TW201117403A - Solar cell and method for fabricating the same - Google Patents

Solar cell and method for fabricating the same Download PDF

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TW201117403A
TW201117403A TW099124342A TW99124342A TW201117403A TW 201117403 A TW201117403 A TW 201117403A TW 099124342 A TW099124342 A TW 099124342A TW 99124342 A TW99124342 A TW 99124342A TW 201117403 A TW201117403 A TW 201117403A
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amorphous
solar cell
polycrystalline
photovoltaic
photovoltaic element
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TW099124342A
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Yoo-Jin Lee
Dong-Jee Kim
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Tg Solar Corp
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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
    • H01L31/04—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
    • H01L31/047—PV cell arrays including PV cells having multiple vertical junctions or multiple V-groove junctions formed in a semiconductor substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0368—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including polycrystalline semiconductors
    • H01L31/03682—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including polycrystalline semiconductors including only elements of Group IV of the Periodic Table
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0376—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors
    • H01L31/03762—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors including only elements of Group IV of the Periodic Table
    • 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
    • H01L31/072—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 heterojunction type
    • H01L31/0725—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
    • Y02E10/546—Polycrystalline 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)
  • Microelectronics & Electronic Packaging (AREA)
  • Electromagnetism (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Disclosed are a solar cell and a production method therefor. The solar cell according to the present invention comprises: a substrate; a polycrystalline photoelectric element which is formed on the substrate and is obtained by the lamination of a plurality of polycrystalline semiconductor layers; a first amorphous photoelectric element which is formed on the polycrystalline photoelectric element and is obtained by the lamination of a plurality of amorphous semiconductor layers; a second amorphous photoelectric element which is formed on the first amorphous photoelectric element and is obtained by the lamination of a plurality of amorphous semiconductor layers; and an upper electrode which is formed on the second amorphous photoelectric element.

Description

201117403 六、發明說明： 【考务明戶斤屬彳街^員】 發明領域 本發明係有關二接面（triple juncti〇n)串接式太陽電 池，更詳而言之，係有關藉由積層之順序而具有適宜的能帶間 隙(energy bandgap)之三接面串接式太陽電池及其製造方法。201117403 VI. Description of the invention: [The invention is related to the two-side (triple juncti〇n) tandem solar cell, more specifically, by layering A three-junction tandem solar cell having a suitable energy band gap and a method of manufacturing the same.

【jivT 名奸]I 發明背景 習知之一般的太陽電池係以單接面構成，而為生產多 量之電力，係要求大面積之太陽電池。然而，此種太陽電 池之大面積化，係連結至設置場所之限制及成本上揚。又， 單接面太陽電池其光電轉換效率最高不過2〇%前後，大部 分入射於太陽電池之光都直接穿透並反射而消失，因此， 光電轉換效率低落。 為解決其等問題，提出有一種將光電元件積層之串接 式(tandem)太陽電池。該串接式太陽電池因於同一基板面積 可生產更多量之電，因此具有相較於習知之單接面太陽電 池，光電轉換效率提高之優點。 作為串接式太陽電池之一般例，有積層非晶質石夕 (amorphous Si : a-Si)光電元件及微晶質矽（mic丨.⑽州仙此[jivT sorcerer] I BACKGROUND OF THE INVENTION Conventional solar cells are constructed by a single junction, and a large area of solar cells is required for the production of a large amount of electricity. However, the large area of such solar cells is limited by the restrictions and cost of connecting to the installation site. Moreover, the photoelectric conversion efficiency of the single-junction solar cell is as high as about 2% before and after, and most of the light incident on the solar cell directly penetrates and reflects and disappears, so the photoelectric conversion efficiency is low. In order to solve such problems, a tandem solar cell in which photovoltaic elements are laminated is proposed. Since the tandem solar cell can produce a larger amount of electricity due to the same substrate area, it has an advantage of improved photoelectric conversion efficiency compared to the conventional single-junction solar cell. As a general example of a tandem solar cell, there is a laminated amorphous Si (a-Si) photovoltaic element and a microcrystalline 矽 (mic).

Si : μο-Si)光電元件之二接面太陽電池，於此構造中，實際 上，係提出有相較於單接面太陽電池，光電轉換效率提高 之報告。 惟，習知之二接面串接式太陽電池於利用電漿輔助化 201117403 學氣相沈積法（Plasma-Enhanced Chemical Vapor Deposition : PECVD)而形成微晶質矽光電元件時，係要求 較低的沈積壓力及較高的沈積功率，但製造程序之控制不 易進行使得製造程序時間增加，而有太陽電池之生產性降 低的問題。 再者，習知之二接面串接式太陽電池其所積層之光電 元件間的能帶間隙之差異大，接受各種波長區域之光的能 力不佳’有太陽電池之光電轉換效率低之問題。 進而，習知之二接面串接式太陽電池其微晶質石夕層之 品質不佳，具有接受長波長區域之光的微晶質⑦光電元件 之光電轉換效率較接受短波長輯之光的非晶質光電元件 之光電轉換效率低落之問題。 【明内容j 發明概要 發明欲解決之課題 …因此’本發明料解決前述習知技術之諸問題而創 元成者’目的在於提供-種可藉由積層 間隙線性地增加而接受各種波帶_ =讓此 之光電轉換效率之三接㈣接式太陽電池； 又，本發明之目的係在於提供 由;=法 多晶質㈣來形成接受長波長區域之光 ：了 光電元件，而增加長波純域之減 I間隙較小 之光電轉換效率之三接面串接式太陽電池及心:: 進而，本發明之目的係在於提供—種可藉由以高品 4 201117403 之多晶質矽層來形成接受長波長區域之光的能帶間隙較小 的光電元件，而讓製造程序之控制易於進行，且製造程序 時間縮短，提高生產性之三接面串接式太陽電池及其製造 方法。 用以欲解決課題之手段 本發明之前述目的係藉由一種太陽電池而達成，該太 陽電池之特徵係在於包含有：基板；多結晶光電元件，係 形成於前述基板上，且積層有複數多結晶半導體層；第1非 晶質光電元件，係形成於前述多結晶光電元件上，且積層 有複數非晶質半導體層；第2非晶質光電元件，係形成於前 述第1非晶質光電元件上，且積層有複數非晶質半導體層； 及上部電極，係形成於前述第2非晶質光電元件上。 又，本發明之前述目的係藉由一種太陽電池之製造方 法而達成，該太陽電池之製造方法之特徵係在於包含有下 述程序，即：（a)於基板上積層複數多結晶半導體層而形成 多結晶光電元件之程序；（b)於前述多結晶光電元件上積層 複數非晶質半導體層而形成第1非晶質光電元件之程序；（c) 於前述第1非晶質光電元件上積層複數非晶質半導體層而 形成第2非晶質光電元件之程序；及(d)於前述第2非晶質光 電元件上形成上部電極之程序。 此時，前述第1非晶質光電元件及前述第2非晶質光電 元件之能帶間隙可相同。 前述多結晶光電元件、前述第1非晶質光電元件及前述 第2非晶質光電元件可具有藉由積層順序而線性地增加之 201117403 能帶間隙。 月j述夕結晶光電元件係可以多晶質碎或多晶質石夕緒之 任一者形成。 