TW201001727A - Photoelectric transducer structure and solar cell - Google Patents

Photoelectric transducer structure and solar cell Download PDF

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Publication number
TW201001727A
TW201001727A TW098107310A TW98107310A TW201001727A TW 201001727 A TW201001727 A TW 201001727A TW 098107310 A TW098107310 A TW 098107310A TW 98107310 A TW98107310 A TW 98107310A TW 201001727 A TW201001727 A TW 201001727A
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TW
Taiwan
Prior art keywords
layer
type semiconductor
semiconductor layer
electrode
contact
Prior art date
Application number
TW098107310A
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English (en)
Inventor
Tadahiro Ohmi
Tetsuya Goto
Kouji Tanaka
Yuichi Sano
Original Assignee
Univ Tohoku Nat Univ Corp
Tokyo Electron Ltd
Sharp Kk
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Application filed by Univ Tohoku Nat Univ Corp, Tokyo Electron Ltd, Sharp Kk filed Critical Univ Tohoku Nat Univ Corp
Publication of TW201001727A publication Critical patent/TW201001727A/zh

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    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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    • Y02E10/548—Amorphous silicon PV cells

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201001727 六、發明說明： 【發明所屬之技術領域】 本發明係關於光電轉換元件構造及包含該光電轉換元件構造 的太陽電池。 【先前技術】 一以往人們提出的太陽電池中，有以薄膜形成之包含光電轉換 〇件構造的太陽電池。此時，有時採用pin構造，其具有使i型半 導體層之兩面分別接觸一導電型(例如p型)爭導體層及逆導電型 (例如n型)半導體層的構造。採用此種pin構造時，藉由對i型半 導體層施加電場，可使載波的擴散長度拉長。又，有人提出：以 非晶質半導體、微晶半導體、單晶半導體、多晶半導體等各種之 半導體，形成光電轉換元件構造的各半導體層。而且，也有人提 出·使用Si、SiC、(3e、SiGe等，作為形成各半導體層的半導體。 ^如上述’包含具有i層之3層構造之光電轉換元件構造的太陽 電池由於必須將3種半導體層成膜，因此無法避免成本的提高。 日專利文獻1及2揭示著包含pin型光電轉換元件構造的薄膜太 1%電池。