂直之方向上朝著作為第3半導體層之第3非晶矽層 2c側前進5 nm之區域、與朝著作為背面介電質膜之氧化矽 膜26側前進5 nm之區域之間的區域上。於此情形時，上述 構成之本實施形態之光電轉換裝置之特性有進一步提高之 傾向。 即，於本發明之光電轉換裝置中，較好的是背面介電質 膜在與第3半導體層之界面附近，含有成為與表面介電質 臈中所含之成為正或負_定電荷之雜質為相反極性之固 定電荷的雜質，而於此情形時，該雜質之至少一部分只要 ❿ 係存在於從第3半導體層與背面介電質膜之界面起，在相 對於該界面而垂直之方向上朝著第3半導體層側前以⑽ 之區域、與朝著背面介電質膜側前進5咖之區域之間的區 域上即可。 又，於上述構成之本實施形態之光電轉換裝置中，自提 尚，體之穿随效應之觀點考慮，背面介電質膜之厚度較好 的是3 nm以了，更好的是！ nm以下。即於本實施形態之 光電轉換裝置中，自提高穿隧效應之觀點考慮，作為；面⑩ 介電質膜之氧化矽膜26之厚度較好的是3 nm以下，更好的 是1 nm以下。 又，於上述構成之本實施形態之光電轉換裝置中，作為 成為負的固定電荷之雜質25’可使用例如包含選自由硼·： 銘、鎵、銦、銘、敗化富勒稀、氧化富勒缔、免、氣、淳 及峨所組成之群中之至少一種者。 、 又，於上述構成之本實施形態之光電轉換裝置中，亦可 H3168.doc -84- 201015731 調換Ρ型與η型之導電型。於此情形時’作為背面介電質膜 中所含之雜質25,可使用成為正的固定電荷之雜質代替成 為負的電荷之雜質。當使用成為正的固定電荷之雜質 作為雜質25時’可使用例如包含選自由鋰、鈉、鉀、铷、 铯、鎂、鈣、锶、鋇、磷、砷及銻所組成之群中之至少一 種者。 又，於上述構成之本實施形態之光電轉換裝置中，背面 介電質膜中所含之雜質25例如可利用塗佈含有料之成為 負的固疋電荷之雜質25的溶液(例如’鹼性水溶液中溶解 有銘者等）之方法、暴露於含有銘等之成為負的固定電荷 之雜質25之蒸氣中之方法、㈣法等而附著於第#晶石夕 層2c之與光人射側之表面為相反側之背面的表面上之後， 利用⑽法、ALD法、電漿氧化法等，於第3非晶石夕層&amp; 之與光人射側之表面為相反側之背面的表面上形成氧化梦 膜26’藉此而配置於第3非晶石夕層2c與氧切 上。 1 wSince the structure is as described in the present embodiment, the vapor-transmission electrode such as a transparent conductive film is used as the back surface electrode 7 so that the light is not only the first amorphous layer 2 as the first-year conductor layer. When incident on the side of the first amorphous fracture layer 2c as the third semiconductor layer, and on the back surface of the third amorphous layer, there is a p-type layer formed by diffusing a P-type impurity. In addition, it is possible to suppress the absorption of light of a short-wavelength light generated by the P-type layer, thereby improving the characteristics of photoelectric conversion efficiency of the photoelectric conversion device, etc. 曰 ' 由于 形成 形成 形成 形成 形成 由于 由于 由于 由于 由于(4) The interface energy level on the back surface of the anode layer is terminated by the positive electricity induced on the back surface inversion layer μ, thereby suppressing the interface on the back side of the third amorphous layer 2c at this stage. In combination, the characteristics of the photoelectric conversion device such as the photoelectric conversion efficiency can be further improved. 143] 68.doc • 82· 201015731 Further, when the back electrode 7 includes a transparent electrode such as a transparent conductive film, as the back surface electrode 7, Can be used, for example, including 玎〇, 1〇, In addition, the back surface electrode 7 may include a metal electrode such as aluminum. Further, in the photoelectric conversion device of the present embodiment configured as described above, a preferred one is preferably a second layer or a plurality of layers. The thickness of the semiconductor layer is equal to or less than the thickness of the second semiconductor layer, and the thickness of the second semiconductor layer is equal to or less than the thickness of the third semiconductor layer. Generally, regarding the photoelectric conversion efficiency of the photoelectric conversion device having the semiconductor layers connected in series, Since the semiconductor of the light incident side is closer to the light of the light incident side, the light generated per unit thickness tends to become larger as the semiconductor layer closer to the light incident side becomes larger. Further, in the photoelectric conversion device including the semiconductor layers connected in series, the current of the semiconductor layer which generates the smallest amount of current limits the amount of current flowing in the entire photoelectric conversion device, and therefore, it is preferable that the current generated in each semiconductor layer The amount is equal. Therefore, the thickness of the semiconductor layer which is further away from the light incident side is made thicker, whereby the electric power generation rate generated in each semiconductor layer can be made substantially uniform, so that the photoelectric conversion efficiency can be improved. Further, in the photoelectric conversion device of the present embodiment having the above-described configuration, the ruthenium oxide film 26 is used as the back surface dielectric film. However, the ruthenium oxide film 26 is not limited thereto, and for example, it may be selected from the group consisting of carbonaceous stone and oxidized stone. At least one of a group consisting of oxynitride and cerium nitride. Further, in the photoelectric conversion device of the present embodiment having the above-described configuration, it is preferable that the portion of the impurity 25 contained in the ruthenium oxide film 26 as the back surface dielectric film is located at a position as the third semiconductor layer. The third amorphous layer. The interface with the yttrium oxide film 26 as the back surface dielectric film is advanced toward the third amorphous layer 2c which is the third semiconductor layer in the direction perpendicular to the interface of 143168.doc - 83 - 201015731. The region of 5 nm is in a region between the region which is 5 nm forward toward the side of the yttrium oxide film 26 which is the back surface of the dielectric film. In this case, the characteristics of the photoelectric conversion device of the present embodiment configured as described above are further improved. That is, in the photoelectric conversion device of the present invention, it is preferred that the back surface dielectric film is in a vicinity of the interface with the third semiconductor layer and is contained in a positive or negative constant charge contained in the surface dielectric material. The impurity is an impurity of a fixed polarity of opposite polarity, and in this case, at least a part of the impurity is present in a direction perpendicular to the interface as long as it is present from the interface between the third semiconductor layer and the back dielectric film. The upper side of the third semiconductor layer side may be in a region between (10) and a region extending toward the back dielectric film side. Further, in the photoelectric conversion device of the present embodiment configured as described above, the thickness of the back surface dielectric film is preferably 3 nm from the viewpoint of the effect of the body wearing effect, and more preferably! Below nm. In the photoelectric conversion device of the present embodiment, the thickness of the ruthenium oxide film 26 of the dielectric film of the surface 10 is preferably 3 nm or less, more preferably 1 nm or less, from the viewpoint of improving the tunneling effect. . Further, in the photoelectric conversion device of the present embodiment configured as described above, as the impurity 25' which becomes a negative fixed charge, for example, it is possible to use, for example, a boron-containing material selected from the group consisting of boron, germanium, gallium, indium, germanium, ruthenium, and oxidized rich. At least one of a group consisting of smuggling, exemption, gas, sputum and sputum. Further, in the photoelectric conversion device of the present embodiment configured as described above, the conductivity type of the Ρ type and the η type may be changed by H3168.doc -84 - 201015731. In this case, as the impurity 25 contained in the back surface dielectric film, an impurity which becomes a positive fixed charge can be used instead of the impurity which becomes a negative charge. When an impurity which becomes a positive fixed charge is used as the impurity 25, for example, at least one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, phosphorus, arsenic and antimony may be used. One kind. Further, in the photoelectric conversion device of the present embodiment configured as described above, the impurity 25 contained in the back surface dielectric film can be applied, for example, by applying a solution containing a negative solid charge 25 (for example, alkaline). The method of dissolving the inventor or the like in the aqueous solution, the method of exposing it to the vapor of the impurity 25 which is a negative fixed charge, etc., the method (4), etc., and attaching to the #石石层2c and the light human side After the surface is on the surface of the back surface on the opposite side, the surface of the third amorphous layer is opposite to the surface on the opposite side of the surface on the light-emitting side by the method of (10), ALD, plasma oxidation, or the like. The oxidized dream film 26' is formed on the third amorphous slab layer 2c and oxygen-cut. 1 w

再者，亦可代替將成為負的固^電荷之雜仏5配置㈣ 3非晶石夕層2e之與光人射側之表面為相反側之背面的表面 上’藉由在形成上述氧化石夕膜26時使CVD或ald等中所用 之氧切媒26之原料氣體中含有包含成為負的固定電荷之 雜質25的分子’來使氧切魏中含有成為負_定電荷 光電轉換裝置中，氧化 如下方法等而形成：以 又，於上述構成之本實施形態之 矽膜26中所含之雜質25例如可藉由 143168.doc -85- 201015731 熱氧化法、CVD法、ALD法或電漿氧化法等在第3非晶石夕 層2c之背面上形成氧化石夕膜26之後’於該氧化石夕膜26中離 子佈植例如雜質25。 本實施形態令之上述以外之說明與實施形態13相同，因 而在此省略其說明。 &lt;實施形態15&gt; 圖29中表示本發明之光電轉換裝置之另一例之剖面示意 圖。此處’圖29所示之構成之本實施形態之光電轉換裝置 的特徵在於.第1非晶石夕層2a之背面之氧化石夕膜32與第2非 晶石夕層2b之表面之氧化矽膜34係經由第1中間透明導電膜 33而接合，第2非晶石夕層2b之背面之氧化石夕膜37與第3非晶 矽層2c之表面之氧化矽膜39係經由第2中間透明導電膜％ 而接合。 此處，於本實施形態之光電轉換裝置中，氧化矽膜6係 在與第1非晶矽層2a之光入射侧之表面之界面附近含有已 離子化之鉋5作為成為正的固定電荷之雜質，並且氧化矽 膜34在與第2非晶矽層2b之光入射側之表面之界面附近含 有已離子化之鉋5作為成為正的固定電荷之雜質，進而， 氧化矽膜39在與第3非晶矽層仏之光入射侧之表面之界面 附近含有已離子化之铯5作為成為正的固定電荷之雜質。 又，氧化矽膜26在與第3非晶矽層及之背面之界面附近 含有成為負的固定電荷之雜質25，並且氧化矽膜37在與第 2非晶矽層2b之背面之界面附近含有成為負的固定電荷之 雜質25，進而’氧化石夕膜32在與第磚晶梦層^之背面之 143168.doc -86 - 201015731 界面附近s有成為負的固定電荷之雜質25。 本實施形態之光電轉換裝置具有上述構成，因此，於第 1非晶矽層2a之光入射側之表面上會誘發電子而形成有作 為η型半導體發揮功能之表面反轉層4，且於第1非晶矽層 2a之背面上會誘發電洞而形成有作為ρ型半導體發揮功能 之背面反轉層3 1。 並且，於第2非晶矽層2b之光入射側之表面上亦會誘發 ❹ 電子而形成有作為η型半導體發揮功能之表面反轉層35, 且於第2非晶矽層2b之背面上會誘發電洞而形成有作為ρ型 半導體發揮功能之背面反轉層36。 進而，於第3非晶矽層2C之光入射側之表面上亦會誘發 電子而形成有作為n型半導體發近功能之表面反轉層4〇, 且於第3非晶矽層2c之背面上會誘發電洞而形成有作為ρ型 半導體發揮功能之背面反轉層24。 藉由使光入射至如以上所述之構成之本實施形態的光電 ❹ 轉換裝置而產生之載體，係自光入射側之透明導電膜9及 背面側之背面電極7分別取出至外部，於光入射側，載體 係利用穿隨效應專通過氧化碎膜6而自透明導電膜9被取 出，於背面側’載體係利用穿隧效應等通過氧化矽膜26而 自背面電極7被取出。 又’例如第2非晶矽層2b上所產生之載體中’電子係利 用穿隨效應等而在背面反轉層36中、氧化石夕膜37中、第2 中間透明導電膜38中、氧化矽膜39中以及表面反轉層4〇中 分別移動，並且電洞係利用穿隧效應等而在表面反轉層35 143168.doc •87· 201015731 中、氧化石夕膜34中、第1中間透明導電膜33中、氧化石夕膜 32中以及背面反轉層31中移動。 於先前專利文IU所揭示之光電動勢元件中，將單位晶 胞間以Pn接合而加以接合’因此該pn接合部分成為高電 阻’從而光電動勢元件之光電轉換效率等之特性有降低之 傾向、。然而’如本實施形態所述形成為利用穿隧效應等使 中門透月導電膜及含有成為正或負的固定電荷之雜質之氧 化石夕膜通過之構成’藉此，與先前專利幻所揭示之光電 動勢接合相比’可形成為更低之電阻。其原因在_ 於，由於在中間透明導電膜之光入射侧之表面及背面上分 J形成之氧化石夕臈含有成為正或負的固定電荷之雜質故 而可提高穿隧效應等之穿透概率。 特別是當如本實施形態般於^半導體層、第2半導體 層 '及第3半導體層中分別使用有非晶石夕時’難以應用高 溫製程’從而於先前專利文⑴所揭示之光電動勢元件 中’構成pn接合之P型層及n型層之載體濃度變低，故而可 認為更為有效果。 ❹ 再者於以上所述中，作為第1中間透明導電膜^及第2 中間透明導電膜38,可分別使用例如包含ιτ〇、ι〇、τ〇4 者加之層的單層或複數層之積層體。再者，作為透明導， 電膜8、第i中間透明導電膜33以及第之中間透明導電膜 38,可分別使用相同材質之透明導電膜，亦可為透明導電 膜9、糾中間透明導電膜33以及第2中間透明導電膜38中 之至少一者包含不同材質之透明導電膜。 143168.doc -88 - 201015731 又，於以上所述中，使用氧化石夕膜6作為第ι表面 膜，使用氧化矽膜32作為第bFurther, instead of forming the above-mentioned oxidized stone, the surface of the surface of the amorphous side layer 2e on the opposite side to the surface of the light-emitting side may be replaced by In the case of the solar cell 26, the material gas containing the impurity 25 which becomes a negative fixed charge is contained in the source gas of the oxygen-removing medium 26 used for CVD or ald, etc., and the oxygen-cut-type is contained in the negative-fixed-charge photoelectric conversion device. Oxidation is formed by the following method: Further, the impurity 25 contained in the ruthenium film 26 of the present embodiment configured as described above can be, for example, 143168.doc-85-201015731 thermal oxidation method, CVD method, ALD method or plasma After the oxidized method or the like forms the oxidized stone film 26 on the back surface of the third amorphous slab layer 2c, for example, the impurity 25 is ion-implanted in the oxidized stone film 26. The description of the embodiment other than the above is the same as that of the thirteenth embodiment, and thus the description thereof will be omitted. &lt;Embodiment 15&gt; Fig. 29 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention. Here, the photoelectric conversion device of the present embodiment having the configuration shown in Fig. 29 is characterized in that the oxidation of the surface of the oxidized stone film 32 and the second amorphous slab layer 2b on the back surface of the first amorphous slab layer 2a. The ruthenium film 34 is bonded via the first intermediate transparent conductive film 33, and the ruthenium oxide film 39 on the back surface of the second amorphous oliw layer 2b and the yttrium oxide film 39 on the surface of the third amorphous ruthenium layer 2c are passed through the second The intermediate transparent conductive film is bonded to the %. Here, in the photoelectric conversion device of the present