前述第1非晶質光電元件係可以非晶質矽或非晶質矽 鍺之任一者形成。 前述第2非晶質光電元件係可以非晶質矽或非晶質碳 化矽之任一者形成。 前述多結晶半導體層係可藉由SPC(Solid Phase Crystallization :固相結晶）、ELA(Excimer Laser Annealing : 準分子雷射退火）、SLS(Sequential Lateral Solidification :連 續橫向固化）、MIC(Metal Induced Crystallization :金屬誘發 結晶）及MILC(Metal Induced Lateral Crystallization :金屬誘 發橫向結晶）之任一個方法而結晶化。 於前述基板與前述多結晶光電元件之間係可進而形成 下部電極。 於前述多結晶光電元件與前述第1非晶質光電元件之 間，以及前述第1非晶質光電元件與前述第2非晶質光電元 件之間之至少一者，係可進而形成透明導電體之連接層。 發明效果 依本發明，三接面串接式太陽電池係可藉由積層光電 元件而讓能帶間隙線性地增加俾接受各種波長區域之光， 提高太陽電池之光電轉換效率。 又，依本發明，二接面串接式太陽電池係可藉由以高 品質之多晶質石夕層來形成接受長波長區域之光的能帶間隙 201117403 較小的光電元件，而增加長波長區域之集光效率，提高太 陽電池之光電轉換效率。 進而，依本發明，2接面串接式太陽電池係可藉由以 多晶質碎層來形成接受長波長區域之光的能帶間隙較小的 光電元件，而讓製造程序之控制易於進行且縮短製造程序 時間，提高生產性。 圖式簡單說明 第1圖係顯示本發明一實施形態之串接式太陽電池之 製造方法的剖面圖。 第2圖係顯示本發明一實施形態之争接式太陽電池之 製造方法的剖面圖。 第3圖係顯示本發明一實施形態之_接式太陽電池之 製造方法的剖面圖。 第4圖係顯示本發明一實施形態之串接式太陽電池之 製造方法的剖面圖。 第5圖係顯示本發明一實施形態之串接式太陽電池之 製造方法的剖面圖。 第6圖係顯示本發明一實施形態之串接式太陽電池之 製造方法的剖面圖。 【實方方式】 用以實施發明之形態 以下，為更明確表示與本發明之前述目的以及技術性 構成與依此之作用效果相關的事項，係參照添附圖式而詳 細說明本發明之較佳實施形態。 7 201117403 於本說明書中，串接式太陽電池係表示光電元件以― 接面而積層之構造，但本發明之串接式太陽電池並不限= 為此者，可為包含三接面以上之概括的概念。 三接面串接式太陽電池之構成 第1圖至第ό圖係顯示本發明一實施形態之串接式 電池之製造方法的剖面圖。 χ 陽 以下’為方便說明’係於包含複數個單位晶月包區域（進 行光電轉換之區域）與位在單位晶包區域之間的複數個酉 線區域(有配線之區域)之基板中，將單位晶胞區域作為中= 而進行說明。 ％ 首先，如第1圖所示，準備基板1〇〇。基板1〇〇之材質係 光學性的透明材質或不透明材質任一者均可加以使用，電 性特性則對於譬如玻璃及塑膠之絕緣性材質、或譬如矽及 金屬之導電性材質都無限制而可予以使用。 此時，藉由導電性材質而形成基板100時，因可發揮之 後所形成之下部電極110之功效，故亦可不形成下部電極 110。該基板100於之後的高溫結晶化程序中，係可使用具 有可耐於基板100之彎曲現象的剛性，且形成於上部之光電 元件（譬如矽層）以及與熱膨脹係數相似之金屬或金屬合 金。作為其一例，可為SUS(Stainless Steel :不錄鋼）、翻 (Mo)、鎢（W)、鉬一鎢合金(Mo — W)或銦鋼（Invar)(Fe - Ni 合金）。 其次，可於基板100之表面進行變形加工(texturing)。 本發明中，變形加工係用以防止因入射至太陽電池之基板 8 201117403 象以反㈣光學性的損失所導致其特性降低之現 成凹j，係指讓基板之表面變得粗链，且於基板表面形 (未予圖式）°譬如’藉由進行變形加卫而讓基板 =^時，曾於表面反射之光係可於太陽電池之 μ次進行反射，因此，可降低光的損失，且光捕獲量 曰加，提高太陽電池之光電轉換效率。 此時，作為代表性的變形加工方法，可例舉喷砂法。 本發明中之噴砂法係包含以壓縮空氣吹付㈣粒子而進行 」之乾式噴砂法’以及共同吹付液體與_粒子而進行 I j之屬式噴紗法二者。另—方面，作為用於本發明之喷 /法之細Hi子’如砂及較小的金屬般，對於能夠藉由物 理性衝擊秘基㈣成凹凸妹子係無關而可加以使用。 其人，可於基板1〇〇上形成導電性材質之下部電極 110。下部電極110之素材係以接觸電阻低且即使進行高 溫程序，電性特性仍不會降低之鉬（M0)、鎢(w)、鎢化鉬 (MoW)之任一者抑或其等之合金為佳，但並不限定於此， 可為一般的導電性素材之銅、鋁、鈦及包含其等之合金。 作為下部電極110之形成方法，可包含如熱蒸鍍法(thermal evaporation)、電子束蒸鑛法（e_beam evaporation)、濺鍵 (sputtering)之物理氣相悉鍵法（physical Vapor Deposition : PVD) ’以及如低壓化學氣相沈積法(l〇w pressure chemical Vapor Deposition : LPCVD)、PECVD、有機金屬化學氣相 沈積法（Metal Organic Chemical Vapor Deposition: MOCVD) 之化學氣相沈積(Chemical Vapor Deposition : CVD)。 201117403 另一方面’亦可於下部電極110上進而形成透明導電性 材質之反射層（未予圖式）。即，反射層係位在下部電極i 10 與之後所形成之多結晶光電元件200之間。反射層係與丁部 電極110電性連接，且可讓由基板1〇〇之上側入射之太陽光 加以反射而提高太陽電池之光電轉換效率。反射層可為 AZO(ZnO : Al)、ITO(Indium Tin Oxide :氧化銦錫）、 IZO(Indium Zinc Oxide :氧化銦鋅）、FT0(Sn02 : F)之任— 者或其等之組合。 作為反射層之形成方法，可包含如濺锻之物理氣相蒸 鍍法，以及如LPCVD、PECVD、MOCVD之化學氣相蒸錢 法等。又，下部電極110之表面與基板100之表面相同地， 為提高太陽電池之光電轉換效率，係可實施前述之變形加 工處理。如所述，基板100由導電性材質構成時，亦可不形 成下部電極110。 接著’於下部電極110上以三接面積層光電元件 200,300,400，可實現本發明一實施形態之串接式太陽電 池。此時，光電元件200,300,400可為複數半導體層加以積 層之構造，可P型與η型之半導體層加以積層，或p型、i型、 η型的半導體層加以積層。 即，可於下部電極110上形成多結晶光電元件200，於 多結晶光電元件200上形成第1非晶質光電元件300，於第1 非晶質光電元件3〇〇上形成第2非晶質光電元件400，構成一 個串接式構造。此時，作為光電元件200,300,400之形成方 法，可使用如PECVD或LPCVD之化學氣相蒸鍍法而形成’ 10 201117403 若更詳細說明各光電元件200,300,400之形成方法係如下所述。 如第2圖及第3圖所示，依多結晶光電元件200之形成方 法，係可於下部電極110上形成第1非晶質半導體層210，於 第1非結晶半導體層210上形成第2非晶質半導體層220，於 第2非晶質半導體層220上形成第3非晶質半導體層230。 接著，可進行將第1非晶質半導體層210、第2非晶質半 導體層220、第3非晶質半導體層230結晶化之過程。即，玎 分別於第1非晶質半導體層210結晶化第1多結晶半導體層 211、於第2非晶質半導體層220結晶化第2多結晶半導體層 221、於第3非晶質半導體層230結晶化第3多結晶半導體層 23卜 此時，結晶化方法係可利用SPC(Solid Phase Crystallization :固相結晶）、ELA(Excimer Laser Annealing : 準分子雷射退火）、SLS(Sequential Lateral Solidification :側 向結晶）、MIC(Metal Induced Crystallization :金屬誘發結 晶）、MILC(Metal Induced Lateral Crystallization :金屬誘發 側向結晶）之任一個方法。非晶質半導體之結晶化方法係周 知之技術，故與此相關之詳細說明於本發明中係省略。 另一方面，前述中係說明於第1非晶質半導體層210、 第2非晶質半導體層220、第3非晶質半導體層230均形成之 後，同時地於該等層加以結晶化’但並不限定於此《譬如 可個別地於各非晶質半導體層進行結晶化程序《又，亦可 同時對兩個非晶質半導體層進行結晶化程序，僅剩餘的一 個非晶質半導體層另外再進行結晶化程序。 201117403 其次，如第4圖所示，依第丨非晶質光電元件3〇〇之形成 方法，係可於多結晶光電元件200上形成第1非晶質半導髀 層310，於第1非晶質半導體層310上形成第2非晶質半導 層320，於第2非晶質半導體層320上形成第3非晶質半導A 層33〇。即’ &lt; 於多結晶光電元件2〇〇上形成第〖非晶質半Z 體層310、第2非晶質半導體層320及第3非晶質半導體層幻〇 組成的第1非晶質光電元件300。 再者，如第5圖所示，依第2非晶質光電元件4〇〇之卅 方法’係可於第1非晶質光電元件300上形成第1非晶質^ = 體層410，於第1非晶質半導體層410上形成第2非晶質半 體層420’於第2非晶質半導體層420上形成第3非晶質半^ 體層430。即，可於第1非晶質光電元件3〇〇上形成第丄曰 質半導體層41〇、第2非晶質半導體層42〇及第3非晶質 體層430組成的第2非晶質光電元件4〇〇。 以上所述之多結晶光電元件200、第！非晶質光電_ 300及第2非晶質光電元件400之半導體層，係可為藉由=件 光所產生之光起電力而生產電力之P型、i型、i很&amp; n尘义平導體 層依序積層之p — i —η二極管之構造。此時， P i、1型、η+ 型之半導體層宜依序積層。此處’ i型係表示未摻雜雜質之 本質(imdnsic)。又，「+」與「-」係表示摻雜濃度的相^ 差，「+」表示相對於「一」具有高濃度之摻雜濃度。譬如 n+相較於η—係表示高摻雜。再者，未表示+或—時，係表 示於摻雜濃度並無特別限制。 進而，多結晶光電元件200、第1非晶質光電元件3〇〇及 12 201117403 第2非晶質光電元件400之半導體 避層’可為藉由接受光所產 生之光起電力而生產電力之η型、丨剂 ΛιΙ , t ^ 1型、P型之半導體層依序 積層之η — i — p二極管之構造。卜吐 此時，n+型、i型、p+型之半 導體層宜依序積層。 又，多結晶光電元件200、第〖非曰 非曰日貝先電凡件300及第 2非晶質光電元件之半導體層，可為藉由接受光所產生 之光起電力而生產電力之p型、p型、n型之半導體層依序積 層之ρ — ρ — η二極管之構造。此拉 寺，ρ+型、ρ—型、η+型之 半導體層宜依序積層。 進而’多結晶光電元件2〇〇、笛]t曰 第1非日日質光電元件300及 第2非晶質光電元件400之半導髂 趙層，可為藉由接受光所產 生之光起電力而生產電力之η型、n和丨 ， 〃 n型、P型之半導體層依序 積層之n-n—p二極管之構造。此 此時，n+型、n—型 型 之半導體層宜依序積層。 另-方面，η型或P型摻雜係以於非晶質石夕層形成時以 原位(in situ)方式進行換雜為宜。作為Ρ型摻雜時之雜質， -般是使㈣⑻，而作為__時之雜f，—般是使用 填(P)或㈣M)，但不限定於此，可。 又，對於多結晶光電元件_、第1非晶質光電元件300 及第2非晶質光電元件4GG’為麵存在於非晶質半導體層 内之缺陷（譬如雜質及懸浮鍵等）並更提高諸特性，係可施行 氫化處理。 最後，如第6圖所示，可於第2非晶質光電元件4〇〇上形 成導電性材質之上部電極寫。上部電極獅之素材係透明 13 201117403 導電性材質，譬如為透明導電層時可使用TC〇，而以 AZO(ZnO : Al)、lT〇(Indium Tin Oxide :氧化銦錫）、 GZO(ZnO : Ga)、BZO(ZnO : B)及FT0(Sn02 : F)之任一者 為宜，但並不限定於此。作為上部電極5〇〇之形成方法，可 包含如濺鍍之物理氣相蒸鍍法，以及如LPCVD、PECVD、 MOCVD之化學氣相沈積法等。 藉此’可形成本發明一實施形態之三接面串接式太陽 電池。另一方面’雖未圖式，可於多結晶光電元件2⑻與第 1非晶質光電元件300之間，或第1非晶質光電元件3〇〇與第2 非晶質光電元件400之間之任一者以上，進而形成透明導電 體之連接層。藉由前述連接層，可於多結晶光電元件與非 晶質光電元件之間進行歐姆接觸（ohmic contact)，而可期待 太陽電池更好的優良光電轉換效率。作為連接層之素材， 以ITO、ZnO、IZO、FTO(Sn〇2 : F) ' BZO之任一者為宜， 但並不限定於此。作為連接層之形成方法，可包含如濺鍍 之物理氣相蒸鍍法，以及如LPCVD、PECVD、M0CVD之 化學氣相沈積法等。 三接面串接式太陽電池之能帶間隙 本發明一實施形態之串接式太陽電池中，多結晶光電 元件200、第1非晶質光電元件3〇〇及第2非晶質光電元件400 較理想的是可具有如下之能帶間隙(Eg)。 首先，多結晶光電元件200、第1非晶質光電元件300及 第2非晶質光電元件4〇〇係可形成為能帶間隙具有「多結晶 光電元件200〈第1 #晶質光電元件300 =第2非晶質光電元 14 201117403 件400」之關係。此係多結晶光電元件200之能帶間隙最小， 第1非晶質電子元件300及第2非晶質光電元件4〇〇為能帶間 隙相同（或類似）之形態。作為一例，係多結晶光電元件2〇〇 由複數多晶質矽(P — Si)(Eg〜1.leV)層組成，第1非晶質光 電元件3〇〇及弟2非晶質光電元件400分別由複數非晶質石夕 (a-Si)(Eg〜1.7eV)層組成之態樣。 