具體而言，專利文獻1所記載的薄膜太陽電池包含pin 型非晶質的光電轉換元件構造，該光電轉換元件構造具有含微晶 相之非晶質矽(μο —Si)層。亦即，專利文獻1所記載的薄膜太陽電 池於形成發電層的pin層中，以含微晶相之半導體層(^_Si)形成 P層’以非晶質矽鍺(a—SiGe)形成i層，並在該p層與i層之間， 設置—層能帶間隙比P層廣，且p型而不純物濃度低的界面層。 該光電轉換元件構造可抑制光照射後之特性的劣化，並可達到效 率的提高。 又，專利文獻2揭示著包含光電轉換元件構造的太陽電池， 該光電轉換元件構造將製造處理之熱擴散所產生的界面特性之劣 化加以抑制，而轉換效率高。專利文獻2提出光電轉換元件構造， 於形成發電層的pin層中，分別以含微晶相之非晶質矽系薄膜(队 —Si)形成p及η塑_導體層，且以非晶質矽系膜形成1型半導體 201001727 層。而且’專利文獻2提出：在p型或” 層之間，設置由複數層構成之界面半導體體層與i型半導體 型半導體層側之界面半導體層的不純物d構造。在此’使i 層側之界面半導體層的不純物添加量，夢、、°篁少於非晶質半導體 型半導體層側接合界面的能帶間隙比f^使1型半導體層之Ρ fb:包含上述光電轉換元件構造的太陽電池 【專利文獻1】曰本特開2001-1683%镜公 【專利文獻2】曰本特開2003-8038號公報 【發明内容】 [發明所欲解決之課題] 如前所述，專利文獻i及2均藉由 發電層的内部構造，財卩制界_彳 ΡΠ層之*3層構成的 提高。 彳|曲将陡的$化，而達到轉換效率的 構；另一方，蛊刹# θ 〇層之間’ δ又置界面層的結 ’ 專文獻2也揭示著在丨型半導體芦鱼D刑式η = Ϊ置界：半導體層的結構。換言之'專利2 : 隨的問題^ n而械之電極層所帶有的鋼電阻將伴 :提供光電轉換元件構造及太陽電池，可降 低電極層與半導體層之間的接觸電阻。 月為’ 3由將接觸於發電層而形成之電極層 口 :丨，、轉換效率高’且經濟性高的光電轉換元件構造 及太陽電池。 祉麻本& ^之^另0的為：藉由改善發電層本身的構造，以提 =使接觸電阻降低的光電轉換元件構造及太陽電池。 [解決課題之手段] 依本發^之第1態樣’提供光電轉換元件構造，其特徵在於： 包含.第1電極層、第2電極層 '與設在該第1及第2電極 201001727 層之間的1個或複數發電疊層體； 該發電疊層體包含：p型半導體層 形成的i型半導體層、與接觸於該i 戎P型半導體層而 體層； 娜層娜柄η型半導 該1個發電疊層體或該複數發 發電疊層體之該Ρ型半導體層接觸於之該第1電極侧的 疊層體或該複數發電疊層體中之該第電極層，該1個發電 η型半導體層接觸於該第2電極層"；電極側的發電疊層體之該 該第2電極層中，至少接觸於該 的金屬具有絕對值小於該接觸之η 触^ 層的部分所含有 矽時絕對值為4.09eV)的功函數。千¥體層之電子親和力(η型 依本發明之弟2態樣’提供来|綠& 一 電極層之至少接觸於該η型半導 牛構造，其中，該第2 紀構成之群_至少-種單體金選自於域、給、 依本發明之第3態樣，提供^成。… -項態樣中，至少1個該㈣晶㊣、轉奐70件構造，係於上述任 微晶非晶質稍非晶質料體^^型半導體層以結晶石夕、 ι=Γί^ t提供光電轉㈣件構造，係於上述任 體層4:親值小於該接觸之η型半導 -項明2?5= 樣’提供光電轉換元件構造，係於上述任 的電極層除接觸於該n型半導體層之部分以外 之電^彳& ^屬比祕料對值小於該接觸之n㉟半導體層 數的金屬係導電率高的金屬。 1 tirt弟6態樣’提供光電轉換元件構造，係於上述任 所目電極層之至少接觸於該P盤半導體層的部分 已3弟1電私層、第2電極層、與設在該第1及第2電極 201001727 層之間的1個或複數發電疊層體； 該發電疊層體包含：p型半 形成的i型半導體層、與接觸於該該P型半導體層而 體層； t半導體層而形成的η型半導 發電疊層體或該複數發電疊層體中之今第i電枉她 發電疊層體之該p型半導體層接觸於；T 气1 ,極侧的 疊層體或該複數發電疊層體中之該筮電極層，f 1個發電 η型半導體層接觸於該第2電極層Λ; 1極側的發電疊層體之該 该第1電極層中，至少接觸於Λ 的金屬具有絕對值大於該接觸之導體層的部分所含有 能階的功函數。 