TWI377685B - Photovoltaic cell structure and manufacturing method thereof - Google Patents

Photovoltaic cell structure and manufacturing method thereof Download PDF

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TWI377685B
TWI377685B TW097147584A TW97147584A TWI377685B TW I377685 B TWI377685 B TW I377685B TW 097147584 A TW097147584 A TW 097147584A TW 97147584 A TW97147584 A TW 97147584A TW I377685 B TWI377685 B TW I377685B
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solar cell
substrate
type semiconductor
semiconductor layer
layer
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TW097147584A
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TW201023372A (en
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Feng Fan Chang
Hsin Chih Lin
Hsin Hung Lin
Chi Hau Hsieh
Tzung Zone Li
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Pvnext Corp
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Description

13.77685 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種太陽能電池元件結構及其製作方法， 尤係關於一種含銅銦鎵硒（簡稱CIGS)或含銅銦硒（簡稱 CIS )之薄膜太陽能電池元件結構及其製作方法。 【先前技術】 薄膜太陽能電池中，銅銦鎵硒太陽能電池（Copper Gallium Diselenide Solar Cells)類型之光電電池計有兩種： 一種含銅銦硒三元素（簡稱CIS)以及一種含銅銦鎵硒四元 素（簡稱CIGS)。由於其高光電效率及低材料成本，被許多 人看好。在實驗室完成的CIGS光電池，光電效率最高可達 約19% ’就模組而言，最高亦可達約丨。 圖1揭露一傳統之CIGS太陽能電池結構1〇，其係層疊結構 且包含一基板11、一金屬層12、一 〇：1(58層13、一緩衝層14 以及一透明電極層（TC0)15。基板n__般為玻璃基板，金屬 層12可以鉬（Mo)金屬層組成，以配合〇1(33的化學性質及可 承受沉積CIGS層13時之相對高溫。（^(^層13屬？型半導體 層。緩衝層14可為硫化鎘（CdS)，其係n型半導體層，且與 CIGS層13形成p-n接合面。透明導電層15可為摻鋁氧化鋅 (AZO)或其他透明導電材料。導電層15亦有稱為窗層 (window layer)，其可讓上方之光線通過而至其下之(：1<^層 13 ° 美國專利US 6,258,620揭露一CIGS太陽能電池結構，其 類似圖1所示之太陽能電池結構。其中透明電極層15係採用 1377685 AZO，且於透明電極15與緩衝層14間設有一本質（丨加^⑽⑷ ZnO層。因CIGS在長晶的過程中’經常會有空隙產生，電 池較容易發生作為陰極（負極）之透明導電層15和作為陽極 (正極）之金屬層12間產生短路的情形。本質Zn〇層具有高阻 值特性’從而可改善短路的情況。惟，如此一來可能降低 太陽能電池元件之發電效率，因此實有待技術上之進一步 突破。 【發明内容】 本發明係提供一種太陽能電池元件結構及其製作方法， 其使用粗糙基板，以有效增加太陽能電池元件中P型半導 體及Π型半導體之p_n接合面的面積，以增加光電流密度。 根據本發明一實施例之太陽能電池元件結構，其包含一 基板、一金屬層、一 p型半導體層、一 n型半導體層及一 透明導電層。該基板具一粗糙面；金屬層可包含麵金屬， 且形成於基板之該粗糙面上1型半導體層形成於該金屬層 上’可包含銅銦鎵硒硫（CIGSS)、銅銦鎵硒（CIGS)、銅銦硫 (CIS)、銅銦硒（CIS)或包含銅、硒或硫二者或二者以上之化 合物材料。η型半導體層形成於該p型半導體層上，且與該 Ρ型半導體層形成粗縫之ρ-η接合面。一實施例中，η型半 導體層可為硫化錢（CdS)。透明導電層形成於該η型半導體 層上。一實施例中，該粗糙面之粗糙度介於〇 〇1至1〇〇 之間。 製作上述之太陽能電池元件結構包含以下步驟：提供一 基板；粗糙化該基板，於該基板形成一粗糙面；形成一金 1377685 屬層於該粗縫面上；形成- p型半導體層於該金屬層上， 該P型半導體層包含銅或銅銦鎵碼之合金材料；形 成- η型半導體層於該p型半導體層上，其中^型半導 體層與該P型半導體層形成㈣之p_n#合面；以及形成 一透明導電層於該η型半導體層上。
一實施例t，基板為玻璃基板，其可利用喷砂、蝕刻進 行粗糙化。其由尤以先行噴砂後蝕刻為優選。另一實施例 中，可搭配鍍金屬膜及蝕刻進行粗糙化。若基板為金屬材 質’可利用機械壓花進行粗糖化。 【實施方式】 以下詳細討論該目前較佳實施例的製作和使用。不過， 應畲理解，本發明提供許多可應用的發明概念，其可在各 種各樣的具體情況下實施。該討論的具體實施例僅說明了 製作和使用該發明的具體方式，並沒有限制本發明的範圍。