embodiment, the ruthenium oxide film 6 contains the ionized planer 5 as a positive fixed charge in the vicinity of the interface with the surface on the light incident side of the first amorphous germanium layer 2a. In the vicinity of the interface with the surface on the light incident side of the second amorphous germanium layer 2b, the cerium oxide film 34 contains the ionized planer 5 as an impurity which becomes a positive fixed charge, and further, the yttrium oxide film 39 is in the same state. The vicinity of the interface of the surface on the light incident side of the amorphous germanium layer contains the ionized germanium 5 as an impurity which becomes a positive fixed charge. Further, the yttrium oxide film 26 contains an impurity 25 which is a negative fixed charge in the vicinity of the interface with the third amorphous layer and the back surface, and the yttrium oxide film 37 is contained in the vicinity of the interface with the back surface of the second amorphous layer 2b. It becomes a negative fixed-charge impurity 25, and further, the oxidized stone film 32 has an impurity 25 which becomes a negative fixed charge in the vicinity of the interface of 143168.doc -86 - 201015731 on the back side of the second brick dream layer. Since the photoelectric conversion device of the present embodiment has the above configuration, the surface inversion layer 4 functioning as an n-type semiconductor is formed on the surface on the light incident side of the first amorphous germanium layer 2a. A back surface inversion layer 31 that functions as a p-type semiconductor is formed on the back surface of the amorphous germanium layer 2a by inducing a hole. Further, a surface inversion layer 35 functioning as an n-type semiconductor is formed on the surface on the light incident side of the second amorphous germanium layer 2b, and is formed on the back surface of the second amorphous germanium layer 2b. A back surface inversion layer 36 functioning as a p-type semiconductor is formed by inducing a hole. Further, on the surface on the light incident side of the third amorphous germanium layer 2C, electrons are induced to form a surface inversion layer 4 which functions as an n-type semiconductor, and is formed on the back surface of the third amorphous germanium layer 2c. A back surface inversion layer 24 functioning as a p-type semiconductor is formed by inducing a hole. The carrier generated by the photoelectric conversion device of the present embodiment configured as described above is taken out from the transparent conductive film 9 on the light incident side and the back electrode 7 on the back side, respectively, to the outside. On the incident side, the carrier is taken out from the transparent conductive film 9 by the oxide film 6 by the wear-through effect, and the carrier is taken out from the back electrode 7 through the ruthenium oxide film 26 by the tunneling effect or the like on the back side. Further, for example, in the carrier generated on the second amorphous germanium layer 2b, the electrons are oxidized in the back surface inversion layer 36, the oxidized oxide film 37, and the second intermediate transparent conductive film 38 by the wear-through effect or the like. The ruthenium film 39 and the surface inversion layer 4 分别 are respectively moved, and the hole system is in the surface inversion layer 35 143168.doc •87· 201015731, the oxidized stone film 34, and the first middle by the tunneling effect or the like. The transparent conductive film 33 moves in the oxidized stone film 32 and the back surface inversion layer 31. In the photovoltaic device disclosed in the prior art, the unit cells are joined by Pn bonding, so that the pn junction portion becomes high resistance, and the characteristics of the photoelectric conversion efficiency of the photovoltaic device are lowered. . However, as described in the present embodiment, the formation of the oxidized stone film of the middle gate and the oxidized stone containing the impurity which becomes a positive or negative fixed charge is formed by the tunneling effect or the like. The disclosed light electromotive force bond can be formed as a lower resistance than '. The reason for this is that the oxide oxide formed by the J on the surface and the back surface of the light-transmissive side of the intermediate transparent conductive film contains impurities which become positive or negative fixed charges, thereby improving the penetration probability of tunneling effects and the like. . In particular, when the amorphous layer is used in the semiconductor layer, the second semiconductor layer', and the third semiconductor layer as in the present embodiment, it is difficult to apply a high-temperature process, and the photoelectromotive force element disclosed in the prior patent (1) is used. In the middle of the 'p-type layer and the n-type layer constituting the pn junction, the carrier concentration is lowered, so that it is considered to be more effective. Further, in the above, as the first intermediate transparent conductive film and the second intermediate transparent conductive film 38, for example, a single layer or a plurality of layers including a layer including ιτ〇, ι〇, and τ〇4 may be used. Laminated body. Further, as the transparent guide, the electric film 8, the i-th intermediate transparent conductive film 33, and the first intermediate transparent conductive film 38 may each be a transparent conductive film of the same material, or may be a transparent conductive film 9, or an intermediate transparent conductive film. At least one of 33 and the second intermediate transparent conductive film 38 includes a transparent conductive film of a different material. 143168.doc -88 - 201015731 Further, in the above description, the oxidized stone film 6 is used as the first surface film, and the yttrium oxide film 32 is used as the bth

電#膜’使用氧切膜37作為第2背面 &quot;電貝膜’使用氧切膜39作為第3表面介電質膜，且使 用氧化梦膜26作為第3f面介電質膜，但作為第！表面介電 質膜、第1背面介電質膜、第2表面介電質膜、第2背面介 電質膜、第3表面介電質膜及第3背面介電質膜，並未分別 限定於氧切膜，亦可使用例如選自由碳切、氧化石夕、 氮氧化矽及氮化矽所組成之群中之至少一種。再者，作為 第1表面介電質膜、第丨背面介電質膜、第2表面介電質 膜、第2背面介電質膜、第3表面介電質膜及第3背面介電 質膜，可分別使用相同材質之介電質膜，亦可為第1表面 介電質膜、第1背面介電質膜、第2表面介電質臈、第2背 面介電質膜、第3表面介電質膜及第3背面介電質膜中之至 少一者包含不同材質之介電質膜。 又，較好的是第1表面介電質膜、第i背面介電質膜、第 2表面介電質膜、第2背面介電質膜及第3表面介電質膜各 自之帶隙為4.2 eV以上。例如，太陽光之大部分係由具有 300 nm以上之波長之光所構成，故而當分別使用帶隙為 4.2 eV以上之第1表面介電質膜、第ι背面介電質膜、第2表 面介電質膜、第2背面介電質膜及第3表面介電質膜而使太 陽光入射時’具有300 nm以上之波長的太陽光不會被吸 收’從而轉換損失變少，因此光電轉換裝置之特性有進一 步提高之傾向。 143168.doc •89· 201015731 又’於上述構成之本實施形態之光電轉換裝置中，較好 的疋’氧化石夕膜32中所含之雜質25存在最多之部位係位於 從第1非晶石夕層2a與氧化矽膜32之界面起，在相對於該界 面而垂直之方向上朝著第1非晶矽層2a側前進5 nm之區 域、與朝著氧化矽膜32側前進5 ηιη之區域之間的區域上。 於此情形時’上述構成之本實施形態之光電轉換裝置之特 性有進一步提高之傾向。 又，於上述構成之本實施形態之光電轉換裝置中，較好 的疋，氧化矽膜34中所含之已離子化之鉋5存在最多之部 位係位於從第2非晶矽層2b與氧化矽膜34之界面起，在相 對於該界面而垂直之方向上朝著第2非晶矽層2b側前進5 πι之區域與朝著氧化石夕膜3 4側前進5 nm之區域之間的區 域上。於此情形時，上述構成之本實施形態之光電轉換裝 置之特性有進一步提高之傾向。 又，於上述構成之本實施形態之光電轉換裝置中，較好 的是，氧化矽膜37中所含之雜質25存在最多之部位係位於 從第2非晶矽層2b與氧化矽膜37之界面起，在相對於該界 面而垂直之方向上朝著第2非晶矽層2b侧前進5 nm之區 域、與朝著氧化矽膜37側前進5 nmi區域之間的區域上。 於此凊形時，上述構成之本實施形態之光電轉換裝置之特 性有進一步提高之傾向。 又，於上述構成之本實施形態之光電轉換裝置中，較好 的是，氧化矽膜39中所含之已離子化之鉋5存在最多之部 位係位於從第3非晶矽層2c與氧化矽膜39之界面起，在相 143168.doc -90- 201015731 對於該界面而垂直之方向上朝著第3非晶石夕層&amp;侧前進$ nm之區域、與朝著氧化石夕膜39側前進5細之區域之間的區 域上於此情形時，上述構成之本實施形態之光電轉換裝 置之特性有進一步提高之傾向。 又於上述構成之本實施形態之光電轉換裝置中，自提 高載體之穿隨效應之觀點考慮，氧切脑、氧化石夕媒 0 ❹ 34、氧切膜37以及氧切㈣之厚度較好的是分別為; nm以下，更好的是分別為1 以下。 又’於上述構成之本實施形態之光電轉換I置中，氧化 石夕膜32例如可利用塗佈含有銘等之成為負的固定電荷之雜 質25的溶液（驗性水溶液中溶解有叙者等）之方法、暴露於 含有銘等之成㈣的固定電荷之雜㈣之蒸氣中之方法、、 減鑛法等，使成為負的固定電荷之雜質25附著於以非曰 石夕層2a之與光入射側之表面為相反側之背面的表面上： 後’利用例如CVD法、ALD法、暴露於含有氧之環境中之 22形成於第1非晶石夕層2a之與光入射側之表面為相 反側之是面的表面上。又私备 佈植雜質25。 ^切㈣中例如亦可離子 又’於上述構成之本實施形態之光電轉換裝置中 中間透明導電膜33例如亦可藉由如下方法等而形成：利用 濺鍍法、蒸鍍法或溶膠凝膠法等，於氧化矽膜 射側之表面為相反側之背面的表面上，對IT〇、I〇、、^ 者ΖΟ等進行蒸鍍。 0或 又’於上述構成之本實施形態之光電轉換裝置中，氧化 143168.doc 91 201015731 =3:係可利用例如CVD法，法或者暴露於含有氧之 之方法等而形成於第！中間透明導電膜^之與光入 ’則之表面為相反側之背面的表 涂蚀备儿&amp; 工再後，可利用例如 塗佈氣化財溶液等之含有*之溶液 鉋蒸氣中之方法等，將鎚5配 /暴露於 侧之表面為相反側之背面的表面上:=4之與光入射 等而形成第2非晶矽層2be 用例如CVD法 又於上述構成之本實施形態之光電轉換裝置中，氧化 =37係可使用例如塗佈含有銘等之成為負的固定電荷之 雜質25之溶液（驗性水溶液巾轉㈣者等）之方法、暴露 :含有鋁等之成為負的固定電荷之雜質25之蒸氣中之方 、、濺鑛法等’使成為負的固定電荷之雜質抑著於第2 非晶石夕層2之與光入射側之表面為相反侧之背面的表面上 例如以CVD法、ALD法、暴露於含氧之環境中之方 法：而形成於第2非晶石夕層2之與光入射側之表面為相反側 的表面上。又，於氧化矽膜37中例如亦可離子佈植 雜質25。 又，於上述構成之本實施形態之光電轉換裝置中，第2 中間透明導電膜38係只要利用例如缝法、蒸链法、溶膠 凝膠法等而在氧切膜37之與光人射側之表面為相反側之 背面的表面上形成ITO、1〇、τ〇或者2〇等即可。 又，於上述構成之本實施形態之光電轉換裝置中，氧化 矽膜39可利用例如CVD法、ALD法或者暴露於含有氧之環 境中之方法等而形成於第2中間透明導電膜38之與光入射 143168.doc 201015731 側之表面為相反側之背面的表面上。其後，可利用例如塗 佈氯化铯水溶液等之含有铯之溶液之方法、或者暴露於鉋 蒸氣中之方法等，將铯5配置於氧化矽膜39之與光入射側 之表面為相反側之背面的表面上之後，利用例如CVD法等 而形成第3非晶矽層2c。 又，第1半導體層、第2半導體層、及第3半導體層之積 層結構例如亦可藉由如下所述之方式而製作。 首先’於單晶矽基板或多晶矽基板等矽基板之表面上， 例如利用熱氧化法或CVD法等而形成氧化矽膜。 其次，於氧化矽膜中，離子佈植作為成為正的固定電荷 之雜質的例如铯。繼而’於800〜110(Γ(：左右，較好的是於 850〜950°C之溫度下進行退火，藉此使絶偏析到氧化矽膜 與矽基板之界面上。 其次，於氧化矽膜上形成透明導電膜。透明導電膜可藉 由例如濺鍍法、蒸鍍法或溶膠凝膠法等而形成。 其次，於透明導電膜上形成氧化矽膜。此處，亦可利用 氫氟酸水溶液等對矽基板之背面進行處理等來去除附著於 矽基板之背面上之氧化矽膜。 其次，將矽基板浸潰於例如含有鋁之溶液（例如鹼性水 溶液中溶解有鋁者）中，以使作為負的固定電荷之鋁附著 於最表面之氧化矽膜及矽基板背面上。 製作複數塊以上述方式所製作之具有積層結構之梦基 板’並使具有積層結構之第1矽基板之背面、與具有上述 積層結構之第2矽基板之表面側的氧化矽膜相接之方式進 143168.doc -93- 201015731 行黏口。其次’以使具有上述積層結構之第2矽基板之背 面與具有上述積層結構之第3矽基板之表面側之氧化矽 膜相接之方式進行黏合。於要形成四層以上之矽基板時， 以與上述同樣之方式黏合矽基板。 ’、:人於上述黏合後之梦基板之背面上形成氧化硬膜之 後，形成背面電極。 最後’亦可於300〜500。(：之氫環境中進行退火。藉此， 懸鍵因氯而終止，故難以產生載體之再結合，從而可提高 光電轉換效率。 本實施形態令之矽之積層數為三層，但並無特別限定， 只要為一層以上即可。 本實施形態中之上述以外之說明與實施形態1S及實施形 態14相同’因而在此省略其說明。 實施例 圖14中表示本實施例中所製作之光電轉換裝置之試樣之 剖面示意圖。此處，圖14所示之光電轉換裝置之試樣係於 P型矽基板101之光入射側之表面之一部分上形成有n+層 102。又，於p型矽基板1〇1之光入射侧之表面上依序形成 有氧化石夕膜105及氮化石夕膜1〇6，且通過設置於氧化矽膜 105及氮化矽膜106上之接觸孔（contact h〇le)而設置有與n+ 層102相接之電極107。進而，氧化矽膜1〇5在與p型矽基板 101之光入射侧之表面之界面附近含有已離子化之铯1〇4， 因此在與氧化矽膜1〇5相接之p型矽基板1〇1之光入射側之 表面之區域上’會誘發負的電荷而形成作為η型半導體發 143168.doc -94- 201015731 揮功此之表面反轉層103。再者，雖未圖示，但於P型矽基 板101之背面上形成有背面電極。 以下，參照圖15所示之流程圖，對圖14所示之構成的光 電轉換I置之試樣之製作方法進行說明。 首先，於步驟S1中，在119(TC2溫度下，對離子佈植有 硼離子之矽進行退火而製作p型矽基板101。 其次，於步驟S2中，於p型矽基板1〇1之光入射側之表面 利用熱氧化法而形成氧化矽膜1〇5之後，利用電漿cvd法 而形成氮化矽膜106。 其次，於步驟S3中，於氧化矽膜105及氮化矽膜1〇6之積 層體之一部分上設置接觸孔之後，自該接觸孔使p〇Cl3擴 散’藉此形成n+層102。 其次，於步驟S4中，在形成於p型矽基板1〇1之光入射側 之表面上的氧化矽膜丨05中，離干佈植铯離子。 其次，於步驟S5中，將進行了鉋離子之離子佈植後之p 型石夕基板101加熱至900°C ’藉此’在與氧化矽膜1〇5相接 之P型石夕基板101之光入射側之表面之區域上形成表面反轉 層 103 〇 其後’於步驟S6中’對通過設置於氧化石夕膜1〇5及氮化 矽膜106之積層體上之接觸孔而形成有電極i〇7ip型石夕基 板101在氫環境中進行退火，藉此製作圖14所示之構成之 光電轉換裝置之試樣。 圖16中表示對圖14所示之構成之光電轉換裝置之試樣進 行在氧化矽膜105與p型矽基板101之界面附近之組成分析 143168.doc -95- 201015731 後所得之結果。此處’圖16所示之結果係使全體氧化矽膜 105中之鉋104之濃度發生各種變化（2xl〇丨5 cm.2、1x1q14 cm·2、及 5xl013 cm·2)後，利用高解像度RBs(Rutherfwd Back Scattering，拉塞福背向散射分析）而進行在氧化石夕媒 105與p型矽基板101之界面附近之組成分析時的結果。 再者’圖16中之橫軸表示自圖14所示之構成之光電轉換 裝置之試樣的氧化矽膜105與p型矽基板101之界面起算之 距離（nm)，縱轴分別表示铯濃度（xio21 cnT3)、石夕漠度（原 子％)以及氧濃度（原子％)。 如圖16所示’可知於使全體氧化矽膜1〇5中之铯1〇4之濃 度發生各種變化之任一情形時，鉋104之大部分均係存在 於自氧化矽膜105與p型矽基板1〇1之界面起朝向氧化珍膜 106側之距離以及朝向p型矽基板ιοί侧之距離分別為5 nm 之範圍内’並且已離子化之絶104偏析到氧化碎膜1〇5與p 型矽基板101之界面附近。 圖17中表示圖14所示之構成之光電轉換裝置之試樣在氧 化矽膜105與p型矽基板1〇1之界面附近的铯之偏析量b、 與藉由铯之偏析而於p型矽基板101之表面上所誘發之電子 反轉層之電子面密度（cm·2)之關係。此處，圖17之橫轴表 示於氧化矽膜105令離子佈植之铯離子之劑量，圖17之縱 轴表示在氧化矽膜105與p型矽基板101之界面附近之鉋的 偏析量（cm·2)、以及藉由鉋之偏析而於p型矽基板1〇1之表 面所誘發之電子反轉層之電子面密度（cm·2)。 又，圖17所示之結果係使於氧化矽膜105中進行離子佈 143168.doc •96· 201015731 植之铯離子之劑量發生各種變化而製作圖14所示之構成之 光電轉換裝置之試樣後，利用霍爾測量（Hall measurement：) 來測定上述電子反轉層之電子面密度。又，圖17所示之絶 之偏析量係根據圖16所示之結果而計算出。又，圖丨7所示 之結果係針對使p型；ε夕基板1 〇 1之硼濃度分別發生變化 (6.5xl014 cm.3、2.9x1016 cm·3、1.4xl017 cm·3、及 6.6χ1017 cnT3)後之各個試樣而求得者。 如圖17所示，可知隨著於氧化矽膜105中進行離子佈植 之鉋離子之劑量的增加’ p型矽基板1〇1之表面上所誘發之 電子反轉層之電子面密度（cm·2)會逐漸增加，但當絶離子 之劑量達到2xl014 cm·2以上時，上述電子反轉層之電子面 密度（cnT2)會變得大致固定（2 xlO13 cm·2左右）。 又，隨著於氧化矽膜105中進行離子佈植之鉋離子之劑 量的增加，氧化矽膜105與p型矽基板ιοί之界面附近之絶 的偏析量（cm·2)亦會逐漸增加，但當鏠離子之劑量達到一 定量以上時，上述铯之偏析量（cm·2)亦會變得大致固定。 因此，於p型矽基板101之表面上所誘發之電子反轉層之 電子面毯'度（cm 2)及铯之偏析量（cm·2)均顯示出相同行為， 故而可為於該等之間存在相關關係’因此可認為p型珍 基板101之表面上所誘發之電子反轉層之電子面密度（cm.2) 可根據鉋之偏析量（cm_2)來控制。 又，將p型矽基板1〇1之表面上所誘發之電子反轉層之電 子面密度（cnT2)達到大致固定時之值設為光電轉換裝置中 最佳的電子反轉層之電子面密度，藉此可確保用以獲得本 143168.doc 97· 201015731 發明之光電轉換裝置中最佳的電子反轉層之電子面密度的 較廣的製程纟限，&amp;而可實現高精度的電子&amp;轉層之電子 面密度之控制。 圖18中表不圖14所示之構成之光電轉換裝置之試樣在氧 化矽膜105中離子佈植之鉋離子之劑量（cm·2)、與p型矽基 板101之已誘發電子之表面的薄片電阻（sheet resisUnce) (kft/〇)之關係。此處，圖18之橫軸表示於氧化矽膜ι〇5中 離子佈植之鉋離子之劑量，圖18之縱軸表示p型矽基板ι〇ι 之表面上所誘發之電子反轉層之薄片電阻（ki2/C]^又， 圖18所示之結果係針對使p型矽基板1〇1之硼濃度分別發生 變化（4.6&gt;&lt;1014(^-3、2.9&gt;&lt;10丨6(^-3、1.4&gt;&lt;1〇”（；111-3以及 6·6χ1 〇17 cm·3)之各個試樣而求得者。 如圖18所示，隨著於氧化矽膜1〇5中離子佈植之鉋離子 之劑量的增加，於p型矽基板1〇1上所誘發之電子反轉層之 薄片電阻（ΙίΩ/匚])逐漸降低，但當鉋離子之劑量達到一定 量以上（2xlO cm2以上）時，上述卩型石夕基板1〇1之表面之 電子反轉層的薄片電阻（kD/[Il)亦會大致固定（約2 kQ/□左 右）。此處，亦將p型矽基板101之表面之電子反轉層之薄 片電阻達到大致固定時之值設為光電轉換裝置中最佳的薄 片電阻’藉此可確保用以獲得本發明之光電轉換裝置中最 佳的上述薄片電阻的較廣的製程容限，從而可實現高精度 的上述薄片電阻之控制。 圖19中表示圖14所示之構成之光電轉換裝置之試樣在p 型碎基板101之表面上所誘發之電子反轉層的電子面密度 143168.doc •98- 201015731 (cm'2)與溫度（K)之關係。此處，圖19之橫軸表示温度 (Κ)，圖19之縱軸表示ρ型矽基板1〇1之表面上所誘發之電 子反轉層之電子面密度（cm_2)。又，圖19所示之結果係使 於氧化矽膜105中離子佈植之铯離子之劑量分別發生變化 (5xl013 cm·2、5x10m cm-2 以及 2xl〇15 cm_2)而求得者。 如圖19所示，隨著溫度（κ)上升，卩型矽基板1〇1之表面 上所誘發之電子反轉層之電子面密度（cm·2)在降低。