又，多結晶光電元件200、第1非晶質光電元件3〇〇及第 2非晶質光電元件400係可形成為能帶間隙具有「多結晶光 電元件200〈第1非晶質光電元件3〇〇〈第2非晶質光電元件 400」之關係。此係多結晶光電元件200與第1非晶質光電元 件300之間的能帶間隙之差，以及第1非晶質光電元件3〇〇與 第2非晶質光電元件400之間的能帶間隙之差彼此相同或類 似之形態。作為一例，多結晶光電元件200可由複數多晶質 石夕鍺(a—SiGe)(Eg&lt; l.iev)層組成，第1非晶質光電元件3〇〇 可由複數非晶質矽鍺(a-SiGe)(Eg= 1.3〜1.6eV)層組成，第 2非晶質光電元件400可由複數非晶質碳化 1.7eV)層組成。作為其他例，多結晶光電元件2〇〇可由複數 多晶質矽(P—Si)(Eg〜i.ieV)層組成，第#晶質光電元件 300可由複數非晶質矽鍺（a_ SiGe)(Eg= i 3〜！ 6eV)層組 成，第2非晶質光電元件400可由複數非晶質矽(a_Si)(Eg〜 1.7eV)層組成。 如前述’本發明之三接面串接式太陽電池係藉由積層 光電元件而讓能帶間隙線性地增加，俾接受各種波長區域 之光’提高太陽電池之光電轉換效率。 15 201117403 又，本發明之三接面串接式太陽電池並非藉由習知之 微晶質矽層而是以高品質的多晶質矽層來形成接受長波長 區域之光之能帶間隙較小的光電元件，而可增加長波長之 集光效率，提高太陽電池之光電轉換效率。又，多晶質矽 較微晶質石夕而老化（aging)特性優異（老化並不容易進展），因 此，採用本發明之多晶質矽層之三接面串接式太陽電池係 可提高壽命及可靠度。 進而，本發明之三接面_接式太陽電池係藉由以多晶 質矽層來形成接受長波長區域之光的能帶間隙較小的光電 元件，而讓製造程序之控制易於進行，且製造程序時間縮 短，可提高生產性。 本發明係如前述，舉出適宜的實施形態並顯示圖示及 進行說明，但並不限定於前述之實施形態，在不脫離本發 明之精神之範圍内，具有本發明所屬技術領域中之一般知 識者係可進行各種變形及變更。此種變形例及變更例均應 視為屬於本發明與所添附之申請專利範圍。 【圖式簡單說明】 第1圖係顯示本發明一實施形態之-接式太陽電池之 製造方法的剖面圖。 第2圖係顯示本發明一實施形態之串接式太陽電池之 製造方法的剖面圖。 第3圖係顯示本發明一實施形態之串接式太陽電池之 製造方法的剖面圖。 第4圖係顯示本發明一實施形態之串接式太陽電池之 16 201117403 製造方法的剖面圖。 第5圖係顯示本發明一實施形態之串接式太陽電池之 製造方法的剖面圖。 第6圖係顯示本發明一實施形態之串接式太陽電池之 製造方法的剖面圖。 【主要元件符號說明】 100.. .基板 110.. .下部電極 200.. .多結晶光電元件 · 210,310,410…第1非晶質半導體層 211.. .第1多結晶半導體層 220.320.420.. .第2非晶質半導體層 221.. .第2多結晶半導體層 230,330,430…第3非晶質半導體層 231.. .第3多結晶半導體層 300.. .第1非晶質光電元件 400.. .第2非晶質光電元件 500.. .上部電極 17Si: μο-Si) Two-junction solar cells of photovoltaic elements. In this structure, in fact, there is a report that the photoelectric conversion efficiency is improved compared to a single-junction solar cell. However, the conventional two-junction tandem solar cell requires lower deposition when forming a microcrystalline germanium photovoltaic element by plasma-assisted chemical vapor deposition (PECVD). Pressure and high deposition power, but the control of the manufacturing process is not easy to make the manufacturing process time increase, and the productivity of the solar cell is lowered. Further, the conventional two-junction tandem solar cell has a large difference in energy band gap between the photovoltaic elements stacked therein, and the ability to receive light of various wavelength regions is poor. The photoelectric conversion efficiency of the solar cell is low. Furthermore, the conventional two-junction tandem solar cell has a poor quality of the microcrystalline layer, and the photoelectric conversion efficiency of the microcrystalline 7 photoelectric element having the light receiving the long wavelength region is higher than that of the short wavelength. The problem of low photoelectric conversion efficiency of amorphous photovoltaic elements. [Explanation of the contents of the invention] The object of the invention is to solve the problems of the prior art described above. The purpose of the invention is to provide a variety of bands that can be linearly increased by the lamination gap. a three-connected (four)-connected solar cell having the photoelectric conversion efficiency; further, the object of the present invention is to provide light that accepts a long-wavelength region by the polymorphic (4) method: a photovoltaic element, and an increase in long-wave purity Three-junction tandem solar cells and cores with reduced photoelectric conversion efficiency with small gaps in the domain: Further, the object of the present invention is to provide a polycrystalline layer of high-grade 4 201117403 A three-junction tandem solar cell and a method of manufacturing the same, which are capable of forming a photovoltaic element having a small band gap of light in a long-wavelength region, facilitating control of a manufacturing process, and shortening a manufacturing process time, and improving productivity. Means for Solving the Problems The foregoing object of the present invention is achieved by a solar cell characterized by comprising: a substrate; a polycrystalline photovoltaic element formed on the substrate, and having a plurality of layers a crystalline semiconductor layer; the first amorphous photovoltaic element is formed on the polycrystalline photovoltaic device, and a plurality of amorphous semiconductor layers are laminated; and the second amorphous photovoltaic element is formed on the first amorphous photoelectric device A plurality of amorphous semiconductor layers are laminated on the device, and an upper electrode is formed on the second amorphous photovoltaic element. Further, the above object of the present invention is achieved by a method of manufacturing a solar cell characterized by comprising: (a) laminating a plurality of polycrystalline semiconductor layers on a substrate; a procedure for forming a polycrystalline photovoltaic device; (b) a step of forming a plurality of amorphous semiconductor layers on the polycrystalline photovoltaic device to form a first amorphous photovoltaic element; (c) forming the first amorphous photovoltaic element a process of forming a plurality of amorphous semiconductor layers to form a second amorphous photovoltaic element; and (d) a process of forming an upper electrode on the second amorphous photoelectric element. In this case, the energy gap between the first amorphous photoelectric element and the second amorphous photoelectric element may be the same. The polycrystalline photovoltaic device, the first amorphous photovoltaic device, and the second amorphous photovoltaic device may have a 201117403 band gap which linearly increases by a lamination order. The crystal optical element of the moon can be formed by any of polycrystalline or polycrystalline stone. The first amorphous photovoltaic element may be formed of either amorphous or amorphous. The second amorphous photovoltaic element may be formed of either amorphous or amorphous tantalum carbide. The polycrystalline semiconductor layer may be formed by SPC (Solid Phase Crystallization), ELA (Excimer Laser Annealing), SLS (Sequential Lateral Solidification), and MIC (Metal Induced Crystallization: Crystallization is carried out by any of the methods of metal induced crystallization and MILC (Metal Induced Lateral Crystallization). A lower electrode may be further formed between the substrate and the polycrystalline photovoltaic element. At least one of the polycrystalline photovoltaic element and the first amorphous photoelectric element, and at least one of the first amorphous photoelectric element and the second amorphous photoelectric element may further form a transparent conductor The connection layer. Advantageous Effects of Invention According to the present invention, a three-junction tandem solar cell can increase the band gap to linearly increase light in various wavelength regions by laminating photovoltaic elements, thereby improving the photoelectric conversion efficiency of the solar cell. Moreover, according to the present invention, the two-joined tandem solar cell system can be formed by forming a photovoltaic element having a small energy band gap 201117403 that receives light of a long wavelength region with a high-quality polycrystalline layer. The light collecting efficiency in the wavelength region improves the photoelectric conversion efficiency of the solar cell. Further, according to the present invention, the two-joined tandem solar cell system can control the manufacturing process easily by forming a photovoltaic element having a small band gap of light receiving a long-wavelength region by a polycrystalline layer. And shorten the manufacturing process time and improve productivity. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a method of manufacturing a tandem solar cell according to an embodiment of the present invention. Fig. 2 is a cross-sectional view showing a method of manufacturing a contiguous solar cell according to an embodiment of the present invention. Fig. 3 is a cross-sectional view showing a method of manufacturing a solar cell according to an embodiment of the present invention. Fig. 4 is a cross-sectional view showing a method of manufacturing a tandem solar cell according to an embodiment of the present invention. Fig. 5 is a cross-sectional view showing a method of manufacturing a tandem solar cell according to an embodiment of the present invention. Fig. 6 is a cross-sectional view showing a method of manufacturing a tandem solar cell according to an embodiment of the present invention. [Embodiment] The present invention will be described in detail with reference to the accompanying drawings and the preferred embodiments of the present invention. Implementation form. 7 201117403 In the present specification, a tandem solar cell system has a structure in which a photovoltaic element is laminated on a "junction surface", but the tandem solar cell of the present invention is not limited to the case, and may include three or more junctions. Generalized concept. The configuration of the three-connected tandem solar cell Fig. 1 to Fig. 1 is a cross-sectional view showing a method of manufacturing a tandem battery according to an embodiment of the present invention. χ 以下 以下 ' 为 为 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The unit cell region will be described as medium =. % First, as shown in Fig. 1, the substrate 1 is prepared. The material of the substrate 1 can be used for any optically transparent material or opaque material. The electrical properties are not limited to insulating materials such as glass and plastic, or conductive materials such as tantalum and metal. Can be used. At this time, when the substrate 100 is formed of a conductive material, since the effect of the lower electrode 110 formed later can be exhibited, the lower electrode 110 may not be formed. In the subsequent high-temperature crystallization process, the substrate 100 can have a rigidity which is resistant to the bending phenomenon of the substrate 100, and is formed on the upper photovoltaic element (e.g., ruthenium layer) and a metal or metal alloy similar in thermal expansion coefficient. As an example, it may be SUS (Stainless Steel), turn (Mo), tungsten (W), molybdenum-tungsten alloy (Mo-W), or invar (Fe-Ni alloy). Next, texturing can be performed on the surface of the substrate 100. In the present invention, the deformation processing is used to prevent the surface of the substrate which is incident on the solar cell 8 201117403 from being degraded by the optical loss of (4) optical properties, which means that the surface of the substrate becomes thick and The surface shape of the substrate (not shown). For example, when the substrate is replaced by deformation and deformation, the light that has been reflected on the surface can be reflected by the solar cell for μ times, thereby reducing the loss of light. Moreover, the amount of light trapping increases, and the photoelectric conversion efficiency of the solar cell is improved. In this case, as a representative deformation processing method, a sand blast method can be exemplified. The blasting method in the present invention includes both a dry blasting method in which (4) particles are blown by compressed air, and a squirting method in which a liquid and a granule are co-powed to perform Ij. On the other hand, as the fine Hi sub- used in the spray/method of the present invention, such as sand and a small metal, it can be used irrespective of the physical impact of the secret base (4). As a person, a conductive material lower electrode 110 can be formed on the substrate 1A. The material of the lower electrode 110 is one of molybdenum (M0), tungsten (w), and molybdenum molybdenum (MoW) which is low in contact resistance and which does not deteriorate in electrical properties even when a high temperature program is performed. Preferably, it is not limited thereto, and may be copper, aluminum, titanium, or an alloy containing the same as a general conductive material. As a method of forming the lower electrode 110, a physical vapor phase deposition (PVD) such as thermal evaporation, e_beam evaporation, and sputtering can be included. And chemical vapor deposition (CVD) such as low pressure chemical vapor deposition (LPCVD), PECVD, and Metal Organic Chemical Vapor Deposition (MOCVD) . 