圖2係本發明一實施例之太陽能電池元件結構。太陽能元 件結構20係層疊結構’其包含一基板21、一金屬層22、一 P型半導體層23、一 η型半導體層24、一載子阻障層25及 一透明導電層26。基板21可為玻璃基板、塑膠軟板、不錄 鋼、鉬、銅、鈦、鋁等金屬板或金屬箔片，其具有一粗縫 面27。上述基板21並非限定為板狀，而僅當作成膜基材之 用，其他例如球狀或其他各種特定或不規則形狀，亦可為 本發明所使用。一實施例中，基板2 1之表面粗輪度Ra範圍 係介於Ο.ΟΙμιη至ΙΟΟμιη之間。金屬層22可包含例如厚度約 I377685 0.5至1 μιη之鉬金屬層，且形成於該基板2i之粗糙面27,作 為電池之背接觸金屬層（Back contact metallayer)。ρ型半導 體層23形成於該金屬層22之表面，例如包含銅钢鎵碼硫 (CIGSS)、銅銦鎵硒（CIGS)、銅銦硫（CIS)、銅銦硒（CIS)或 包含銅、硒或硫二者或二者以上之化合物材料，其厚度約2 至3 μιη。η型半導體層24形成於該p型半導體層23之表面， 且與Ρ型半導體層23形成粗糙之ρ-η接合面28。一實施例 中’ η型半導體層24可為硫化鎘（CdS)、硫化辞（ZnS)、硫化 銦（InS) ’其必須遠薄於ρ型半導體層23(例如厚度約 5 0 nm) ’且必須足夠透明以利太陽光線通過。載子阻障層 25形成於該η型半導體層24之表面，其可為本質ZnO層，以 防止金屬層22及透明導電層26間短路。透明導電層26形成 於載子阻障層25之表面，其可選自銦錫氧化物（IT〇)、銦辞 氧化物（ιζο)、鋁鋅氧化物（ΑΖ0)、鎵鋅氧化物（GZ〇)、鋁鎵 鋅氧化物（GAZO)、鎘錫氧化物、氧化鋅及二氧化錯。 參照圖3，其顯示本發明之太陽能元件結構之製造方法流 程示意圖。於步驟S31中，將基板21進行粗糙化處理。一實 施例中’基板21之表面粗糙度Ra範圍係介於〇 〇1μιη至 100 μιη之間》若粗糙度不夠，ρ_η接合面28增加之面積及增 加之光線吸收量有限；若過於粗糙，會造成後續金屬膜22 不易成膜其上。 於步驟S32中，濺鍍形成金屬層22。一實施例中，選擇鉬 (Mo)金屬層組成，以配合〇18或(：1(33的化學性質及其可承 受沉積P型半導體層23(例如CIGS層）時之相對高溫。 於步驟S33中，形成p型半導體層23，本實施例係進行 CIGS鍍膜製程於金屬層22上。CIGS鍍膜可利用元素源共同 蒸鑛（Co-evaporation from elemental sources)、金屬前驅物 涵 4匕（Selenization of metallic precursor layer)、化合物源蒸 鍵（Evaporation from compound source)、化學氣相沉積 (chemical vapor deposition)、 封閉空間氣相傳輸 (close-spaced vapor transport)、喷霧熱解（spray pyrolysis)、 電锻（electrodeposition)、前驅物低溫液相沉積（low temperature liquid phase method for precursor deposition) ' 粒狀前驅物黃銅晶化（chalcogenization of particulate precursor layer)等方法製作。 於步驟S34中，形成n型半導體層24，即緩衝層。一實施 例中，使用化學浴沉積法（chemical bath deposition)，形成 一厚度約50nm之硫化鎘（CdS)層。硫化鎘層可提供對CIGS 層之保護，以避免後續濺鍍（ZnO層）製程時造成結構的損 壞。 因基板21經粗糙化後，後續彼覆其上之p型半導體層23 及η型半導體層24間將依粗糙面形狀成膜，而形成粗糙接合 面，亦即，可增加ρ型半導體層23及η型半導體層24間ρ-η接 合面28之表面積。 於步驟S35中，形成載子阻障層25，一實施例中，載子阻 障層25可為本質ZnO層（Ι-ZnO)，其可利用RF濺鍍方法形成。 1377685 • 於步驟S36中，形成透明導電層36於該載子阻障層35上。 只把例中，同樣利用濺鍵法，形成一厚度約〇 3 5至〇 5 pm之摻雜氧化辞作為透明導電層，其中使用鋁做施體。此 層可記載為Ζη〇:Α1。 由於本發明之太陽能電池元件結構係採上面照光，因此 基板21本身可為透光或不透光。若基板21採用透光之玻 璃基板，其可利用蝕刻、喷砂或喷砂後蝕刻等方式進行粗 φ 縫化 使用钱刻粗縫化之一實施例中係使用 BaS〇4+(NH4)HF2+H2〇進行蝕刻。喷砂後蝕刻方式之蝕刻 液可包含氫氟酸（HF)，以去除喷砂完成後之玻璃碎片殘 留，其流程如圖4所示。若因喷砂導致粗糙面27過於粗糙， . 可先對基板21作初步研磨後再進行蝕刻。一般而言蝕刻後 之粗糙面較平坦，而喷砂後之粗糙面較粗糙，喷砂後加蝕 刻可擷取兩者之優點。 另外，亦可於基板21上先行形成第一金屬膜，之後以乾 φ #刻或濕钮刻方式银刻第一金屬膜而形成粗链面，並接著 形成第二金屬膜而形成粗糙化基板21，其流程如圖5所示。 此外，若基板21本身即為金屬基板，則可利用機械壓花 方式粗糙化基板2 1。 下表顯不太陽能電池結構中包含經粗糙化之基板及未經 粗糙化之基板之電性實驗結果。其中Jsc係短路電流密度，· Μ係開路電麼]max係最大功率時之電流密度；二 係最大功率時之電屋；Fill fact〇r係填充因子；細以㈣ -10- 1377685 之製作實施例。 【主要元件符號說明】 10 太陽能電池元件結構 11 基板 12 金屬層 13 CIGS 層 14 緩衝層 15 透明導電層 20 太陽能電池元件結構 21 基板 22 金屬層 23 ρ型半導體層 24 η型半導體層 25 載子阻障層 26 透明導電層 27 粗糖面 28 ρ-η接合面 S31-S36 步驟