此顯 不出與摻雜於矽中之磷或砷等之通常的摻雜劑所形成之n+ 層為相反的溫度依存性。 圖20(a)中表示ρ型矽基板與氧化矽膜之界面上所存在之 雜質在離子化前的狀態下ρ型矽基板與氧化矽膜之界面附 近之能帶（energy band)圖。又，圖20(b)中表示卩型矽基板 與氧化矽膜之界面上所存在之雜質在離子化後的狀態下ρ 型矽基板與氧化矽膜之界面附近之能帶圖。 圖20(a)中，在氧化矽膜與15型矽基板之界面上存在有雜 質，該雜質形成雜質能階200。雜質能階2〇〇形成於p型矽 基板之傳導帶下端之上方_EA(EA表示藉由雜質而生成電子 載體之活化能）的位置。當形成上述狀態時，如圖20(b)所 示，將電子自雜質能階200釋放至？型矽基板，變為空的雜 質能階作為正電荷而動作（雜質離子化）。繼而，藉由該正 電荷所產生之電場而會在氧化矽膜與1&gt;型矽基板之界面附 近產生ρ型矽基板之能帶之彎曲，從而於上述界面附近形 成電子反轉層。再者，對應於已離子化之雜質能階2〇1， 於P型矽基板之表面形成有與表面反轉層相對應之能階 143168.doc -99- 201015731 202 ° 根據圖20⑷及圖20⑻所示之能帶圖進行數值計算後得The electric film # uses the oxygen cut film 37 as the second back surface, the electric film, the oxygen film 39 as the third surface dielectric film, and the oxidized dream film 26 as the third surface dielectric film, but The first! The surface dielectric film, the first back dielectric film, the second surface dielectric film, the second back dielectric film, the third surface dielectric film, and the third back dielectric film are not limited, respectively. For the oxygen cut film, for example, at least one selected from the group consisting of carbon cut, oxidized rock, bismuth oxynitride, and tantalum nitride may be used. Further, the first surface dielectric film, the second surface dielectric film, the second surface dielectric film, the second back dielectric film, the third surface dielectric film, and the third back dielectric The film may be a dielectric film of the same material, or may be a first surface dielectric film, a first back dielectric film, a second surface dielectric, a second back dielectric film, or a third At least one of the surface dielectric film and the third back dielectric film includes a dielectric film of a different material. Further, it is preferable that a band gap of each of the first surface dielectric film, the ith back dielectric film, the second surface dielectric film, the second back dielectric film, and the third surface dielectric film is 4.2 eV or more. For example, most of the sunlight is composed of light having a wavelength of 300 nm or more, so that the first surface dielectric film having a band gap of 4.2 eV or more, the first dielectric film, and the second surface are respectively used. The dielectric film, the second back surface dielectric film, and the third surface dielectric film prevent solar light having a wavelength of 300 nm or more from being incident when sunlight is incident, and thus conversion loss is reduced, so photoelectric conversion is performed. The characteristics of the device have a tendency to be further improved. 143168.doc •89· 201015731 Further, in the photoelectric conversion device of the present embodiment configured as described above, the most abundant portion of the impurity 25 contained in the cerium oxide film 32 is located from the first amorphous stone. The interface between the layer 2a and the yttrium oxide film 32 advances 5 nm toward the first amorphous ruthenium layer 2a side and 5 ηιη toward the ruthenium oxide film 32 side in a direction perpendicular to the interface. On the area between the areas. In this case, the characteristics of the photoelectric conversion device of the present embodiment having the above configuration tend to be further improved. Further, in the photoelectric conversion device of the present embodiment configured as described above, it is preferable that the most ionized planer 5 contained in the yttrium oxide film 34 is located in the second amorphous layer 2b and oxidized. The interface between the ruthenium films 34 is between 5 πι in the direction perpendicular to the interface and 5 nm in the direction toward the second amorphous ruthenium layer 2b. On the area. In this case, the characteristics of the photoelectric conversion device of the present embodiment configured as described above tend to be further improved. Further, in the photoelectric conversion device of the present embodiment configured as described above, it is preferable that the portion of the impurity 25 contained in the yttrium oxide film 37 is the most located from the second amorphous layer 2b and the yttrium oxide film 37. The interface is in a region that is 5 nm toward the second amorphous germanium layer 2b side and a region between the 5 nmi region toward the yttrium oxide film 37 side in the direction perpendicular to the interface. In the case of this shape, the characteristics of the photoelectric conversion device of the present embodiment configured as described above are further improved. Further, in the photoelectric conversion device of the present embodiment configured as described above, it is preferable that the portion of the ionized planer 5 contained in the yttrium oxide film 39 is most located in the third amorphous layer 2c and oxidized. From the interface of the ruthenium film 39, in the direction of the interface 143168.doc -90-201015731, the direction of the vertical direction toward the third amorphous slab layer & side advances to the region of $ nm, and toward the oxidized stone film 39 In this case, the characteristics of the photoelectric conversion device of the present embodiment configured as described above tend to be further improved. Further, in the photoelectric conversion device of the present embodiment configured as described above, the thickness of the oxygen-cut brain, the oxidized oxide medium ❹ 34, the oxygen-cut film 37, and the oxygen cut (4) is good from the viewpoint of improving the wear-through effect of the carrier. It is respectively below; nm is better, and is preferably 1 or less. In the photoelectric conversion I of the present embodiment, the oxidized oxide film 32 can be applied, for example, by applying a solution containing an impurity 25 which is a negative fixed charge, etc. a method of exposing it to a vapor containing a fixed charge of (4), or a method of reducing ore, etc., so that an impurity 25 which becomes a negative fixed charge is attached to the non-small layer 2a The surface on the light incident side is on the surface on the opposite side of the back side: the latter is formed on the surface of the first amorphous layer 2a and the light incident side by, for example, a CVD method, an ALD method, and exposure to an environment containing oxygen. On the opposite side is the surface of the face. Also privately planted with impurities 25. The intermediate transparent conductive film 33 in the photoelectric conversion device of the present embodiment having the above-described configuration, for example, may be formed by, for example, a sputtering method, an evaporation method, or a sol-gel. In the method, etc., on the surface on the opposite side of the surface on the side of the yttrium oxide film, IT〇, I〇, ^, ^, etc. are vapor-deposited. In the photoelectric conversion device of the present embodiment having the above configuration, the oxidation 143168.doc 91 201015731 = 3: can be formed by, for example, a CVD method or a method of exposure to oxygen; The surface of the intermediate transparent conductive film and the surface on the opposite side of the surface of the light-transfer can be used, for example, by coating a vapor-containing solution containing a gasification solution or the like. For example, the surface of the back surface of the hammer 5 is exposed/exposed to the surface on the opposite side: the fourth amorphous germanium layer 2b is formed by the light incident or the like, and the present embodiment is constituted by, for example, the CVD method. In the photoelectric conversion device, for example, a method of applying a solution containing an impurity 25 which is a negative fixed charge such as a seal (in the case of an aqueous solution of the aqueous solution), or the like, may be used. The side of the vapor of the impurity 25 of the fixed charge, the sputtering method, etc., the impurity which becomes a negative fixed charge is suppressed on the surface of the second amorphous layer 2 opposite to the surface on the light incident side. The upper surface of the second amorphous layer 2 is formed on the surface opposite to the surface on the light incident side by, for example, a CVD method, an ALD method, or a method of exposure to an oxygen-containing environment. Further, for example, the yttrium oxide film 37 may be ion-implanted with impurities 25. Further, in the photoelectric conversion device of the present embodiment, the second intermediate transparent conductive film 38 is on the light-emitting side of the oxygen-cut film 37 by, for example, a slit method, a vapor chain method, a sol-gel method or the like. ITO, 1 〇, τ 〇 or 2 〇 may be formed on the surface of the back surface on the opposite side. Further, in the photoelectric conversion device of the present embodiment configured as described above, the yttrium oxide film 39 can be formed on the second intermediate transparent conductive film 38 by, for example, a CVD method, an ALD method, or a method of exposure to an atmosphere containing oxygen. Light incidence 143168.doc 201015731 The surface on the side is the surface on the opposite side of the back side. Thereafter, the crucible 5 can be disposed on the opposite side of the surface of the tantalum oxide film 39 from the light incident side by, for example, a method of coating a solution containing ruthenium chloride or the like, or a method of exposure to a planer vapor. After the surface of the back surface, the third amorphous germanium layer 2c is formed by, for example, a CVD method. Further, the laminated structure of the first semiconductor layer, the second semiconductor layer, and the third semiconductor layer can be produced, for example, as follows. First, a ruthenium oxide film is formed on the surface of a tantalum substrate such as a single crystal germanium substrate or a polycrystalline germanium substrate by, for example, thermal oxidation or CVD. Next, in the yttrium oxide film, ion implantation is used as an impurity which becomes a positive fixed charge, for example. Then, at 800 to 110 (Γ (: about, preferably, annealing at a temperature of 850 to 950 ° C, thereby segregating to the interface between the ruthenium oxide film and the ruthenium substrate. Second, the ruthenium oxide film A transparent conductive film is formed thereon. The transparent conductive film can be formed by, for example, a sputtering method, a vapor deposition method, a sol-gel method, or the like. Next, a ruthenium oxide film is formed on the transparent conductive film. Here, hydrofluoric acid can also be used. The back surface of the ruthenium substrate is treated with an aqueous solution or the like to remove the ruthenium oxide film attached to the back surface of the ruthenium substrate. Next, the ruthenium substrate is immersed in, for example, a solution containing aluminum (for example, aluminum dissolved in an alkaline aqueous solution). The aluminum as a negative fixed charge is adhered to the ruthenium oxide film on the outermost surface and the back surface of the ruthenium substrate. A plurality of the first substrate having the laminated structure and the first substrate having the laminated structure are produced in the above-described manner. The back surface is in contact with the ruthenium oxide film on the surface side of the second ruthenium substrate having the above-mentioned laminated structure, and is 143168.doc-93-201015731. The second surface of the second ruthenium substrate having the above laminated structure is formed.Bonding is performed in contact with the ruthenium oxide film on the surface side of the third ruthenium substrate having the above-mentioned laminated structure. When four or more ruthenium substrates are to be formed, the ruthenium substrate is bonded in the same manner as described above. After forming an oxidized hard film on the back surface of the bonded dream substrate, a back surface electrode is formed. Finally, annealing can be performed in a hydrogen atmosphere of 300 to 500. The dangling bond is terminated by chlorine, so that it is difficult to produce In the present embodiment, the number of layers to be laminated is three, but the number of layers is not particularly limited, and may be one or more layers. The descriptions and embodiments other than the above in the embodiment 1S is the same as that of the embodiment 14. Therefore, the description of the sample of the photoelectric conversion device produced in the present embodiment is shown in Fig. 14. Here, the test of the photoelectric conversion device shown in Fig. 14 is