料導體層的價電子帶上限之 依本發明之第8態樣，提供 電極層之至少接觸於該P型半導=於由二第1 :)。、綱與摩臟之群 电位層以具有絕對值大於該接觸之p啷本厣的價雷子;^ 之能階的功函數的金屬構成。p i + v體層如貝電子▼上限 依本發明之帛10態樣，提供光造， 1電極層除接觸於續创本道 轉換兀件構 /、 Μ弟 屬比起具有絕^大層之部分以外的料所使用的金 能階的功p型半導體層的價電子帶上限之 月bu的功函數的金屬係導電率高的金屬。 包第..11祕，提供光電轉換元件構造，其特徵在於： 體犀之：声二半導體層，—導電型半導體層，接觸於該i型半導 4面而形成；與金屬層，直接接觸於該丨辨導體層之另 =，，且由事先決定之金屬構成。 屬層料紐，提供光電轉換7^件構造，其中，該金 ϋ私日日+導體層及該—導電型半導體層—同形成發電區。 一電極，i接13態樣，提供光電轉換元件構造，其中，包含 直接接觸於該—導電型半導體層而形成，或者隔著其他 201001727 發電區接觸於該—導電型半導體層而形成。 力电位增接觸於该金屬層而形成。 於該’提絲賴換元件構造，射，接觸 -體層。 豆曰之一表面而形成的一導電型半導體層為ρ型半導 11〜日mi6 ’提供光電轉換元件構造，係於上述第 成的金屬觸於該1型半導體層之另一表面而形 時，、係且;於構成该1型半導體層之半導體為11型半導體 屬Ί有纟_值小於該n财賴之電子親和力之功函數的金 1卜月十之第17態樣’提供光電轉換元件構造，係於上述第 的型，層為η型半導體層;接;半^ 絕對值大於該p型半導體的價電子帶上限之 ‘含找d18^'樣’提供光電轉換元件構造，其特徵在於： 斤之二i ^ f層、第2電極層、與設在該第1及第2 « “妾觸於該;電疊層體包含沖型半導體 型半導體居而i i H形成的1型半導體層、與接觸於該i 發電疊層體巾二^ ϋν體層；該1個發電疊層體或該複數 觸於鄕1電極層，_ 層體之該ρ型半導體層接 該第1電極側的發電；豐層f或該複數發電疊層體中之 層；該第2電極層中半導體層接觸於該㈣極 A1 ^ Ag ^ ^ 態樣換元件構造，係於第α 自於由猛與結構成之群組的至少—種單以選 201001727 依本發明之第20態樣，提供光電轉換元件構造，其特徵在於： 包含：第1電極層、第2電極層、與設在該第1及第2電極 層之間的1個或複數發電疊層體，該發電疊層體包含：p型半導體 層二接觸於該p型半導體層而形成的i型半導體層、與接觸於該1 =半導體層而形成的η型半導體層；該[個發電疊層體或該複數 發電疊層體中之該第1電極侧的發電疊層體之該p型半導體層接 觸=該第〗電極層，該1個發電疊層體或該複數發電疊層體中之 該第^，極侧的發電疊層體之該η塑半導體層接觸於該第【電極 層，該第1電極層中，至少接觸於該{)型半導體層的部分 有絕對值大於ΖηΟ之功函數的金屬。 ’、 t依本發明之第21態樣，提供光電轉換元件構造，係於第2〇 態樣中，該第1電極層之至少接觸於該p型半導體層的部 (Co)或其合金形成。 ’’ 依本發明之第22態樣，提供光電轉換元 U〜態樣中之任-項，該丨型半導體層卿形成。伙上述弟 述第!態樣，提供太陽電池，其特徵在於：包含上 11 22恶樣中任一項所記載的光電轉換元 [發明之效果] 轉換=光與半導體層之接觸電阻，可得到 【實施方式】 [貫施發明之最佳形態] 原理參f ^ :杨之光㈣換元件的賴電路®，綱本發明的 阻触，相當於因該發電層1〇妾)人〇 j照射產生電；並聯電 流；電阻Rs，係與夾持發電層】Q ^匹配所產生的漏電 阻Rs為各電極本身的電阻、各 2個電極間的電阻。在此，電 的接觸電阻的合成電阻。由圖亦可知m電層之半導體層之間 負載連接於2個電阻Rs間。 201001727 位挪t發明的原理在於藉由降低圖1所示之等價電路的電阻Rs的 電1^’以提高光電轉換元件構造的轉換效率。 參照圖2,依本發明之第1實施形態的光電轉換元件構造如圖 =不’包含：第1電極21，以透明電極形成；第2電極22，如 1或Ag’具有高反射率；與發電層25，設在第1及第2電極21、 二由PU1之3層構成。