201117403 On the other hand, a reflective layer of a transparent conductive material (not shown) may be further formed on the lower electrode 110. That is, the reflective layer is between the lower electrode i 10 and the polycrystalline photovoltaic element 200 formed thereafter. The reflective layer is electrically connected to the butt electrode 110, and reflects sunlight incident from the upper side of the substrate 1 to improve the photoelectric conversion efficiency of the solar cell. The reflective layer may be a combination of AZO (ZnO: Al), ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), FT0 (Sn02: F), or the like. As the method of forming the reflective layer, physical vapor deposition such as sputtering, and chemical vapor deposition such as LPCVD, PECVD, and MOCVD may be included. Further, the surface of the lower electrode 110 is the same as the surface of the substrate 100, and the above-described deformation processing can be performed in order to improve the photoelectric conversion efficiency of the solar cell. As described above, when the substrate 100 is made of a conductive material, the lower electrode 110 may not be formed. Next, a tandem solar cell according to an embodiment of the present invention can be realized by three-layered photovoltaic elements 200, 300, and 400 on the lower electrode 110. At this time, the photovoltaic elements 200, 300, and 400 may have a structure in which a plurality of semiconductor layers are laminated, and a P-type and an n-type semiconductor layer may be laminated, or a p-type, i-type, or n-type semiconductor layer may be laminated. That is, the polycrystalline photovoltaic device 200 can be formed on the lower electrode 110, the first amorphous photovoltaic device 300 can be formed on the polycrystalline photovoltaic device 200, and the second amorphous material can be formed on the first amorphous photovoltaic device 3? The photovoltaic element 400 constitutes a tandem structure. At this time, the method of forming the photovoltaic elements 200, 300, and 400 can be formed by a chemical vapor deposition method such as PECVD or LPCVD. [10 201117403] The method of forming each of the photovoltaic elements 200, 300, and 400 will be described in more detail below. As shown in FIGS. 2 and 3, in the method of forming the polycrystalline photovoltaic device 200, the first amorphous semiconductor layer 210 can be formed on the lower electrode 110, and the second amorphous semiconductor layer 210 can be formed on the first amorphous semiconductor layer 210. In the amorphous semiconductor layer 220, the third amorphous semiconductor layer 230 is formed on the second amorphous semiconductor layer 220. Next, a process of crystallizing the first amorphous semiconductor layer 210, the second amorphous semiconductor layer 220, and the third amorphous semiconductor layer 230 can be performed. In other words, the first polycrystalline semiconductor layer 211 is crystallized in the first amorphous semiconductor layer 210, the second polycrystalline semiconductor layer 221 is crystallized in the second amorphous semiconductor layer 220, and the third amorphous semiconductor layer is formed in the third amorphous semiconductor layer. 230 crystallizes the third polycrystalline semiconductor layer 23. In this case, the crystallization method can utilize SPC (Solid Phase Crystallization), ELA (Excimer Laser Annealing), and SLS (Sequential Lateral Solidification: Any method of lateral crystallization, MIC (Metal Induced Crystallization), and MILC (Metal Induced Lateral Crystallization). The crystallization method of the amorphous semiconductor is a well-known technique, and thus the detailed description thereof is omitted in the present invention. On the other hand, in the above description, after the first amorphous semiconductor layer 210, the second amorphous semiconductor layer 220, and the third amorphous semiconductor layer 230 are formed, they are simultaneously crystallized in the layers. It is not limited to this, for example, the crystallization process can be performed individually for each amorphous semiconductor layer. Alternatively, the crystallization process of the two amorphous semiconductor layers can be performed simultaneously, and only the remaining one of the amorphous semiconductor layers is additionally provided. The crystallization procedure is carried out. 201117403 Next, as shown in FIG. 4, the first amorphous semiconducting layer 310 can be formed on the polycrystalline photovoltaic device 200 according to the method for forming the second amorphous optical element 3, in the first non- The second amorphous semiconductor layer 320 is formed on the crystalline semiconductor layer 310, and the third amorphous semiconductor A layer 33 is formed on the second amorphous semiconductor layer 320. That is, &lt; forming a first amorphous photoelectric composition of the amorphous half-Z body layer 310, the second amorphous semiconductor layer 320, and the third amorphous semiconductor layer phantom composition on the polycrystalline photovoltaic device 2A Element 300. Further, as shown in FIG. 5, the second amorphous photo-electric device 300 can be formed on the first amorphous photovoltaic device 300 by the method of the second amorphous photovoltaic device. The first amorphous semiconductor layer 430 is formed on the amorphous semiconductor layer 410, and