performed. An n+ layer 102 is formed on a portion of the surface of the light incident side of the P-type germanium substrate 101. Further, an oxide oxide is sequentially formed on the surface of the light incident side of the p-type germanium substrate 1〇1. The film 105 and the nitride film 1〇6 are provided with an electrode 107 that is in contact with the n+ layer 102 through a contact hole provided on the tantalum oxide film 105 and the tantalum nitride film 106. Further, The yttrium oxide film 1〇5 contains the ionized 铯1〇4 in the vicinity of the interface with the surface on the light incident side of the p-type ruthenium substrate 101, and thus the p-type ruthenium substrate 1 adjacent to the ruthenium oxide film 1〇5〇 On the surface of the light incident side of the light, a negative charge is induced to form a surface inversion layer 103 as an n-type semiconductor 143168.doc-94-201015731. Further, although not shown, A back surface electrode is formed on the back surface of the P-type germanium substrate 101. Hereinafter, a method of fabricating a sample of the photoelectric conversion I of the configuration shown in Fig. 14 will be described with reference to a flowchart shown in Fig. 15. First, in step S1, a p-type germanium substrate 101 is formed by annealing an ion implanted with boron ions at TC2 temperature. Next, in step S2, light is applied to the p-type germanium substrate 1〇1. After the surface of the incident side is formed by the thermal oxidation method to form the hafnium oxide film 1〇5, the tantalum nitride film 106 is formed by the plasma cvd method. Next, in step S3, the hafnium oxide film 105 and the tantalum nitride film are stacked. After the contact hole is provided in a portion of the laminate of 6 , p〇Cl 3 is diffused from the contact hole to thereby form the n + layer 102. Next, in step S4, on the light incident side formed on the p-type germanium substrate 1〇1 On the surface of the ruthenium oxide film 丨05, the ruthenium ions are separated from the dry sputum. Next, in step S5, the p-type slate substrate 101 after the ion implantation of the dicing ions is heated to 900 ° C. 'A surface inversion layer 103 is formed on a region of the surface on the light incident side of the P-type slab substrate 101 which is in contact with the yttrium oxide film 1〇5, and then 'in step S6' is passed through the oxidized stone film. 1〇5 and a contact hole on the laminated body of the tantalum nitride film 106 are formed with an electrode i〇7ip type Shixi substrate 101 in hydrogen Annealing in the environment is performed to prepare a sample of the photoelectric conversion device having the configuration shown in Fig. 14. Fig. 16 shows a sample of the photoelectric conversion device of the configuration shown in Fig. 14 in the ruthenium oxide film 105 and p-type ruthenium. The composition obtained in the vicinity of the interface of the substrate 101 was analyzed after 143168.doc -95-201015731. Here, the result shown in Fig. 16 causes various changes in the concentration of the planer 104 in the entire ruthenium oxide film 105 (2xl〇丨5). After cm.2, 1x1q14 cm·2, and 5×l013 cm·2), the interface between the oxidized oxide medium 105 and the p-type ruthenium substrate 101 is performed by using a high resolution RBs (Rutherfwd Back Scattering). The result of the composition analysis in the vicinity. Further, the horizontal axis in Fig. 16 indicates the distance from the interface between the ruthenium oxide film 105 and the p-type ruthenium substrate 101 of the sample of the photoelectric conversion device constituted as shown in Fig. 14 (nm) The vertical axis indicates the yttrium concentration (xio21 cnT3), the Shiki desert degree (atomic %), and the oxygen concentration (atomic %). As shown in Fig. 16, it is known that the total yttrium oxide film 1〇5 is 铯1〇. When any of the various changes in the concentration of 4, most of the planer 104 The average is present in the range from the interface between the yttrium oxide film 105 and the p-type ruthenium substrate 1 〇1 toward the side of the oxidized film 106 and the distance toward the side of the p-type 矽 substrate ιοί, respectively, and is in the range of 5 nm, respectively. The film 104 is segregated to the vicinity of the interface between the oxidized fragment film 1〇5 and the p-type ruthenium substrate 101. Fig. 17 shows a sample of the photoelectric conversion device of the configuration shown in Fig. 14 in the ruthenium oxide film 105 and the p-type ruthenium substrate 1 The relationship between the segregation amount b of the yttrium near the interface of 〇1 and the electron surface density (cm·2) of the electron inversion layer induced on the surface of the p-type ruthenium substrate 101 by segregation of ruthenium. Here, the horizontal axis of Fig. 17 indicates the dose of the erbium ions implanted by the yttrium oxide film 105, and the vertical axis of Fig. 17 indicates the segregation amount of the planer near the interface between the yttrium oxide film 105 and the p-type ruthenium substrate 101 ( Cm·2) and the electron areal density (cm·2) of the electron inversion layer induced on the surface of the p-type germanium substrate 1〇1 by the segregation of the planer. Further, the result shown in Fig. 17 is a sample of the photoelectric conversion device of the composition shown in Fig. 14 in which the dose of the ion cloth of the ion cloth 143168.doc • 96· 201015731 is changed in the ruthenium oxide film 105. Thereafter, Hall surface measurement was used to measure the electron areal density of the above electron inversion layer. Further, the absolute segregation amount shown in Fig. 17 was calculated based on the results shown in Fig. 16. Further, the result shown in Fig. 7 is for changing the boron concentration of the p-type; ε 夕 substrate 1 〇 1 (6.5xl014 cm.3, 2.9x1016 cm·3, 1.4xl017 cm·3, and 6.6χ1017 cnT3). The individual samples were obtained afterwards. As shown in Fig. 17, it is understood that the electron inversion layer of the electron inversion layer induced on the surface of the p-type germanium substrate 1〇1 increases with the dose of the ion implanted in the yttrium oxide film 105. 2) It will gradually increase, but when the dose of the absolute ion reaches 2xl014 cm·2 or more, the electronic areal density (cnT2) of the above-mentioned electron inversion layer becomes substantially constant (about 2 x lO13 cm·2). Further, as the dose of the ion implanted in the ruthenium oxide film 105 is increased, the segregation amount (cm·2) near the interface between the ruthenium oxide film 105 and the p-type ruthenium substrate ιοί is gradually increased. However, when the dose of the cerium ion reaches a certain amount or more, the segregation amount (cm·2) of the above cerium is also substantially fixed. Therefore, the electronic blanket 'degree (cm 2) and the segregation amount (cm·2) of the electron inversion layer induced on the surface of the p-type germanium substrate 101 all exhibit the same behavior, and thus may be such There is a correlation between them. Therefore, it is considered that the electronic areal density (cm.2) of the electron inversion layer induced on the surface of the p-type substrate 101 can be controlled according to the segregation amount (cm_2) of the planer. Moreover, the value of the electronic surface density (cnT2) of the electron inversion layer induced on the surface of the p-type germanium substrate 1〇1 is substantially fixed, and the electronic surface density of the electron inversion layer is optimal in the photoelectric conversion device. Thereby, it is ensured that a high-precision electronic &amp; high precision can be achieved by obtaining a wider process limit of the electronic surface density of the best electron inversion layer in the photoelectric conversion device of the invention of 143168.doc 97·201015731 ; control of the electronic areal density of the transition layer. In Fig. 18, the dose (cm·2) of the ion implanted in the yttrium oxide film 105 of the sample of the photoelectric conversion device shown in Fig. 14 and the surface of the induced electron of the p-type ruthenium substrate 101 are shown. The sheet resistance (sheet resisUnce) (kft / 〇) relationship. Here, the horizontal axis of Fig. 18 indicates the dose of ion implanted in the ruthenium oxide film 〇5, and the vertical axis of Fig. 18 indicates the electron inversion layer induced on the surface of the p-type 〇 substrate ι〇ι Sheet resistance (ki2/C)^ Again, the results shown in Fig. 18 are for changing the boron concentration of the p-type germanium substrate 1〇1 (4.6 &gt;&lt; 1014 (^-3, 2.9 &gt;&lt; 10丨6(^-3, 1.4&gt;&lt;1〇" (; 111-3 and 6·6χ1 〇17 cm·3) were obtained for each sample. As shown in Fig. 18, along with yttrium oxide The increase in the dose of the ion implanted ion in the film 1〇5 gradually decreases the sheet resistance (ΙίΩ/匚) of the electron inversion layer induced on the p-type germanium substrate 1〇1, but when the dose of the planing ion is decreased When the amount is more than a certain amount (2x10 cm2 or more), the sheet resistance (kD/[Il) of the electron inversion layer on the surface of the above-mentioned 石-type substrate 〇1 is also substantially fixed (about 2 kQ/□). Also, the value of the sheet resistance of the electron inversion layer on the surface of the p-type germanium substrate 101 is substantially fixed to the optimum sheet resistance in the photoelectric conversion device, thereby ensuring the use of the present invention. The optimum process tolerance of the above-mentioned sheet resistance in the electric conversion device enables high-precision control of the sheet resistance. The sample of the photoelectric conversion device of the configuration shown in Fig. 14 is shown in Fig. 19 The electronic areal density of the electron inversion layer induced on the surface of the fractured substrate 101 is 143168.doc • 98- 201015731 (cm'2) in relation to the temperature (K). Here, the horizontal axis of Fig. 19 indicates the temperature (Κ). The vertical axis of Fig. 19 indicates the electron areal density (cm_2) of the electron inversion layer induced on the surface of the p-type germanium substrate 1〇1. Further, the result shown in Fig. 19 is the ion cloth in the hafnium oxide film 105. The dose of the sputum ion was changed (5xl013 cm·2, 5x10m cm-2, and 2xl〇15 cm_2), respectively. As shown in Fig. 19, as the temperature (κ) increased, the 矽-type 矽 substrate 1〇 The electron areal density (cm·2) of the electron inversion layer induced on the surface of 1 is lowered. This shows that the n+ layer formed by the usual dopant such as phosphorus or arsenic doped in the crucible is The opposite temperature dependence. Figure 20(a) shows the presence of impurities on the interface between the p-type germanium substrate and the hafnium oxide film. An energy band diagram near the interface between the p-type ruthenium substrate and the ruthenium oxide film in the state before the formation. Further, FIG. 20(b) shows the presence of impurities at the interface between the ruthenium-type ruthenium substrate and the ruthenium oxide film. An energy band diagram near the interface between the p-type ruthenium substrate and the ruthenium oxide film in the state after ionization. In Fig. 20(a), there is an impurity at the interface between the ruthenium oxide film and the 15-type ruthenium substrate, and the impurity forms impurity energy. Step 200. The impurity level 2〇〇 is formed above the lower end of the conduction band of the p-type germanium substrate _EA (EA indicates the activation energy of the electron carrier generated by the impurity). When the above state is formed, as shown in Fig. 20(b), electrons are released from the impurity level 200 to ? In the type of germanium substrate, the impurity level that becomes empty acts as a positive charge (impurity ionization). Then, by the electric field generated by the positive electric charge, the energy band of the p-type germanium substrate is bent near the interface between the hafnium oxide film and the 1&gt; type germanium substrate, thereby forming an electron inversion layer in the vicinity of the interface. Furthermore, corresponding to the ionized impurity energy level 2〇1, an energy level corresponding to the surface inversion layer is formed on the surface of the P-type germanium substrate 143168.doc -99 - 201015731 202 ° according to Fig. 20 (4) and Fig. 20 (8) The energy band diagram shown is numerically calculated.