發電層25包含：p型半導體層251， ==於弟1電極21而形成·，η型半導體層252，接觸於第2電極 μ触，成；與丨型半導體層253，設在ρ型半導體層251與η型半 挪麻曰252之間。又，本實施形態中，構成發電層25的Ρ型半導 二二25卜1型半導體層253與η型半導體層252使用結晶矽⑸）。 寸二結晶石夕形成之p—Si的價電子帶上限之能階為， 读極21使用具有絕對值大於此能階之功函數的金屬。或者， 第f亟21使用具有絕對值大於Zn〇之功函數的金屬或其合金。 用呈Ϊ二方面別的電子親和力為—4.09eV，第2電極&使 =具有絕對值小於ai及知之功函數m合金 明之第1貫施形態令，著眼於第2電極22，即背面電極 又，_ D㈣Μm Λ層之間的接觸電阻。 赤ιΓ ® 通常使用具有—4.麟之功函數的紹⑽ 或八有~ 4.26eV之功函數的銀(Ag)。 . 在此，以具有絕對值小於半導體(n〜Si)之雷子 = = ==:=:料糊; 觸的ί屬:料而^構^ ^ 一他二特基能障 1上述可降低接____可藉健觸電阻。 二。：下’以_表示金屬㈣之功:數ϋ 功 丰導體(在此為n —Si)之電子親和力。 山数以0s表不 現在’參照圖3A及圖3B，顯示著對真空位準之功函數的關 9 201001727
#時之接觸前的狀態與接觸後的狀態。當此 f ί導體與f屬接觸，如圖3B所示，形成歐姆接觸。n —Si之0S 係”因此具有絕對值小於動—⑴之功函 之工“的金屬材料可利用功函數一 3.7eV之Mg、功函數 功函數—3aev之γ等，藉由使用該等金屬，比 起使 g接觸於n —Si的情況可降低接觸電阻。 凰L 藉由使用具有絕對值小於A1及Ag之功函數的金
Ag接觸於n — &的情況也可降低接觸電阻。 =如，功函數一4.leV之Mn及Zr係與一4】ev之A丨、— ;二/之?同樣地’比n —Si之功函數一4.09eV猶微小，形成 關係。此時’上述金屬材料接觸於n—si前的狀態下， 之狀態；另—方面，當二者接觸，如圖4b所示， ‘雷、(障壁）°但是’當n—Si之表面被過度推雜，因隧 I電机通過卩早壁而形成歐姆接觸則與A卜Ag相同。 /由Mn、&之功函數比起八卜接近n —Si之功函數 第^，電極、22 小於A1 * ~的功函數，因此以*、&形成 一眘防v起使用Al、Ag的情況，也可降低接觸電阻。 之—杳t / ’A!與1卜&的接觸電阻為5χιο—6ω，2左右，金屬 ϋΓι s tfV’、n —Sl之功函數4s的差為0-05eV的Mn、Zr中， Y Ω •⑽2左右的接觸電阻。甚至，在其他Mg、Hf、 Y也可降低接觸電阻到丨(Γ8Ω . cm2左右。 阻進中圖2所不之第2電極22與n-S”_接觸電 ϊ於弟1電極21與13—Si251，也可降低P—Si與第 ===，的接觸電阻。通常，卜Si的價電子帶上限之能階# 金屬二，具^絕對值大於此能階之功函數的 #卜5 p—si的偶子帶上限之能階 觸。而士，=的金屬(即心〈㈣時，形成歐姆接 : 2於N]之功函數㈣-5.2eV，故使用见作為 數分別A 低與P —&的接觸電阻。k、Pd、Pt也由於功函 数刀別為-5.3eV、—5.2eV、—5.7eV，係屬適當。 10 201001727 造。圖 實施形態的光麵元件構 設有附加金屬層30。圖示之ttn — Sl252與第2電極22之間， Ag ^2 22 5 A1 ^ Q-oco «Ρ, J及对羊’另一方面’第2電極22盘n .層;^^=電_的附加金屬層3ΰ。形成附加金屬 Λ，-I -- 可降低接觸電阻。藉由使用此種八M g 11 Υ Ζι等）， 形成歐姆接觸。 種金屬，可與卜犯52之間實質性 的接^電具_^15eV之功函數的P —_與第1電極21 S —Γ251與第1電極21之間設置附加金 極時，藉由使用—5二數502=Z=^-Si侧的電