the third amorphous semiconductor layer 430 is formed on the second amorphous semiconductor layer 420. In other words, the second amorphous photovoltaic layer composed of the second amorphous semiconductor layer 41, the second amorphous semiconductor layer 42 and the third amorphous layer 430 can be formed on the first amorphous photovoltaic element 3A. Element 4〇〇. The polycrystalline photovoltaic device 200 described above, the first! The semiconductor layer of the amorphous photoelectric _300 and the second amorphous photovoltaic element 400 can be a P-type, an i-type, an i- & a n-dust of electricity generated by the light generated by the light of the piece of light. The flat conductor layer is sequentially constructed of p-i-n diodes. At this time, the semiconductor layers of the P i , 1 type, and η + type should be laminated in order. Here, the 'i type indicates the imdsic of undoped impurities. Further, "+" and "-" indicate the phase difference of the doping concentration, and "+" indicates a doping concentration having a high concentration with respect to "one". For example, n+ is more highly doped than η-. Further, when + or - is not indicated, it is indicated that the doping concentration is not particularly limited. Further, the polycrystalline photovoltaic device 200, the first amorphous photovoltaic device 3A, and the 12201117403 semiconductor thin layer of the second amorphous photovoltaic device 400 can generate electric power by receiving light generated by light. The structure of the η-i-p diode of the n-type, the bismuth ΛιΙ, the t ^ 1 type, and the P-type semiconductor layer sequentially. At this time, the n+ type, i type, and p+ type semiconductor layers should be laminated in order. Further, the polycrystalline photovoltaic element 200, the semiconductor layer of the non-曰 曰 曰 先 先 先 及 及 及 and the second amorphous photoelectric element can be used to generate electric power by receiving light generated by light. The structure of the ρ-ρ-η diode of the type, p-type, and n-type semiconductor layers is sequentially laminated. In this case, the semiconductor layers of ρ+ type, ρ-type, and η+ type should be laminated in sequence. Further, the 'polycrystalline photoelectric element 2', the flute, the first non-Japanese solar cell 300, and the semi-conducting layer of the second amorphous photo-electric element 400 may be light generated by receiving light. The n-type, n- and 丨-type, 〃n-type, and P-type semiconductor layers of electric power are used to sequentially construct a nn-p diode. At this time, the n + -type and n-type semiconductor layers should be laminated in order. On the other hand, the n-type or P-type doping is preferably carried out in situ in the formation of an amorphous layer. As the impurity in the doping type doping, it is common to use (4) (8), and as the impurity f in __, it is generally used to fill (P) or (4) M), but it is not limited thereto. Further, the polycrystalline photovoltaic element_, the first amorphous photovoltaic element 300, and the second amorphous photovoltaic element 4GG' are defects (such as impurities and suspension bonds) which are present in the amorphous semiconductor layer. The properties can be hydrotreated. Finally, as shown in Fig. 6, a conductive material upper electrode can be formed on the second amorphous photovoltaic element 4A. The material of the upper electrode lion is transparent 13 201117403 Conductive material, such as TC〇 for transparent conductive layer, and AZO(ZnO: Al), lT〇(Indium Tin Oxide), GZO(ZnO : Ga Any of BZO (ZnO: B) and FT0 (Sn02: F) is preferable, but is not limited thereto. As a method of forming the upper electrode 5, a physical vapor deposition method such as sputtering, a chemical vapor deposition method such as LPCVD, PECVD, or MOCVD, or the like can be included. Thus, a three-junction tandem solar cell according to an embodiment of the present invention can be formed. On the other hand, although it is not shown, it can be between the polycrystalline photovoltaic element 2 (8) and the first amorphous photoelectric element 300, or between the first amorphous photoelectric element 3 〇〇 and the second amorphous photoelectric element 400. Any one or more of them further forms a connection layer of a transparent conductor. By the aforementioned connection layer, ohmic contact can be performed between the polycrystalline photovoltaic element and the non-crystalline photovoltaic element, and a better photoelectric conversion efficiency of the solar cell can be expected. As the material of the connection layer, any of ITO, ZnO, IZO, and FTO (Sn〇2: F) 'BZO is preferable, but it is not limited thereto. As a method of forming the connection layer, physical vapor deposition such as sputtering, and chemical vapor deposition such as LPCVD, PECVD, and M0CVD may be included. In the tandem solar cell according to the embodiment of the present invention, the polycrystalline photovoltaic device 200, the first amorphous photovoltaic device 3, and the second amorphous photovoltaic device 400 are included in the solar cell of the tandem solar cell. It is desirable to have the following energy band gap (Eg). First, the polycrystalline photovoltaic device 200, the first amorphous photovoltaic device 300, and the second amorphous photovoltaic device 4 can be formed into a band gap having "polycrystalline photovoltaic device 200 < first # crystalline photovoltaic device 300 = relationship of the second amorphous photoelectric element 14 201117403 piece 400". The polycrystalline photoelectric element 200 has the smallest band gap, and the first amorphous electronic component 300 and the second amorphous photovoltaic element 4 have the same (or similar) band gap. As an example, the polycrystalline photovoltaic element 2 is composed of a plurality of polycrystalline germanium (P—Si) (Eg~1.leV) layers, and the first amorphous photovoltaic element 3〇〇 and the 2nd amorphous photoelectric element. 