知，藉由作為雜質之绝而生成電子載體之活化能〜為_〇 U em3 eV，特別是為_〇12 eV。即，已閘明，存在於氧 化矽臈與P型矽基板之界面附近之铯係於p型矽基板之傳導 帶下端之上方約（M2 eV的位置形成雜f能階，藉由來自該 雜質能階之電子釋出而於?型矽基板之表面形成電子反轉 層。 再者於圖19中，一點鏈線表示藉由作為雜質之鉋而生 成電子載體之活化能EaU13 eV時之行為，實線表示該 活化能EA為·〇·12 eV時之行為，虛線表示該活化能Ea為 -〇·11 eV時之行為，但當藉由作為雜質之绝而生成電子載 體之活化能E^-G_ll eV〜_G.13 eV時，特別為12 ^時 之行為係與圖19所示之結果一致。 圖21至圖25中分別表示於圖2〇(a)及圖2〇(b)所示之能帶 圖之構成中，在氧化矽膜與口型矽基板之界面附近之電子 反轉層之電子面密度（cm-2)、及氧化矽膜與p型矽基板之界 面上所存在之雜質之面密度（cm·2)的關係。 此處，於圖21至圖25中，橫軸表示上述雜質之面密度 (cm2)，縱軸表示上述電子反轉層之電子面密度…工·2)。 又於圖21至圖25中’分別用線來表示使活化能Ea自_〇 〇〇 〇·2〇 eV為止依次以每次_〇 〇2 ev發生變化時存在於 氧化矽膜與p型矽基板之界面上的雜質之面密度（cm·2)、與 電子反轉層之電子面密度（cm-2)之關係。再者，根據上述 143168.doc 201015731 a与-0.12 eV之 實驗結果，使用鉋作為雜質之情形相當於 情形。 田、A、- 又 關係 關係 關係 圖21表示p型矽基板中 農度為lxl〇16 cm·3時之 表不P型石夕基板中之衛農度為lx1〇” cm-3時之 圖23表示口型矽基板中之硼濃度為lx10'm-3時之 又’圖24表示p型石夕基板中之蝴遭度為3_3 時之關係’圖25表示p型妙基板中 P土令吞奴〒之硼濃度為6χΐ〇18 時之關係。It is known that the activation energy of the electron carrier generated by the impurity is _〇 U em3 eV, especially _〇12 eV. That is, it is known that the yttrium present in the vicinity of the interface between the yttrium oxide and the P-type ruthenium substrate is above the lower end of the conduction band of the p-type ruthenium substrate (the position of the M2 eV forms a hetero-fi-level, by which the impurity is derived from the impurity The electrons of the energy level are released to form an electron inversion layer on the surface of the ?-type substrate. Further, in Fig. 19, the one-dot chain line indicates the behavior when the activation energy EaU13 eV of the electron carrier is generated by the planer as an impurity. The solid line indicates the behavior when the activation energy EA is 〇·12 eV, and the broken line indicates the behavior when the activation energy Ea is -〇·11 eV, but when the activation energy E^ of the electron carrier is generated by the impurity as an impurity -G_ll eV~_G.13 eV, especially the behavior at 12 ^ is consistent with the results shown in Figure 19. Figure 21 to Figure 25 are shown in Figure 2 (a) and Figure 2 (b) In the composition of the energy band diagram, the electron inversion layer (cm-2) of the electron inversion layer near the interface between the yttrium oxide film and the die-shaped germanium substrate, and the interface between the yttrium oxide film and the p-type germanium substrate exist. The relationship between the areal density (cm·2) of the impurities. Here, in Figs. 21 to 25, the horizontal axis represents the areal density (cm2) of the above impurities. The vertical axis represents the electron density of the surface inversion layer electron work ... 1.2). In addition, in FIG. 21 to FIG. 25, the activation energy Ea is present in the yttrium oxide film and the p-type enthalpy when the activation energy Ea changes from _〇〇·2〇eV to _〇〇2 ev. The relationship between the areal density (cm·2) of the impurity on the interface of the substrate and the electron areal density (cm-2) of the electron inversion layer. Furthermore, according to the above experimental results of 143168.doc 201015731 a and -0.12 eV, the use of planing as an impurity is equivalent to the case. Field, A, and relationship relationship Fig. 21 shows the graph when the agronomic degree of the p-type 矽 substrate is lxl 〇 16 cm·3, and the auxiliaries in the P-type Shixi substrate are lx1〇” cm-3. 23 indicates that the boron concentration in the die-shaped ruthenium substrate is lx10'm-3. FIG. 24 shows the relationship when the butterfly degree in the p-type shi shi substrate is 3_3. FIG. 25 shows the P-soil order in the p-type substrate. The relationship between the boron concentration of the swallows is 6χΐ〇18.

又，圖21至圖25令之斜線部分表示作 不邗為先電轉換裝置而 顯示優異特性之範圍。gp，若超出上述斜線部分之範圍之 上限，則電子反轉層之電子面密度會過度變大，使p型石夕 基板之表面金屬（metalie)化轉以人射光，&amp;而特性降 低，若低於上述斜線部分之範圍之下限，則電子反轉層之 電子面密度會過度變小，使電阻上升，從而特性降低。 如圖21至圖25所示，當雜質為绝時（Ea%_〇.i2…時）， 對於？型♦基板中之贿度為任—濃度之情況，雜質之面 密度（cm·2)與電子反轉層之電子面密度（cm_2)均不會一致。 先前，認為氧化矽膜中之铯均為離子化者，故而認為存在 於氧化矽膜與p型矽基板之界面上的绝之面密度（cm·2)與已 離子化之链（正的固定電荷）之面密度（cm·2)為一致。此 處，已離子化之鉋之面密度係表示為p型矽基板上所誘發 之電子反轉層之電子面密度、與形成於？型矽基板之表面 上之空乏層中的空間電荷密度之和，在p型矽基板中之硼 濃度較低之情形、或者電子反轉層之電子面密度卜^2)充 143168.doc -101- 201015731 分两之情形時，存在於該界面上之铯之面密度㈣力與p 型石夕基板上所誘發之電子反轉層之電子面密度㈣力變得 大致一致。然而，根據_21至圖25所示之斜線部分之範 圍内上述已離子化之絶之面密度（cm_2)小於上述電子反轉 層之電子面密度（^)之情況可知，$ 了獲得所期望之電 子反轉層之電子面密度(cm，，,必需以使存在於氧化矽膜 與p型石夕基板之界面上的絶之面密度（cm_2)高於上述所期望 之電子反轉層之電子面密度(cm-2)的方式，將鉋離子導入 至氧化矽膜。 圖26(a)中表示如先前之專利文獻丨所述的於p型矽基板之 表面上形成有氧化㈣ '於氧化石夕膜上形成有氮化石夕膜、 f於氮化矽膜與氧化矽膜之界面上配置有成為正的固定電 荷之雜質時的能帶圖。又’圖辱）中表示如圖㈣示之構 成之光電轉換裝置之試樣般的於？型矽基板之表面上形成 有氧化矽膜、且於氧化矽膜與p型矽基板之界面上配置有 成為正的固定電荷之雜質時的能帶圖。 I而5，在成為正的固定電荷之雜質之能階與p型矽 基板之間會引起電子之移動，當存在充分之密度之雜質 時，會引起電子之移動，直至成為正的固定電荷之雜質之 月t* 1%與p型石夕基板之費米能階（Fermi ievei)大致一致為止。 然而，如圖26(a)所示，當在成為正的固定電荷之雜質與 P型矽基板之間存在氧化矽膜時，由於氧化矽膜中之電位 梯度，成為正的固定電荷之雜質之活化能〜會有效地增加 (成為正的固定電荷之雜質之能階201之位置會有效下降）。 143168.doc 201015731 藉此’移動至P型矽基板之表面之與反轉層相對應之能階 202上的電子量將減少，從而p型矽基板之表面上之反轉層 的電子面密度會變小。 另一方面，如圖26(b)所示，當直接形成於p型矽基板之 表面上之氧化矽膜在與p型矽基板之表面之界面上含有成 為正的固定電荷之雜質時，與圖26(a)之情形不同，並不存 在有插入之介電質膜’故而不會產生成為正的固定電荷之 雜質之活化能EA之有效的增加。因此，於此情形時，移動 至P型矽基板之表面之與反轉層相對應之能階202上的電子 量不會降低，故而p型矽基板之表面上之反轉層之電子面 密度不會變小。 再者’圖14所示之光電轉換裝置之試樣並未形成為利用 穿随效應而使載體移動之構成，但可認為，本實施例中之 實驗結果亦可適用於例如圖27至圖29所例示之利用穿隨效 應等而使載體移動之構成的光電轉換裝置。 應當認為，此次所揭示之實施形態及實施例在所有方面 均為例示而並非限制本發明。本發明之範圍並非由上述說 明而是由申請專利範圍所揭示，且意圖包含與申請專利範 圍均等之意義及範圍内之所有的變更。 產業上之可利用性 本發明之光電轉換裝置可能會可適用於例如太陽電池等 中。 【圖式簡單說明】 圖1 (a)係本發明之光電轉換裝置之一例的光入射側之表 143168.doc -103- 201015731 面之俯視示意圖’ (b)係沿著⑷之lb ib之剖面示意圖，⑷ 係沿著（a)之lc-lc之剖面示意圖； 圖2⑷係本發明之光電轉換裝置之另—例的光入射侧之 表面之俯視不意圖’⑻係沿著⑷之m之剖面示意圖， (c)係沿著（a)之2c-2c之剖面示意圖； 圖3(a)係本發明之光電轉換裝置之另—例的光入射侧之 表面之俯視示意圖，(b)係沿著⑷之3b-3b之剖面示意圖， (c)係沿著（a)之3c-3c之剖面示意圖； 本發明之光電轉換裝置之另—例的光入射側之 表面之俯視示意圖’ (b)係沿著⑷之4b-4b之剖面示意圖， (c)係沿著（a)之4c-4c之剖面示意圖； 圖5係本發明之光電轉換裝置之另一例之剖面示意圖； 圖6係本發明之光電轉換裝置之另—例之剖面示意圖； 圖7係本發明之光電轉換裝置之另—例之剖面示意圖； 圖8係本發明之光電轉換裂置之另一例之剖面示意圖； 圖9係本發明之光電轉換裝置之另一例之剖面示意圖； 圖10係本發明之光電轉換裝置之另—例之立體示意圖； 圖11係本發明之光電轉換裝置之另-例之立體示意圖； 圖12係本發明之光電轉換|置之另—例之剖面示意圖； 圖13係圖解圖12所示之構成之光電轉換裝置之製造方法 之一例的步驟之一部分之剖面示意圖； 圖14係本發明之實施例中所製作之光電轉換裝置之試樣 的剖面示意圖； 圖15係圖14所示之構成之光電轉換裝置之試樣之製作方 143168.doc -104· 201015731 法的流程圖； 圖16係表示對圖14所示之構成之光電轉換裝置之試樣進 行在氧化矽膜與p型矽基板之界面附近之組成分析所得之 結果的示圖； 圖17係表示圖14所示之構成之光電轉換裝置之試樣在氧 化矽膜與p型矽基板之界面附近之鎚之偏析量、與因鉋之 偏析而於P型石夕基板之表面所誘發之電子反轉層之電子面 密度之關係的示圖； 圖18係表示圖14所示之構成之光電轉換裝置之試樣於氧 化石夕膜中離子佈植之鉋離子之劑量、及p型矽基板之已誘 發電子的電子反轉層之薄片電阻之關係的示圖； 圖19係表示圖14所示之構成之光電轉換裝置之試樣於p 型石夕基板之表面上所誘發之電子反轉層之電子面密度與溫 度之關係的示圖； 圖20(a)係p型矽基板與氧化矽膜之界面上所存在之雜質 在離子化前的狀態下p型矽基板與氧化矽膜之界面附近之 能帶圖，（b)係p型矽基板與氧化矽膜之界面上所存在之雜 質在離子化後的狀態下p型矽基板與氧化矽膜之界面附近 之能帶圖； 圖21係表示於圖20(a)及圖20(b)所示之能帶圖之構成 中’氧化矽膜與p型矽基板之界面附近之電子反轉層之電 子面密度（cnT2)、與p型矽基板的表面之雜質之面密度 (cnT2)之關係的示圖； 圖22係表示於圖20(a)及圖20(b)所示之能帶圖之構成 143168.doc -105- 201015731 中’氧化矽膜與p型矽基板之界面附近之電子反轉層之電Further, the hatched portions of Figs. 21 to 25 show the range in which excellent characteristics are exhibited as the first electric conversion device. Gp, if the upper limit of the range of the oblique line portion is exceeded, the electronic surface density of the electron inversion layer is excessively increased, so that the surface metal of the p-type slab substrate is converted to human light, and the characteristics are lowered. If the lower limit of the range of the oblique line portion is lower than the lower limit of the range of the oblique line portion, the electronic surface density of the electron inversion layer is excessively small, and the electric resistance is increased, so that the characteristics are lowered. As shown in Fig. 21 to Fig. 25, when the impurity is absolute (Ea%_〇.i2...), for ? Type ♦ The bribe degree in the substrate is the case of any concentration, and the surface density (cm·2) of the impurity and the electronic surface density (cm_2) of the electron inversion layer do not coincide. Previously, it was considered that the ruthenium oxide film was ionized, so it was considered that the surface density (cm·2) and the ionized chain (positive fixation) existed at the interface between the yttrium oxide film and the p-type ruthenium substrate. The surface density (cm·2) of the charge) is uniform. Here, the surface density of the ionized planer is expressed as the electron surface density of the electron inversion layer induced on the p-type germanium substrate, and is formed in? The sum of the space charge densities in the depletion layer on the surface of the ruthenium substrate, the case where the boron concentration in the p-type ruthenium substrate is low, or the electron surface density of the electron reversal layer is 143168.doc -101 - 201015731 In the case of two, the surface density (4) force existing on the interface is substantially the same as the electron surface density (4) force of the electron inversion layer induced on the p-type Si Xi substrate. However, according to the case where the surface density (cm_2) of the ionized surface is smaller than the electron surface density (^) of the electron inversion layer in the range of the oblique line portion shown in _21 to FIG. 25, it is understood that the desired value is obtained. The electron areal density (cm, of the electron inversion layer must be such that the areal density (cm_2) existing at the interface between the yttrium oxide film and the p-type shi 基板 substrate is higher than the above-mentioned desired electron inversion layer In the manner of the electron areal density (cm-2), the planer ions are introduced into the ruthenium oxide film. Fig. 26(a) shows that an oxidation (four) is formed on the surface of the p-type germanium substrate as described in the prior patent document. An energy band diagram is formed on the oxidized stone film, and an impurity band which is a positive fixed charge at the interface between the tantalum nitride film and the yttrium oxide film is formed on the oxidized stone film, and the figure is shown in FIG. What is the sample of the photoelectric conversion device shown in the figure? An energy band diagram in which a ruthenium oxide film is formed on the surface of the ruthenium substrate and an impurity which becomes a positive fixed charge is disposed on the interface between the ruthenium oxide film and the p-type ruthenium substrate. I and 5, between the energy level of the impurity which becomes a positive fixed charge and the p-type germanium substrate, causes electrons to move. When there is sufficient density of impurities, the electrons are moved until they become positive fixed charges. The month t* 1% of the impurity is approximately the same as the Fermi ievei of the p-type Shishi substrate. However, as shown in Fig. 26(a), when a ruthenium oxide film is present between the impurity which becomes a positive fixed charge and the P-type ruthenium substrate, it becomes a positive fixed charge impurity due to the potential gradient in the ruthenium oxide film. The activation energy ~ is effectively increased (the position of the energy level 201 which becomes an impurity of a positive fixed charge is effectively lowered). 