Zn〇iiSf ^ 产之功Hn, Μ52。錢屬層35使用具有與1 卜犯52同等程 t ^ 材/?為#具有與帶有—條V之功函數 _之功函數函數知的金屬，可使用具有- 將且了^252/換成金屬層％的例子，但也可 之11 形成金屬層的金屬材料，也可降低接觸電阻。 士入施形態中，僅說明使用結㈣的情況；但本發明並不 ，凡王限方；此，同樣也可適用於使用含微晶之非晶 = ^此時’考慮非晶質微叫 — Si的功函數而選擇金屬，係屬^ 降低===率適用於使用其他半導體時，也可 201001727 【產業上利用性】 依本發明之光電轉換元件不限於太陽電池，也可適用於其他 電子設備用的光電轉換元件。 【圖式簡單說明】 圖1顯示說明本發明之原理的光電轉換元件構造的等價電路。 圖2係說明依本發明之一實施形態的光電轉換元件構造的概 略圖。 圖3A顯示n — Si與金屬接觸前之功函數成（/) s < 0 m之關係 時的能帶構造與接觸後的能帶構造。 圖3B顯示n —Si與金屬接觸前之功函數成4s< 4m之關係 時的能帶構造與接觸後的能帶構造。 圖4A顯示n — Si與金屬接觸前之功函數成4s> c/uii之關係 時的能帶構造與接觸後的能帶構造。 圖4B顯示η — Si與金屬接觸前之功函數成4s> 0m之關係 時的能帶構造與接觸後的能帶構造。 圖5係說明依本發明之另一實施形態的光電轉換元件構造的 概略圖。 圖6係說明依本發明之又另一實施形態的光電轉換元件構造 的概略圖。 【主要元件符號說明】 10〜發電層（電池部分） 21〜第1電極 22〜第2電極 25〜發電層 30〜附加電極層（附加金屬層） 35〜金屬層 251〜p型半導體層 252〜η型半導體層 12 201001727 253〜i型半導體層 Rs〜電阻 Rsh〜並聯電阻 0 s〜η — Si之電子親和力 0 m〜金屬材料之功函數 13

Claims (1)

  1. 201001727 七、申請專利範圍： 1.一種光電轉換元件構造，其特徵在於： 包含：第]電極層、第2電極層、與設在該第丨及第2電極 層之間的1個或複數發電疊層體； 該發電疊層體包含：p型半導體層、接觸於該p型半導體層而 形成的i型半導體層、及接觸於該i型半導體層而形成的n型半導 體層； ’ 該1個發電疊層體或該複數發電疊層體中之該第丨電極側的 ^電疊層體之該P型半導體層接觸於該第i電極層，該丨個發電 複數發電叠層體中之該第1電極側的^電疊層體^該 η里半V體層接觸於該第2電極層；且 μ古ϊΐΐ 1極層中之至少接觸於該η型半導體層的部分，包含 ίίΪ 接觸之η型半賴層之電子親和力為小的功函數 利Ϊ圍第1項所述之光電轉換元件構造，其中，該第2 2二於該Π型半導體層的部分，係以選自於由鎂、 、’構成之群_至少—種單體金屬或其合金形成。 3少 1 項所述之光電轉換元件構造，其中，秦 石夕與非晶質石m ’係以結晶碎、彳《非晶質 其中，3項巾任—項所述之光電轉換元件構造， 之電子親她^侧_之η型半導體廣 其中，ί亥Hm1至3項中任一項所述之光電轉換元件構造’ 分，其構成金接觸於該n型半導體層之部分以外的部 屬之V電率比具有絕對值小於該接觸之n型半導體 14 201001727 層之電子親和力的功函數之金屬為高。 6. 如申請專利範圍第1裏5項中任—項所奸夕止帝一 其中，該第1電極層之至少接觸於該p型半導牛構造， 的功函數之金屬。 外電子社限之能階為大 7. —種光電轉換元件構造，其特徵在於： 包含··第1電極廣、第2電極層'、與 層之間的1個或複數發電疊層體； ^弟及第2電極 該發電疊層體包含：P型半導體層 形成的i型半導體層、及接觸於該i型该p型半導體層而 體層； ，半^體層而形成的η型半導 該1個發電疊層誠該複數發電4 言電疊層體之該Ρ型半導II層接觸於“ Τ 弟」電極側的 疊層體或該複數發電疊層體中之該第Λ 電極層，戎1個發電 η型半導體層接觸於該第2電極層"；且電極側的發電疊層體之該 5亥弟1電極層中之至少接網 具有絕對值較該接觸之ρ型半導^半導體層的部分，包含 ：的功函數之金屬。 且θ的價電子帶之上限能階為大 8.如申請專利範圍第6或7 第1電極層之至少接觸於該ρ型’.= 專換兀件構造，其中，該 鎳㈣、鉉⑻、把(ρ層的部分，係以選自於由 其合金形成。 、’冓成之群組的至少一種單體金屬或 9.如申請專利範圍第6 其中，該第1電極項所述之光電轉換元件構造， 價電子帶之上限能階為=:=^之。