400 is composed of a plurality of amorphous a-Si (Eg~1.7eV) layers, respectively. Further, the polycrystalline photovoltaic device 200, the first amorphous photovoltaic device 3A, and the second amorphous photovoltaic device 400 can be formed as a band gap having "polycrystalline photovoltaic device 200" first amorphous photovoltaic device 3 〇〇 <The relationship between the second amorphous photovoltaic element 400 ”. The difference in energy band gap between the polycrystalline photovoltaic device 200 and the first amorphous photovoltaic device 300, and the energy band between the first amorphous photovoltaic device 3 and the second amorphous photovoltaic device 400 The difference in the gaps is the same or a similar form to each other. As an example, the polycrystalline photovoltaic element 200 may be composed of a plurality of polycrystalline stone a-SiGe (Eg &lt; l.iev) layers, and the first amorphous photovoltaic element 3 may be composed of a plurality of amorphous germanium (a) -SiGe) (Eg = 1.3 to 1.6 eV) layer composition, and the second amorphous photovoltaic element 400 may be composed of a plurality of amorphous carbonized 1.7 eV) layers. As another example, the polycrystalline photovoltaic element 2A may be composed of a plurality of polycrystalline germanium (P-Si) (Eg~i.ieV) layers, and the first crystalline optical element 300 may be composed of a plurality of amorphous germanium (a_SiGe). (Eg=i 3~! 6eV) layer composition, and the second amorphous photovoltaic element 400 may be composed of a plurality of amorphous yttrium (a_Si) (Eg to 1.7 eV) layers. As described above, the three-junction tandem solar cell of the present invention allows the band gap to linearly increase by stacking photovoltaic elements, and the light of various wavelength regions is received to increase the photoelectric conversion efficiency of the solar cell. 15 201117403 Moreover, the three-junction tandem solar cell of the present invention does not have a small energy band gap formed by a high-quality polycrystalline germanium layer by a high-quality polycrystalline germanium layer by a conventional microcrystalline germanium layer. The photoelectric element can increase the light collecting efficiency of the long wavelength and improve the photoelectric conversion efficiency of the solar cell. Moreover, the polycrystalline germanium is superior to the microcrystalline stone and has excellent aging characteristics (aging is not easy to progress), and therefore, the three-junction tandem solar cell system using the polycrystalline germanium layer of the present invention can be improved. Life and reliability. Further, the three-junction solar cell of the present invention allows the control of the manufacturing process to be easily performed by forming a photovoltaic element having a small band gap in which light of a long wavelength region is received by a polycrystalline germanium layer, and The manufacturing process time is shortened to improve productivity. The present invention has been described with reference to the preferred embodiments of the present invention, and is not limited to the embodiments described above, and is intended to be within the scope of the invention. The knowledgeable person can make various changes and changes. Such modifications and variations are considered to be within the scope of the invention and the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a method of manufacturing a solar cell according to an embodiment of the present invention. Fig. 2 is a cross-sectional view showing a method of manufacturing a tandem solar cell according to an embodiment of the present invention. Fig. 3 is a cross-sectional view showing a method of manufacturing a tandem solar cell according to an embodiment of the present invention. Fig. 4 is a cross-sectional view showing a manufacturing method of a tandem solar cell according to an embodiment of the present invention. Fig. 5 is a cross-sectional view showing a method of manufacturing a tandem solar cell according to an embodiment of the present invention. Fig. 6 is a cross-sectional view showing a method of manufacturing a tandem solar cell according to an embodiment of the present invention. [Description of main component symbols] 100.. substrate 110.. lower electrode 200.. polycrystalline photovoltaic element 210, 310, 410... first amorphous semiconductor layer 211.. first polycrystalline semiconductor layer 220.320.420.. Second amorphous semiconductor layer 221.. second polycrystalline semiconductor layer 230, 330, 430... third amorphous semiconductor layer 231.. third polycrystalline semiconductor layer 300.. first amorphous photovoltaic element 400. . . 2nd amorphous photoelectric element 500.. . upper electrode 17

Claims (1)

201117403 七、申請專利範圍： 1. 一種太陽電池，其特徵在於包含： 基板； 多結晶光電元件，係形成於前述基板上，且積層有 複數的多結晶半導體層； 第1非晶質光電元件，係形成於前述多結晶光電元 件上，且積層有複數的非晶質半導體層； 第2非晶質光電元件，係形成於前述第1非晶質光電 元件上，且積層有複數的非晶質半導體層；及 上部電極，係形成於前述第2非晶質光電元件上。 2. 如申請專利範圍第1項之太陽電池，其中前述第1非晶質 光電元件及前述第2非晶質光電元件之能帶間隙係相 同。 3. 如申請專利範圍第1項之太陽電池，其中前述多結晶光 電元件、前述第1非晶質光電元件及前述第2非晶質光電 元件，係具有藉由積層順序而線性地增加之能帶間隙。 4. 如申請專利範圍第1項之太陽電池，其中前述多結晶光 電元件係以多晶質矽或多晶質矽鍺之任一者而形成。 5. 如申請專利範圍第1項之太陽電池，其中前述第1非晶質 光電元件係以非晶質矽或非晶質矽鍺之任一者形成。 6. 如申請專利範圍第1項之太陽電池，其中前述第2非晶質 光電元件係以非晶質矽或非晶質碳化矽之任一者形成。 7. 如申請專利範圍第1項之太陽電池，其中前述多結晶半 導體層係藉由SPC(Solid Phase Crystallization:固相結 晶）、ELA(Excimer Laser Annealing :準分子雷射退火）、 18 201117403 SLS(Sequential Lateral Solidification :連續橫向固化）、 MIC(Metal Induced Crystallization :金屬誘發結晶）及 MILC(Metal Induced Lateral Crystallization:金屬誘發橫 向結晶）之任一個方法而結晶化。 8. 如申請專利範圍第1項之太陽電池，其係進而於前述基 板與前述多結晶光電元件之間形成下部電極。 9. 如申請專利範圍第1項之太陽電池，其係於前述多結晶 光電元件與前述第1非晶質光電元件之間以及前述第1 非晶質光電元件與前述第2非晶質光電元件之間之至少 一者進，而形成透明導電體之連接層。 10. —種太陽電池之製造方法，其特徵在於包含下述步驟， 即： (a) 於基板上積層複數的多結晶半導體層而形成多 結晶光電元件之步驟； (b) 於前述多結晶光電元件上積層複數的非晶質半 導體層而形成第1非晶質光電元件之步驟； (c) 於前述第1非晶質光電元件上積層複數的非晶質 半導體層而形成第2非晶質光電元件之步驟；及 (d) 於前述第2非晶質光電元件上形成上部電極之步 驟。 