143168.doc 201015731 whereby the amount of electrons on the energy level 202 corresponding to the inversion layer on the surface of the P-type germanium substrate will be reduced, so that the electron surface density of the inversion layer on the surface of the p-type germanium substrate will be Become smaller. On the other hand, as shown in FIG. 26(b), when the ruthenium oxide film directly formed on the surface of the p-type ruthenium substrate contains an impurity which becomes a positive fixed charge at the interface with the surface of the p-type ruthenium substrate, In the case of Fig. 26(a), there is no effective increase in the activation energy EA of the intervening dielectric film, so that no impurity which becomes a positive fixed charge is generated. Therefore, in this case, the amount of electrons on the energy level 202 corresponding to the inversion layer that is moved to the surface of the P-type germanium substrate is not lowered, so that the electron areal density of the inversion layer on the surface of the p-type germanium substrate It won't get smaller. Further, the sample of the photoelectric conversion device shown in FIG. 14 is not formed to move the carrier by the wear-through effect, but it is considered that the experimental results in the present embodiment can also be applied to, for example, FIGS. 27 to 29. A photoelectric conversion device having a configuration in which a carrier is moved by a wear-through effect or the like is exemplified. It is to be understood that the embodiments and examples disclosed herein are illustrative and not restrictive. The scope of the present invention is defined by the scope of the claims and the scope of the claims Industrial Applicability The photoelectric conversion device of the present invention may be applicable to, for example, a solar battery or the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (a) is a plan view of a light incident side of an example of a photoelectric conversion device of the present invention, 143168.doc -103 - 201015731 (b) is a section along the lb ib of (4) Fig. 2(4) is a schematic cross-sectional view taken along line lc-lc of (a); Fig. 2(4) is a plan view of the surface of the light incident side of another example of the photoelectric conversion device of the present invention, which is not intended to be '(8) along the section of (4) m (c) is a schematic cross-sectional view taken along line 2c-2c of (a); Fig. 3(a) is a top plan view showing the surface of the light incident side of another example of the photoelectric conversion device of the present invention, (b) (c) is a schematic cross-sectional view of 3b-3b, (c) is a schematic cross-sectional view taken along line 3c-3c of (a); a top view of the surface of the light incident side of another example of the photoelectric conversion device of the present invention' (b) A schematic cross-sectional view taken along line 4b-4b of (4), (c) is a schematic cross-sectional view taken along line 4c-4c of (a); FIG. 5 is a schematic cross-sectional view of another example of the photoelectric conversion device of the present invention; FIG. 7 is a cross-sectional view showing another example of the photoelectric conversion device of the present invention; FIG. Figure 8 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention; Figure 9 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention; and Figure 10 is a perspective view showing another example of the photoelectric conversion device of the present invention. Fig. 11 is a perspective view showing another embodiment of the photoelectric conversion device of the present invention; Fig. 12 is a schematic cross-sectional view showing another embodiment of the photoelectric conversion of the present invention; and Fig. 13 is a view showing the photoelectric conversion of the composition shown in Fig. 12. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 14 is a cross-sectional view showing a sample of a photoelectric conversion device produced in an embodiment of the present invention; FIG. 15 is a photoelectric conversion device of the configuration shown in FIG. Sample preparation 143168.doc -104· 201015731 The flow chart of the method; FIG. 16 shows the composition of the sample of the photoelectric conversion device of the configuration shown in FIG. 14 in the vicinity of the interface between the yttrium oxide film and the p-type ruthenium substrate. FIG. 17 is a view showing the segregation amount of the hammer in the vicinity of the interface between the yttrium oxide film and the p-type yttrium substrate of the sample of the photoelectric conversion device of the configuration shown in FIG. FIG. 18 is a view showing a relationship between the electron inversion layer of the electron inversion layer induced on the surface of the P-type slab substrate; FIG. 18 is a view showing the sample of the photoelectric conversion device having the configuration shown in FIG. FIG. 19 is a view showing the relationship between the dose of the ion implanted ion in the film and the sheet resistance of the electron inversion layer of the electron-inducing layer of the p-type germanium substrate; FIG. 19 is a view showing the photoelectric conversion device of the composition shown in FIG. A diagram showing the relationship between the electron surface density of the electron inversion layer induced on the surface of the p-type slab substrate and temperature; FIG. 20(a) is an impurity present at the interface between the p-type ruthenium substrate and the ruthenium oxide film. The energy band diagram near the interface between the p-type ruthenium substrate and the ruthenium oxide film in the state before ionization, and (b) the impurity present at the interface between the p-type ruthenium substrate and the ruthenium oxide film in the state after ionization An energy band diagram near the interface between the ruthenium-based substrate and the ruthenium oxide film; FIG. 21 is a view showing the structure of the energy band diagram shown in FIGS. 20(a) and 20(b), and the p-type ruthenium film and the p-type ruthenium substrate. The electron areal density (cnT2) of the electron inversion layer near the interface, and the surface of the p-type germanium substrate Fig. 22 is a diagram showing the relationship between the density of the surface density (cnT2) and Fig. 22 showing the composition of the energy band diagram shown in Figs. 20(a) and 20(b) 143168.doc-105-201015731 The electrical inversion layer near the interface of the p-type germanium substrate

子面密度（cm )、與p型碎基板的表面之雜暂+ I 〜潍A之面密度 (cm_2)之關係的示圖； 圖23係表示於圖20(a)及圖20(b)所示之泸塊 义此帶圖之構成 中’氧化矽膜與p型矽基板之界面附近之電子反轉層之電 子面密度（cm·2)、與p型矽基板的表面之 〜雅員之面密度 (cm·2)之關係的示圖； 圖24係表示於圖20(a)及圖20(b)所示之能帶圖之構成 中，氧化矽膜與p型矽基板之界面附近之電子反轉層之電 子面密度（cm·2)、與p型矽基板的表面之雜質之面密度 (cm_2)之關係的示圖； &amp; 圖25係表示於圖20⑷及圖2〇(b)所示之能帶圖之構成 中，氧化矽膜與p型矽基板之界面附近之電子反轉層之電 子面密度(cm。、肖p型矽基板的纟面之雜質之面密度 (cm·2)之關係的示圖； 又 圖26⑷係如先前之專利文獻1所揭示的於p型矽基板之表 面上形成有氧化石夕膜、於氧化石夕膜上形成有氮切膜、且 於氮切膜與氧化㈣之界面上配置有成為正的固定 之雜質時的能帶圖，（b)係如圖14所示之構成之光電轉換裝 ，之試樣的於PM基板之表面上形成有氧切膜、且於 氧化矽膜與P型矽基板之界 06置有成為正的固定電荷 之雜質時的能帶圖； 圖27係本發明之光電轉換裝 心力例之剖面示意圖.； 圖28係本發明之光電轉換裝晋 兴衮置之另一例之剖面示意圖； 143168.doc 201015731 圖29係本發明之光電轉換裝置之另一例之剖面示意圖。The relationship between the sub-surface density (cm) and the surface temporary density of the surface of the p-type substrate + I ~ 潍 A (cm_2); Figure 23 is shown in Figure 20 (a) and Figure 20 (b) The block shown in the figure shows the electronic surface density (cm·2) of the electron inversion layer near the interface between the yttrium oxide film and the p-type germanium substrate, and the surface of the p-type germanium substrate. FIG. 24 is a view showing the relationship between the surface density (cm·2) and the p-type germanium substrate in the configuration of the energy band diagrams shown in FIGS. 20(a) and 20(b). A graph showing the relationship between the electronic areal density (cm·2) of the nearby electron inversion layer and the areal density (cm_2) of the impurity on the surface of the p-type germanium substrate; &amp; Figure 25 is shown in Fig. 20 (4) and Fig. 2 (b) The energy band diagram shown in the figure, the electron inversion layer of the electron inversion layer near the interface between the yttrium oxide film and the p-type yttrium substrate (cm., the surface density of the impurity of the surface of the pp-type 矽 substrate) FIG. 26(4) shows that an oxide film is formed on the surface of the p-type germanium substrate and a nitrogen film is formed on the oxide film as disclosed in the prior patent document 1. Nitrogen An energy band diagram in which a positively fixed impurity is disposed at an interface between the slit film and the oxidation (4), and (b) is a photoelectric conversion device having a structure as shown in FIG. 14, and the sample is formed on the surface of the PM substrate. FIG. 27 is a cross-sectional view showing an example of a photoelectric conversion device according to the present invention; FIG. 28 is a cross-sectional view showing an example of a photoelectric conversion device according to the present invention; A cross-sectional view showing another example of the photoelectric conversion device of the present invention; 143168.doc 201015731 FIG. 29 is a schematic cross-sectional view showing another example of the photoelectric conversion device of the present invention.

【主要元件符號說明】 1 p +層 2 p型矽基板 2a 第1非晶矽層 2b 第2非晶矽層 2c 第3非晶矽層 3、102 n+層 4 、 35 、 40 、 103 表面反轉層 4a 第1反轉層 4b 第2反轉層 4c 第3反轉層 4d 第4反轉層 5 ' 104 絶 6、6a、6b、6c、26、 氧化矽膜 32 、 34 、 37 、 39 、 60 7 背面電極 8 金屬電極 9 透明導電膜 10 金屬矽化物 11 邊緣部 12a、12b 薄膜矽層 13 蓄積層 14 玻璃基板 143168.doc -107- 201015731 15 16 17 18 19 20 ' 21 ' 50 24、 31、36 25 33 38 40 51 52 53 101 105 106 107 109 、111 、 113 110 、112 200 、201 202 凹凸 P型半導體層 η型半導體層 η型用電極 ρ型用電極 雜質 背面反轉層 雜質 第1中間透明導電膜 第2中間透明導電膜 背面反轉層 第1光電轉換層 第2光電轉換層 第3光電轉換層 Ρ型矽基板 氧化矽膜 氮化矽膜 電極 ρ型層 η型層 雜質能階 能階 143168.doc[Description of main component symbols] 1 p + layer 2 p-type germanium substrate 2a first amorphous germanium layer 2b second amorphous germanium layer 2c third amorphous germanium layer 3, 102 n+ layer 4, 35, 40, 103 surface inverse Transition layer 4a First inversion layer 4b Second inversion layer 4c Third inversion layer 4d Fourth inversion layer 5' 104 Absolute 6, 6a, 6b, 6c, 26, hafnium oxide film 32, 34, 37, 39 60 7 Back electrode 8 Metal electrode 9 Transparent conductive film 10 Metal halide 11 Edge portion 12a, 12b Thin film layer 13 Accumulation layer 14 Glass substrate 143168.doc -107- 201015731 15 16 17 18 19 20 ' 21 ' 50 24, 31,36 25 33 38 40 51 52 53 101 105 106 107 109 , 111 , 113 110 , 112 200 , 201 202 Concave-convex P-type semiconductor layer n-type semiconductor layer n-type electrode p-type electrode impurity backside inversion layer impurity 1 intermediate transparent conductive film 2nd intermediate transparent conductive film back surface inversion layer 1st photoelectric conversion layer 2nd photoelectric conversion layer 3rd photoelectric conversion layer Ρ type 矽 substrate 矽 矽 film tantalum nitride film electrode p type layer η type layer impurity energy Order energy level 143168.doc

Claims (1)

201015731 七、申請專利範圍： 1· 一種光電轉換裝置，其包含： 半導體層（2、2a、2b、2C、12a、12b、1〇1);及 介電質膜（6、6a、6b、6c、26、32、34、37、Μ、 . 60、1〇5)，其係以與上述半導體層（2、2a、2b、2c、 12a、12b、101)之表面相接之方式而設置； 上述介電質膜（6、6a、6b、6c、26、32、34、P、 39、60、105)在與上述半導體層（2、2&amp;、沘、2c、仏、 ❿ 12b、1G1)之界面附近’含有成為正或負的固定電荷之雜 質（5、20 ' 21、25、50、1〇4)。 2. 如請求項1之光電轉換裝置，其中上述半導體層（2、 2b、2c、12a、12b、1〇1)包含結晶石夕、非晶石夕或微晶 石夕。 3. 如請求項1之光電轉換裝置，其中上述介電質膜（6、6a、 6b、6c、26、32 ' 34、37 ' 39、60、105)之帶隙為 4 2 eV以上。 _ 4·如請求項1之光電轉換裝置，其中上述介電質膜（6、6a、 6b、6c、26、32、34、37、39、60、1〇5)包含選自由氧 化石夕、氮氧化石夕及IL化石夕所組成之群中之至少一種。 . 5.如請求項1之光電轉換裝置，其中成為正的固定電荷之 雜質（5、20、104)包含選自由鋰、鈉、鉀、铷、绝、 鎂、鈣、勰、鋇、磷、砷及銻所組成之群中之至少— 種。 6.如請求項1之光電轉換裝置，其中成為負的固定電荷之 143168.doc 201015731 雜：(21、25' 50)包含選自由硼、鋁、鎵、銦、鉑、氟 化田勒烯、氧化富勒烯、氟、氣、溴及碘所組成之群中 之至少一種。 7. 8. 如請求項1之光電轉換裝置’其中在與上述介電質膜（6、 6b、6c、26、32、34、37、39、60、105)相接之上 述半導體層(2、2a、2b、2c、12a、12b、1〇1)UM 區域的至少—部分上，包含第!導電型或第2導電型之表 面反轉層（4、4a、4c、35、40、1〇3)。 如請求項7之光電轉換裝置，其中包含 雜質含有層（3、102)，其係於上述半導體層（2、2a、 2b、2c、12a、i2b、1〇1)之表面之至少一部分上含有 與上述表面反轉層（4、4a、4c、35、4〇、1〇3)為相同導 電型之雜質，且更包含 電極（8、9、1〇、107)，其係與上述雜質含有層、 102)相接。 9·如請求項8之光電轉換裝置，其中上述電極（8、9、、 107)包3選自由金屬、金屬碎化物以及透明導電膜所組 成之群中之至少一種。 10.如請求項1之光電轉換裝置，其中上述雜質（5、2〇、21、 25、50、104)存在最多之部位，係位於從上述半導體層 (2、2a、2b、2c、12a、12b、101)與上述介電質膜（6、 6a、6b、6c、26、32、34、37、39、60、1〇5)之界面 起，在相對於上述界面而垂直之方向上朝著上述半導體 層（2、2a、2b、2c、12a、12b、101)側前進 5 nm 之區 143168.doc 201015731 域、與朝著上述介電質膜（6、6a、6b、6c、26、32、 34 37、39、60、105)側前進5 nm之區域之間的區域。 11.如請求項丨之光電轉換裝置，其中於上述半導體層（2、 2a' 2b、2e' 12a、12b、1〇1)之表面形成有凹凸。 12_ —種光電轉換裝置，其包含： 第1光電轉換層（51);及 第2光電轉換層（52); 上述第1光電轉換層（51)包含：第1半導體層（2a);表 面介電質膜（6) ’其係以與上述第1半導體層（2a)之表面相 接之方式而設置，並且在與上述第丨半導體層（2a)之界面 附近含有成為正或負的固定電荷之雜質（5);第1導電型 或第2導電型之表面反轉層（4)，其係設置在與上述表面 介電質膜⑹相接之上述第鲆導體層⑽之表面之區域的 至乂部分上，及第1雜質含有層（1)，其係設置於與上 述第1半導體層（2a)之表面為相反側之背面上，並且含有 與上述表面反轉層（4)為相反導電型之第丨雜質； 上述第2光電轉換層（52)包含：第2半導體層（2b);第2 雜質含有層（3)，其係設置於上述第2半導體層（2b)之表 面，並且含有與上述第1雜質含有層（1)為相反導電型之 第2雜質，及第3雜質含有層⑴，其係設置於與上述第] 半導體層（2b)之表面為相反側之背面上，並且含有與上 述第2雜質為相反導電型之第3雜質；且 該光電轉換裝置具有積層結構，其係將上述第丨光電 轉換層⑼之上述第i雜質含有層⑴與上述第2光電轉換 143168.doc 201015731 層（52)之上述第2雜質含有層（_合，由上光㈣ 換層（51)與上述第2光電轉換層（52)積層而成。 13. —種先電轉換裝置，其包含： 半導體層（2); 表面介電質_)，其係以與上料導體層⑺之表面 上相接之方式而設置；及 背面介電質膜（60)，其係以與上述半導體層（2)之表面 為相反側之背面相接之方式而設置； 上述表面介電質膜（6)在與上述半導體層（2)之界面附 近，含有成為第1極性之固定電荷之雜質， 上述背面介電質膜（60)在與上述半導體層（2)之界面附 近，含有成為與上述第1極性相反之第2極性之固定電荷 的雜質。 14. 一種光電轉換裝置，其包含： 第1半導體層（12a); 第1介電質膜（6a) ’其係與上述第1半導體層（12a)之表 面相接合； 第2介電質膜（6b) ’其係與上述第1半導體層（12a)之背 面相接合；及 第2半導體層（〖2b)，其係與上述第2介電質膜（6b)之背 面相接合； 上述第1介電質膜（6a)在與上述第1半導體層（i2a)之界 面附近’含有成為第1極性或第2極性之固定電荷的雜質 (20)， 143168.doc 201015731 上述第2介電質膜（6b)在與上述第〗半導體層（12a)之界 面附近、以及與上述第2半導體層（12b)之界面附近，含 有成為與上述第1介電質膜（6a)中所含之雜質（2〇)為相反 極性之固定電荷的雜質（21) » 15. —種光電轉換裝置，其包含： 半導體層（2a、2b、2c);及 介電質膜（6、26、32、34、37、39)，其係以與上述半 導體層（2a、2b、2c)之表面相接之方式而設置； 上述介電質膜（6、26、32、34、37、39)在與上述半導 體層（2a、2b、2c)之界面附近，含有成為正或負的固定 電荷之雜質（5、25)， 於上述介電質膜（6、26、32、34、37' 39)之表面上含 有透明導電膜（9、33、38)， 使載體通過上述介電質膜（6、26、32、34、37、39)並 自上述透明導電膜（9、33、38)被取出至外部。 