型半導體層的 201001727 Ϊ如項中任—項所述之光電轉換元件構 Ϊ分，、Ι·=電ϊίΓ觸於該p型半導體層之部分以外的 體層的價電子帶之上限能階的功函數之金屬為高。 + 1]·一種光電轉換元件構造，其特徵在於包含： i型半導體層； 及-導電型半導體層，接觸於該i型半導體層之—表面而形成； 金屬層，直接接觸於該i型半導體展 事先決定之金屬構成。 +導體層之另—表面而形成，且由 12.如申請專利範圍第^項所述 屬層與該i型半暮舻厗^ _电平寻谀兀件構k，其中，該金 體層㈣-導電型半導體層—同形成發電區。 π·如申睛專利範圍第u或ι2項 J含-電極，直接接觸於該—導 構造，其中’ 其他發魏翻該—導電料物成，或者隔著 14. 如申請專利範圍第n至 造，其中，包含另中技成^ 任項所述之光電轉換元件構 3另一電極層，接觸於該金屬層而形成午構 15. 如申請專利範圍第η至14項 造，其中，接觸於該丨型半導體芦 、斤述之光電轉換元件構 體層為p型半導體層。 θ 表面而形成的一導電型半導 16. 如申請專利範圍第丨】至& f ’射，接觸於該i型半導體一矣所述之光電轉換元件構 f’於構成該i型半導_之半二疒=而形成的金屬層之金 對值小於該η型半導體之電子時，係具 201001727 一項所述之光電轉換元件構 造，其中 造，其中，
    17·如申請專利範圍第11至14項中任 之一表面而形成的一導電型半導體層 表面而形成的金屬層的金屬，於 型半導體時，係具有絕對值大於 ;階的功函數之金屬。 與设在§玄第1及弟2電極 • ^重^電轉換元件構造，其特徵在於： 包含’第1電極層、第2電極層、與 运之間的1個或複數發電疊層體； ^層體包含：ρ型料體層、接觸於該ρ型半導體層而 ▲層·、半導體層、及接觸於該1型半導體層而形成的η型半導 於f1個發電疊層體或該複數發電疊層體中之該第1電極側的 聂屏二層體之5亥p型半導體層接觸於該第1電極層’該1個發電 或該複數發電疊層體中之該第1電極側的發電疊層體之該 n 土半導體層接觸於該第2電極層；且 JL古nf第2電極層中之至少接觸於該η型半導體層的部分，包含 、有絕對值小於Α1及Ag之功函數的金屬。 如申凊專利範圍第18項所述之光電轉換元件構造，其中，該第 電極層之至少接觸於該η型半導體層的部分，係以選自於由錳盥 …構成之群組的至少一種單體金屬或其合金形成。 〃、 種光電轉換元件構造，.其特徵在於： 包含：第1電極層、第2電極層、與設在該第1及第2電極 Η之間的1個或複數發電疊層體； ^邊發電疊層體包含：Ρ型半導體層、接觸於該Ρ型半導體層而 形成的丨型半導體層、及接觸於該i型半導體層而形成的11型半導 201001727 體層 該】個發電疊層體或該複數發電疊層體 發電叠層體之該P型半導體層接觸於該第i = 電極側的 第且1電極。電= 具有絕對值大於= 型半導體層的部分，包含 專利範圍第2G項所述之光電轉換元件構造，t中，兮m 1電極層之至少接觸於該p型半導體犀 十稱”甲5亥弟 金形成。 P W雑層的部分，係峨03)或其合 22.如申請專利範圍第n至21中 造，其中，該丨财導體層係邮所述之光電轉換元件構 23.—種太陽電池，其特徵在於： 項所記載的光電轉換元 包含申請專利範圍第1至？2項中权 件構造。 、任 八、圖式： 18
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JP2007005663A (ja) * 2005-06-27 2007-01-11 Matsushita Electric Ind Co Ltd 半導体装置
JP5242009B2 (ja) * 2005-09-29 2013-07-24 国立大学法人名古屋大学 カーボンナノウォールを用いた光起電力素子

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TWI578553B (zh) * 2012-01-05 2017-04-11 洪儒生 結晶矽太陽能電池及其製造方法

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