11. 如申請專利範圍第10項之太陽電池之製造方法，其中前 述第1非晶質光電元件及前述第2非晶質光電元件之能 帶間隙係形成為相同。 12. 如申請專利範圍第10項之太陽電池之製造方法，其中前 19 201117403 述多結晶光電元件、前述第1非晶質光電元件及前述第2 非晶質光電元件，係形成為具有藉由積層順序而線性地 增加之能帶間隙。 13. 如申請專利範圍第10項之太陽電池之製造方法，其中前 述多結晶光電元件係以多晶質矽或多晶質矽鍺之任一 者形成。 14. 如申請專利範圍第10項之太陽電池之製造方法，其中前 述第1非晶質光電元件係以非晶質矽或非晶質矽鍺之任 一者形成。 15. 如申請專利範圍第10項之太陽電池之製造方法，其中前 述第2非晶質光電元件係以非晶質矽或非晶質碳化矽之 任一者形成。 16. 如申請專利範圍第10項之太陽電池之製造方法，其中前 述多結晶半導體層係藉由SPC(Solid Phase Crystallization :固相結晶）、ELA(Excimer Laser Annealing :準分子雷射退火）、SLS(Sequential Lateral Solidification :連續橫向固化）、MIC(Metal Induced Crystallization :金屬誘發結晶）及MILC(Metal Induced Lateral Crystallization:金屬誘發橫向結晶）之任一個方 法而結晶化。 17. 如申請專利範圍第10項之太陽電池之製造方法，其係進 而於前述基板與前述多結晶光電元件之間形成下部電極。 18. 如申請專利範圍第10項之太陽電池之製造方法，其係於 前述多結晶光電元件與前述第1非晶質光電元件之間以 20 201117403 及前述第1非晶質光電元件與前述第2非晶質光電元件 之間之至少一者，進而形成透明導電體之連接層。 21201117403 VII. Patent application scope: 1. A solar cell, comprising: a substrate; a polycrystalline photovoltaic element formed on the substrate and having a plurality of polycrystalline semiconductor layers laminated thereon; a first amorphous photoelectric element, a plurality of amorphous semiconductor layers are formed on the polycrystalline photovoltaic element, and a plurality of amorphous semiconductor layers are laminated; and the second amorphous photovoltaic element is formed on the first amorphous photovoltaic element, and a plurality of amorphous layers are laminated The semiconductor layer and the upper electrode are formed on the second amorphous photovoltaic element. 2. The solar cell according to claim 1, wherein the first amorphous photovoltaic element and the second amorphous photoelectric element have the same energy band gap. 3. The solar cell according to claim 1, wherein the polycrystalline photovoltaic device, the first amorphous photovoltaic device, and the second amorphous photovoltaic device have a linear increase in energy by a lamination sequence. With a gap. 4. The solar cell according to claim 1, wherein the polycrystalline photovoltaic element is formed by any one of polycrystalline germanium or polycrystalline germanium. 5. The solar cell according to claim 1, wherein the first amorphous photovoltaic element is formed of either amorphous or amorphous. 6. The solar cell according to claim 1, wherein the second amorphous photovoltaic element is formed of any one of amorphous germanium or amorphous tantalum carbide. 7. The solar cell of claim 1, wherein the polycrystalline semiconductor layer is by SPC (Solid Phase Crystallization), ELA (Excimer Laser Annealing), 18 201117403 SLS ( Crystallization by either of Sequential Lateral Solidification, MIC (Metal Induced Crystallization), and MILC (Metal Induced Lateral Crystallization). 8. The solar cell according to claim 1, wherein the lower electrode is formed between the substrate and the polycrystalline photovoltaic element. 9. The solar cell according to claim 1, wherein the first amorphous optical element and the second amorphous photoelectric element are between the polycrystalline photovoltaic element and the first amorphous photoelectric element; At least one of them enters to form a connecting layer of transparent conductors. 10. A method of manufacturing a solar cell, comprising the steps of: (a) forming a polycrystalline photovoltaic element by laminating a plurality of polycrystalline semiconductor layers on a substrate; (b) said polycrystalline photovoltaic a step of forming a plurality of amorphous semiconductor layers on the element to form a first amorphous photoelectric element; (c) forming a plurality of amorphous semiconductor layers on the first amorphous photoelectric element to form a second amorphous material a step of forming a photovoltaic element; and (d) a step of forming an upper electrode on the second amorphous photovoltaic element. 11. The method of manufacturing a solar cell according to claim 10, wherein the band gaps of the first amorphous photovoltaic element and the second amorphous photovoltaic element are the same. 12. The method of manufacturing a solar cell according to claim 10, wherein the polycrystalline photoelectric device, the first amorphous photovoltaic device, and the second amorphous photovoltaic device are formed by the above-mentioned 19 201117403. The stacking sequence increases the energy band gap linearly. 13. The method of producing a solar cell according to claim 10, wherein the polycrystalline photovoltaic element is formed by any one of polycrystalline germanium or polycrystalline germanium. 14. The method of manufacturing a solar cell according to claim 10, wherein the first amorphous photovoltaic element is formed of either amorphous or amorphous. 15. The method of producing a solar cell according to claim 10, wherein the second amorphous photovoltaic element is formed of either amorphous germanium or amorphous tantalum carbide. 16. The method of manufacturing a solar cell according to claim 10, wherein the polycrystalline semiconductor layer is by SPC (Solid Phase Crystallization), ELA (Excimer Laser Annealing), SLS Crystallization is carried out by any one of (Sequential Lateral Solidification), MIC (Metal Induced Crystallization), and MILC (Metal Induced Lateral Crystallization). 17. The method of manufacturing a solar cell according to claim 10, wherein the lower electrode is formed between the substrate and the polycrystalline photovoltaic element. 18. The method of manufacturing a solar cell according to claim 10, wherein the first amorphous photoelectric element and the first amorphous photoelectric element are between 20201117403 and the first amorphous photoelectric element; 2 at least one of the amorphous photovoltaic elements further forms a connection layer of the transparent conductor. twenty one
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