16. 如請求項15之光電轉換裝置，其中於上述透明導電膜 (9、33、38)之表面上包含透明基板（14)。 17·如請求項15之光電轉換裝置，其中在與上述介電質膜 (6、26、32、34、37、39)相接之上述半導體層…、 几、2c)之表面之區域的至少一部分上，含有第1導電型 或第2導電型之表面反轉層（4、24、31、35、刊、4())。 18. 如請求項15之光電轉換裝置，其巾上述半導體層…、 2b、2c)包含結晶矽、非晶矽或微晶矽。 19. 如請求項15之光電轉換裝置’其中上述半導體層伽、 143168.doc 201015731 2b、2c)之厚度較上述半導體層（2a、2b、2c)内之載體擴 散長度更薄。 20.如請求項15之光電轉換裝置’其中上述介電質膜（6、 26、32、34、37、39)之帶隙為 4.2 eV以上。 21·如請求項15之光電轉換裝置，其中上述介電質膜（6、 26、32、34、37、39)包含選自由碳化矽、氧化矽、'氮氧 化石夕及氮化石夕所組成之群中之至少一種。 22·如請求項15之光電轉換裝置’其中上述介電質膜（6、 26、32、34、37、39)之厚度為 3 nm以下。 23·如請求項15之光電轉換裝置，其中成為正的固定電荷之 雜質(5)包含選自由鋰、鈉、鉀、铷、铯、鎂、鈣、锶、 鋇、磷、砷及銻所組成之群中之至少一種。 24.如請求項15之光電轉換裝置，其中成為負的固定電荷之 雜質（25)包含選自由蝴、銘、嫁、鋼、翻、氣化富勒 烯、氧化富勒烯、氟、氣、溴及碘所組成之群中之至少 一種0 25·如請求項15之光電轉換裝置，其中成為上述固定電荷之 雜質（5、25)存在最多之部位’係位於從上述半導體層 (2a、2b、2〇與上述介電質膜（6、％、32、34、^、叫 之界面起’在相對於上述界面而垂直之方向上朝著上述 +導鱧層（2a、2b、2c)側前進5⑽之區域、與朝著上述 介電質膜（6、26、32、34、37、39)側前進511111之區域之 間的區域上。 26 -種光電轉換裝置，其包含： 143168.doc -6 - 201015731 第1半導體層（2a); 表面介電質膜（6)，其係以與上述第1半導體層（2a)之 表面相接之方式而設置； 第1導電型雜質含有層（109)，其係形成於上述第1半導 體層（2a)之背面； 第2半導體層（2b)，其係設置於上述第丨半導體層（2a) 之背面側； 第2導電型雜質含有層（11〇)，其係形成於第2半導體層 (2b)之表面； 第1導電型雜質含有層（m)，其係形成於上述第2半導 體層（2b)之背面； 第3半導體層（2c)，其係設置於上述第2半導體層（2b) 之背面側； 第2導電型雜質含有層（112)，其係形成於上述第3半導 體層（2c)之表面；及 第1導電型雜質含有層（u 3)，其係形成於上述第3半導 體層（2c)之背面； 將上述第1半導體層（2a)之背面之上述第丨導電型雜質 含有層（109)、與上述第2半導體層（2b)之表面之上述第2 導電型雜質含有層（110)加以接合， 將上述第2半導體層（2b)之背面之上述第丨導電型雜質 含有層（111)、與形成於上述第3半導體層（2c)之表面之第 2導電型雜質含有層（112)加以接合， 上述表面介電質膜（6)在與上述第丨半導體層（2a)之界 143168.doc 201015731 面附近，含有成為正或負的固^電荷之雜質⑺， 在與上述表面介電質膜（6)相接之上述第^導體層 ⑽之表面之區域的至少一部分上，形成有第2導電型之 表面反轉層（4)， 於上述表面介電質膜⑹之表面上’含有透明導電膜 (9)， 使載體通過上述表面介電質膜⑹並自上述透明導電膜 (9)被取出至外部。 27. —種光電轉換裝置，其包含： 第1半導體層（2a); 表面介電質膜（6)，其係以與上述”半導體層（2a)之 表面相接之方式而設置； 第1導電型雜質含有層（109)，其係形成於上述第i半導 體層（2a)之背面； 第2半導體層（2b)，其係設置於上述第】半導體層㈣ 之背面側； 第2導電型雜質含有層（11〇)，其係形成於第2半導體層 (2b)之表面； 第1導電型雜質含有層（111)，其係形成於上述第2半導 體層（2b)之背面； 第3半導體層（2c)，其係設置於上述第2半導體層（2b) 之背面側； 第2導電型雜質含有層（112)，其係形成於上述第3半導 體層（2c)之表面；及 143168.doc 201015731 背面介電質膜（26)，其係形成於上述第3半導體層（2c) 之背面； 將上述第1半導體層（2a)之背面之上述第丨導電型雜質 含有層（109)、與上述第2半導體層（2b)之表面之上述第2 導電型雜質含有層（110)加以接合， 將上述第2半導體層（2b)之背面之上述第丨導電型雜質 含有層（111)、與形成於上述第3半導體層（2c)之表面之第 2導電型雜質含有層（112)加以接合， 上述表面介電質膜（6)在與上述第1半導體層（2a)之界 面附近，含有成為正或負的固定電荷之雜質（5)， 在與上述表面介電質膜相接之上述第1半導體層 (2a)之表面之區域的至少一部分上，形成有第2導電型之 表面反轉層（4)， 上述背面介電質膜（26)含有成為與上述表面介電質膜 (6)中所含之上述雜質（5)為相反極性之固定電荷的雜質 (25) ， 在與上述背面介電質膜（26)相接之上述第3半導體層 (2c)之背面之區域的至少一部分上，形成有第丨導電型之 背面反轉層（24)， 於上述表面介電質膜（6)之表面上含有透明導電膜 (9)， 於上述背面介電質膜（26)之背面上含有背面電極， 使載體通過上述表面介電質膜（6)及上述背面介電質膜 (26) ’並自上述透明導電膜（9)及上述背面電極（7)分別被 143168.doc 201015731 取出至外部。 28. —種光電轉換裝置，其包含： 第1半導體層（2a); 第1表面；1電質骐（6)’其係以與上述第1半導體層（2a) 之表面相接之方式而設置； 第1背面介電質膜（32)，其係以與上述第丨半導體層 (2a)之背面相接之方式而設置； 第2半導體層（2b)，其係設置於上述第1半導體層（2a) 之背面侧； 第2表面介電質膜（34)，其係以與上述第2半導體層 (2b)之表面相接之方式而設置； 第2背面介電質膜（3 7)，其係以與上述第2半導體層 (2b)之背面相接之方式而設置； 第3半導體層（2匀，其係設置於上述第2半導體層（2b) 之背面側； 第3表面介電質膜（39)，其係以與上述第3半導體層 (2c)之表面相接之方式而設置；及 第3背面介電質膜（26)，其係以與上述第3半導體層 (2c)之背面相接之方式而設置； 上述第1半導體層（2a)之背面之上述第〗背面介電質膜 (32)、與上述第2半導體層（2b)之表面之上述第2表面介 電質膜（34)係介著第1中間透明導電膜而接合， 上述第2半導體層（2b)之背面之上述第2背面介電質膜 (3 7)、與上述第3半導體層之表面之上述第3表面介電 143168.doc 201015731 質膜（39)係介著第2中間透明導電膜（38)而接合， 上述第1表面介電質膜（6)在與上述第1半導體層（2a)之 界面附近’含有成為正或負的固定電荷之雜質（5)， 在與上述第1表面介電質臈（6)相接之上述第1半導體層 (2a)之表面之區域的至少一部分上，形成有第丨導電型或 第2導電型之第1表面反轉層（4)， 上述第2表面介電質膜（34)在與上述第2半導體層（2b) 之界面附近，含有成為與上述第i表面介電質膜（6)所含 之上述雜質（5)為相同極性之固定電荷的雜質， 在與上述第2表面介電質膜（34)相接之上述第2半導體 層（2b)之表面之區域的至少一部分上，形成有與上述第】 表面反轉層（4)為相同導電型之第2表面反轉層（35)， 上述第3表面介電質膜（39)在與上述第3半導體層（2c) 之界面附近，含有成為與上述第1表面介電質膜（6)所含 之上述雜質（5)為相同極性之固定電荷的雜質， 在與上述第3表面介電質膜（39)相接之上述第3半導體 層（2c)之表面之區域的至少一部分上，形成有與上述第j 表面反轉層（4)為相同導電型之第3表面反轉層（4〇)， 上述第1背面介電質膜（32)在與上述第1半導體層（2a) 之界面附近’含有成為與上述第1表面介電質膜（6)所含 之上述雜質（5)為相反極性之固定電荷的雜質（25)， 在與上述第1背面介電質膜（32)相接之上述第1半導體 層（2a)之背面之區域的至少一部分上，形成有與上述第j 表面反轉層（4)為相反導電型之第1背面反轉層（3 1}， 143I68.doc 11 201015731 上述第2背面介電質膜（3 7)在與上述第2半導髏層（2b) 之界面附近，含有成為與上述第丨背面介電質膜（32)所含 之上述雜質（25)為相同極性之固定電荷的雜質（25)， 在與上述第2背面介電質膜（37)相接之上述第2半導體 層（2b)之背面之區域的至少一部分上，形成有與上述第j 者面反轉層（31)為相同導電型之第2背面反轉層（3 6)， 上述第3背面介電質膜（26)在與上述第3半導體層（2c) 之界面附近，含有成為與上述第丨背面介電質膜（32)所含 之上述雜質（25)為相同極性之固定電荷的雜質（25)， 在與上述第3背面介電質膜（26)相接之上述第3半導體 層（2c)之背面之區域的至少一部分上，形成有與上述第^ 者面反轉層為相同導電型之第3背面反轉層（24)， 於上述第1表面介電質膜（6)之表面上含有透明導電膜 (9)， 、 於上述第3背面介電質膜（26)之背面上含有背面電極 ⑺， 使載體通過上述表面介電質膜⑹及上述背面介電質膜 (26) ’並自上述透明導電膜（9)及上述背面電極⑺分別被 取出至外部。 143168.doc201015731 VII. Patent application scope: 1. A photoelectric conversion device comprising: a semiconductor layer (2, 2a, 2b, 2C, 12a, 12b, 1〇1); and a dielectric film (6, 6a, 6b, 6c) , 26, 32, 34, 37, Μ, . 60, 1 〇 5), which are disposed in contact with the surfaces of the semiconductor layers (2, 2a, 2b, 2c, 12a, 12b, 101); The dielectric film (6, 6a, 6b, 6c, 26, 32, 34, P, 39, 60, 105) is in contact with the above semiconductor layer (2, 2 &amp;, 沘, 2c, 仏, ❿ 12b, 1G1) Near the interface, 'containing impurities that become positive or negative fixed charges (5, 20 '21, 25, 50, 1〇4). 2. The photoelectric conversion device of claim 1, wherein the semiconductor layer (2, 2b, 2c, 12a, 12b, 1〇1) comprises a crystalline stone, an amorphous stone or a microcrystalline stone. 3. The photoelectric conversion device of claim 1, wherein the dielectric film (6, 6a, 6b, 6c, 26, 32' 34, 37' 39, 60, 105) has a band gap of 4 2 eV or more. The photoelectric conversion device of claim 1, wherein the dielectric film (6, 6a, 6b, 6c, 26, 32, 34, 37, 39, 60, 1〇5) is selected from the group consisting of At least one of a group consisting of nitrogen oxynitride and IL fossil. 5. The photoelectric conversion device of claim 1, wherein the impurity (5, 20, 104) which becomes a positive fixed charge comprises a substance selected from the group consisting of lithium, sodium, potassium, rubidium, magnesium, calcium, barium, strontium, phosphorus, At least one of the group consisting of arsenic and antimony. 6. The photoelectric conversion device of claim 1, wherein the negative fixed charge is 143168.doc 201015731: (21, 25' 50) comprises a material selected from the group consisting of boron, aluminum, gallium, indium, platinum, and fluorinated olefin. At least one of a group consisting of oxidized fullerenes, fluorine, gas, bromine, and iodine. 7. The photoelectric conversion device of claim 1, wherein the semiconductor layer is in contact with the dielectric film (6, 6b, 6c, 26, 32, 34, 37, 39, 60, 105) , at least part of the 2a, 2b, 2c, 12a, 12b, 1〇1) UM region, including a surface inversion layer of the second conductivity type or the second conductivity type (4, 4a, 4c, 35, 40, 1 〇 3). A photoelectric conversion device according to claim 7, comprising an impurity-containing layer (3, 102) which is contained on at least a part of a surface of said semiconductor layer (2, 2a, 2b, 2c, 12a, i2b, 1〇1) The surface inversion layer (4, 4a, 4c, 35, 4〇, 1〇3) is an impurity of the same conductivity type, and further includes an electrode (8, 9, 1〇, 107) which is contained with the above impurity Layers, 102) are connected. 9. The photoelectric conversion device of claim 8, wherein the electrode (8, 9, 107) package 3 is at least one selected from the group consisting of metal, metal scrap, and a transparent conductive film. 10. The photoelectric conversion device of claim 1, wherein the impurity (5, 2, 21, 25, 50, 104) has the most portion, and is located from the semiconductor layer (2, 2a, 2b, 2c, 12a, 12b, 101) from the interface of the dielectric film (6, 6a, 6b, 6c, 26, 32, 34, 37, 39, 60, 1〇5), in a direction perpendicular to the interface The semiconductor layer (2, 2a, 2b, 2c, 12a, 12b, 101) side is advanced by 5 nm in the region 143168.doc 201015731, and toward the above dielectric film (6, 6a, 6b, 6c, 26, 32, 34 37, 39, 60, 105) The area between the 5 nm areas on the side. 11. The photoelectric conversion device according to claim 1, wherein the surface of the semiconductor layer (2, 2a' 2b, 2e' 12a, 12b, 1〇1) is formed with irregularities. a photoelectric conversion device comprising: a first photoelectric conversion layer (51); and a second photoelectric conversion layer (52); wherein the first photoelectric conversion layer (51) comprises: a first semiconductor layer (2a); The electric film (6)' is provided in contact with the surface of the first semiconductor layer (2a), and contains a positive or negative fixed charge in the vicinity of the interface with the second semiconductor layer (2a). The impurity (5); the surface inversion layer (4) of the first conductivity type or the second conductivity type is provided in a region of the surface of the second conductor layer (10) which is in contact with the surface dielectric film (6) The first impurity-containing layer (1) is provided on the back surface opposite to the surface of the first semiconductor layer (2a), and is opposite to the surface inversion layer (4). Conductive type of second impurity; the second photoelectric conversion layer (52) includes: a second semiconductor layer (2b); and a second impurity containing layer (3) provided on a surface of the second semiconductor layer (2b) Further, the second impurity containing the opposite conductivity type from the first impurity-containing layer (1) and the third impurity-containing layer (1) Provided on the back surface opposite to the surface of the semiconductor layer (2b), and containing a third impurity having a conductivity opposite to that of the second impurity; and the photoelectric conversion device has a laminated structure. The second impurity-containing layer (1) of the second photoelectric conversion layer (9) and the second impurity-containing layer of the second photoelectric conversion layer 143168.doc 201015731 (52) are replaced by a glazing layer (4) The second photoelectric conversion layer (52) is laminated with the second photoelectric conversion layer (52). 13. A first electrical conversion device comprising: a semiconductor layer (2); a surface dielectric _), which is attached to the surface of the conductive layer (7) Provided in an upper contact manner; and a back dielectric film (60) disposed in contact with a back surface opposite to a surface of the semiconductor layer (2); the surface dielectric film (6) In the vicinity of the interface with the semiconductor layer (2), an impurity which is a fixed charge of a first polarity is contained, and the back surface dielectric film (60) is contained in the vicinity of the interface with the semiconductor layer (2). 1 fixed charge of the second polarity of opposite polarity Impurities. A photoelectric conversion device comprising: a first semiconductor layer (12a); a first dielectric film (6a) 'which is bonded to a surface of the first semiconductor layer (12a); and a second dielectric film (6b) 'which is bonded to the back surface of the first semiconductor layer (12a); and a second semiconductor layer (2b) bonded to the back surface of the second dielectric film (6b); The dielectric film (6a) contains an impurity (20) having a fixed charge of a first polarity or a second polarity in the vicinity of the interface with the first semiconductor layer (i2a), 143168.doc 201015731 the second dielectric The film (6b) contains impurities in the vicinity of the interface with the semiconductor layer (12a) and the interface between the second semiconductor layer (12b) and the first dielectric film (6a). (2〇) is a fixed-charge impurity of opposite polarity (21) » 15. A photoelectric conversion device comprising: a semiconductor layer (2a, 2b, 2c); and a dielectric film (6, 26, 32, 34) 37, 39), which are disposed in contact with the surface of the semiconductor layer (2a, 2b, 2c); the dielectric (6, 26, 32, 34, 37, 39) containing an impurity (5, 25) which is a positive or negative fixed charge in the vicinity of the interface with the semiconductor layer (2a, 2b, 2c), in the above dielectric The surface of the film (6, 26, 32, 34, 37' 39) contains a transparent conductive film (9, 33, 38) through which the carrier passes through the dielectric film (6, 26, 32, 34, 37, 39). And the transparent conductive film (9, 33, 38) is taken out to the outside. 16. The photoelectric conversion device of claim 15, wherein the transparent substrate (14) is included on a surface of the transparent conductive film (9, 33, 38). The photoelectric conversion device of claim 15, wherein at least a region of a surface of said semiconductor layer ..., several, 2c) which is in contact with said dielectric film (6, 26, 32, 34, 37, 39) A part of the surface inversion layer (4, 24, 31, 35, and 4 ()) of the first conductivity type or the second conductivity type is contained. 18. The photoelectric conversion device of claim 15, wherein the semiconductor layer ..., 2b, 2c) comprises crystalline germanium, amorphous germanium or microcrystalline germanium. 19. The thickness of the photoelectric conversion device of claim 15 wherein said semiconductor layer gamma, 143168.doc 201015731 2b, 2c is thinner than the carrier diffusion length in said semiconductor layer (2a, 2b, 2c). 20. The photoelectric conversion device of claim 15 wherein the dielectric film (6, 26, 32, 34, 37, 39) has a band gap of 4.2 eV or more. The photoelectric conversion device of claim 15, wherein the dielectric film (6, 26, 32, 34, 37, 39) comprises a material selected from the group consisting of niobium carbide, niobium oxide, niobium oxynitride and nitinite. At least one of the groups. 22. The photoelectric conversion device of claim 15, wherein the dielectric film (6, 26, 32, 34, 37, 39) has a thickness of 3 nm or less. The photoelectric conversion device according to claim 15, wherein the impurity (5) which becomes a positive fixed charge comprises a substance selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, phosphorus, arsenic and antimony. At least one of the groups. 24. The photoelectric conversion device of claim 15, wherein the impurity (25) which becomes a negative fixed charge comprises a material selected from the group consisting of butterfly, mound, marry, steel, turned, gasified fullerene, oxidized fullerene, fluorine, gas, At least one of the group consisting of bromine and iodine. The photoelectric conversion device according to claim 15, wherein the portion (5, 25) which is the most abundant impurity (5, 25) is located in the semiconductor layer (2a, 2b). And 2 〇 with the dielectric film (6, %, 32, 34, ^, the interface from the 'in the direction perpendicular to the interface in the direction of the + guiding layer (2a, 2b, 2c) side The region of the advance 5 (10) and the region between the regions 511111 advancing toward the dielectric film (6, 26, 32, 34, 37, 39) side. 26 - A photoelectric conversion device comprising: 143168.doc -6 - 201015731 first semiconductor layer (2a); surface dielectric film (6) provided in contact with the surface of the first semiconductor layer (2a); first conductivity type impurity containing layer ( 109) formed on the back surface of the first semiconductor layer (2a); the second semiconductor layer (2b), The second conductive type impurity-containing layer (11) is formed on the surface of the second semiconductor layer (2b), and the first conductive type impurity-containing layer is provided on the back surface side of the second semiconductor layer (2a). m) is formed on the back surface of the second semiconductor layer (2b); the third semiconductor layer (2c) is provided on the back side of the second semiconductor layer (2b); and the second conductivity type impurity-containing layer ( 112) formed on the surface of the third semiconductor layer (2c); and a first conductivity type impurity containing layer (u3) formed on the back surface of the third semiconductor layer (2c); The second conductivity type impurity-containing layer (109) on the back surface of the semiconductor layer (2a) and the second conductivity type impurity-containing layer (110) on the surface of the second semiconductor layer (2b) are bonded to each other The second conductivity type impurity-containing layer (111) on the back surface of the semiconductor layer (2b) is bonded to the second conductivity type impurity-containing layer (112) formed on the surface of the third semiconductor layer (2c). The electric film (6) is at the boundary with the above-mentioned second semiconductor layer (2a) 143168.doc In the vicinity of the surface of 201015731, an impurity (7) containing a positive or negative solid charge is formed, and at least a part of a region of the surface of the first conductor layer (10) that is in contact with the surface dielectric film (6) is formed with a second portion. a conductive surface inversion layer (4) having a transparent conductive film (9) on the surface of the surface dielectric film (6), passing the carrier through the surface dielectric film (6) and from the transparent conductive film (9) It is taken out to the outside. 27. A photoelectric conversion device comprising: a first semiconductor layer (2a); a surface dielectric film (6) disposed in contact with a surface of the above-mentioned "semiconductor layer (2a); a conductive impurity-containing layer (109) formed on the back surface of the ith semiconductor layer (2a), and a second semiconductor layer (2b) provided on the back side of the MEMS layer (4); An impurity-containing layer (11 Å) formed on the surface of the second semiconductor layer (2b); and a first conductivity-type impurity-containing layer (111) formed on the back surface of the second semiconductor layer (2b); a semiconductor layer (2c) provided on a back side of the second semiconductor layer (2b); a second conductivity type impurity containing layer (112) formed on a surface of the third semiconductor layer (2c); and 143168 Doc 201015731 The back dielectric film (26) is formed on the back surface of the third semiconductor layer (2c); and the 丨-conductive impurity-containing layer (109) on the back surface of the first semiconductor layer (2a) And the second conductivity type impurity containing the surface of the second semiconductor layer (2b) (110) bonding, the second conductive type impurity containing layer (111) on the back surface of the second semiconductor layer (2b) and the second conductive type impurity formed on the surface of the third semiconductor layer (2c) The layer (112) is bonded, and the surface dielectric film (6) contains an impurity (5) which is a positive or negative fixed charge in the vicinity of the interface with the first semiconductor layer (2a), and is dielectrically bonded to the surface. a surface-inverted layer (4) of a second conductivity type is formed on at least a portion of a region of the surface of the first semiconductor layer (2a) where the plasma film is in contact with the surface, and the back surface dielectric film (26) is included The impurity (5) contained in the surface dielectric film (6) is a fixed charge impurity (25) of opposite polarity, and the third semiconductor layer (2c) is in contact with the back surface dielectric film (26). a back surface inversion layer (24) of a second conductivity type is formed on at least a portion of the back surface region, and a transparent conductive film (9) is formed on the surface of the surface dielectric film (6). The back surface of the electrolyte membrane (26) contains a back electrode for passing the carrier through The surface dielectric film (6) and the back surface dielectric film (26)' are taken out from the transparent conductive film (9) and the back surface electrode (7), respectively, to the outside by 143168.doc 201015731. A photoelectric conversion device comprising: a first semiconductor layer (2a); a first surface; and a first dielectric layer (6)' disposed in contact with a surface of the first semiconductor layer (2a); a back dielectric film (32) provided to be in contact with the back surface of the second semiconductor layer (2a); and a second semiconductor layer (2b) provided on the first semiconductor layer (2a) a back surface side; a second surface dielectric film (34) provided in contact with a surface of the second semiconductor layer (2b); and a second back dielectric film (37) Provided so as to be in contact with the back surface of the second semiconductor layer (2b); the third semiconductor layer (which is disposed on the back side of the second semiconductor layer (2b); and the third surface dielectric film (39), which is provided in contact with the surface of the third semiconductor layer (2c); and a third back dielectric film (26). Provided to be in contact with the back surface of the third semiconductor layer (2c); the front surface dielectric film (32) on the back surface of the first semiconductor layer (2a) and the second semiconductor layer ( The second surface dielectric film (34) on the surface of 2b) is bonded via the first intermediate transparent conductive film, and the second back dielectric film on the back surface of the second semiconductor layer (2b) (37) The third surface dielectric 143168.doc 201015731 on the surface of the third semiconductor layer is bonded to the second intermediate transparent conductive film (38), and the first surface dielectric film (38) is bonded to the first surface dielectric film (38). 6) an impurity (5) containing a positive or negative fixed charge in the vicinity of the interface with the first semiconductor layer (2a), and the first semiconductor in contact with the first surface dielectric 臈 (6) A first surface inversion layer (4) of a second conductivity type or a second conductivity type is formed on at least a portion of a surface of the layer (2a), and the second surface dielectric film (34) is 2 in the vicinity of the interface of the semiconductor layer (2b), containing the above impurity (5) contained in the ith surface dielectric film (6) The impurity having a fixed charge of the same polarity is formed on at least a part of a region of the surface of the second semiconductor layer (2b) that is in contact with the second surface dielectric film (34) The layer (4) is a second surface inversion layer (35) of the same conductivity type, and the third surface dielectric film (39) is included in the vicinity of the interface with the third semiconductor layer (2c) The impurity (5) contained in the surface dielectric film (6) is a fixed charge of the same polarity, and the third semiconductor layer (2c) is in contact with the third surface dielectric film (39). A third surface inversion layer (4〇) having the same conductivity type as the j-th surface inversion layer (4) is formed on at least a portion of the surface region, and the first back dielectric film (32) is The vicinity of the interface of the first semiconductor layer (2a) includes an impurity (25) which is a fixed charge having a polarity opposite to the impurity (5) contained in the first surface dielectric film (6), and At least one of the regions of the back surface of the first semiconductor layer (2a) to which the back dielectric film (32) is in contact In part, a first back surface inversion layer (3 1}, 143I68.doc 11 201015731 having the opposite conductivity type to the j-th surface inversion layer (4) is formed, and the second back dielectric film (37) is formed. In the vicinity of the interface with the second semiconductive layer (2b), an impurity (25) having a fixed charge of the same polarity as the impurity (25) contained in the second back surface dielectric film (32) is contained. At least a portion of a region of the back surface of the second semiconductor layer (2b) that is in contact with the second back surface dielectric film (37) is formed to have the same conductivity type as the j-th surface inversion layer (31). The second back surface inversion layer (36), the third back dielectric film (26) is included in the vicinity of the interface with the third semiconductor layer (2c) and the second back surface dielectric film (32) The impurity (25) contained in the first polarity is a fixed charge impurity (25) of the same polarity, and is in a region of the back surface of the third semiconductor layer (2c) which is in contact with the third back dielectric film (26). a third back surface inversion layer (24) having the same conductivity type as the above-described surface inversion layer is formed on at least a portion of the surface, a transparent conductive film (9) is disposed on a surface of the first surface dielectric film (6), and a back electrode (7) is disposed on a back surface of the third back dielectric film (26) to pass the carrier through the surface The electric film (6) and the back surface dielectric film (26)' are taken out from the transparent conductive film (9) and the back electrode (7), respectively. 143168.doc
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