Claims (1)

1377685 十、申請專利範圍： 1. 一種太陽能電池元件結構，包含： 一基板，具一粗糙面； 一金屬層，形成於該基板之該粗糙面上； 一 P型半導體層，形成於金屬層之表面，包含銅銦鎵硒 硫、銅銦鎵硒、銅銦硫、銅銦硒或包含銅、硒或硫二者或 二者以上之化合物材料； 一η型半導體層，形成於兮
&於该Ρ型半導體層上，且與該ρ型 半導體層形成粗糖之ρ_η接合面. -透明導電層，形成於該η型二及體層上。 2.根據請求項1之太陽能電池元件結構，其中該粗縫面之粗 糙度介於0.01至100 1^間。 3 ·根據請求項1之太陽能電池 疋件結構，其中該ρ_η接合面之 粗縫度介於0.01至100 μηι間。 4.根據請求項1之太陽能電池 ^ 疋件結構，其中該基板為玻璃 基板、塑膠軟板、不銹鋼、相 屬笔片。 鋼、鈦、銘等金屬板或金 5. 6.
根據請求項4之太陽能電 喷砂或蝕刻形成。 根據請求項4之太陽能電 喷砂後進行钱刻形成。 根據請求項1之太陽能電 基板。 池元件結構，其中該粗糙面係由 t 池元件結構’其中該粗糙面係由 池疋件結構，其中該基板為金屬 8.根據請求項7之太陽能 元件結構’其中該粗趟面係由 • 13 - Μ刻或機械壓花形成。 9·根據請求項1之太陽能電池元件結構，其中該金屬層包含 鉬。 1().根據請求項丨之太陽能電池元件結構，其中該11型半導體層 包含硫化鎘、硫化鋅、硫化銦。 u·根據請求項1之太陽能電池元件結構，其中該11型半導體層 與透明導電層間另包含一載子阻障層。 12·根據請求項丨之太陽能電池元件結構，其中該透明導電層 係選自銦錫氧化物、銦鋅氧化物、叙鋅氧化物、鎵辞氧化 物、鋁鎵鋅氧化物、鎘錫氧化物、氧化鋅及二氧化錯。 13.—種太陽能電池元件結構之製造方法，包含： 提供一基板； 粗輪化該基板，於該基板形成一粗链面； 形成一金屬層於該粗輪面上； 形成一 p型半導體層於該金屬層上，該p型半導體層包 含銅銦鎵硒硫、銅銦鎵硒、銅銦硫、銅銦硒或包含銅、 碼或硫二者或二者以上之化合物材料； 形成一 η型半導體層於該p型半導體層上，其中該η型半 導體層與該ρ型半導體層形成粗糙之ρ-η接合面；以及 形成一透明導電層於該η型半導體層上。 根據請求項13之太陽能電池元件結構之製造方法，其中該 粗糙面之粗糙度介於0.01至100 μιη間。 1 5·根據請求項13之太陽能電池元件結構之製造方法，其中該 ρ-η接合面之粗糙度介於〇 〇1至1〇〇 μιη間。 1377685 16. 根據請求項13之太陽能電池元件結構之製造方法其中該 基板係玻璃基板，粗韃化該基板之步驟包含餘刻、喷砂: 17. 根據請求項16之太陽能電池元件結構之製造方法其中粗 糙化該基板之步驟係包含喷砂後钱刻。 18. 根據請求項16之太陽能電池元件結構之製造方法，其中钱 刻係利用氫氟酸。
19·根據請求項13之太陽能電池元件結構之製造方法其中該 基板係金屬基板’粗糙化該基板之步驟包含钱刻、機械壓 *务 化0 2〇·根據請求項13之太陽能電池元件結構之製造方法，其中粗 糙化該基板包含： ” 形成一第一金屬膜於該基板； 餘刻粗糙化該第一金屬膜；以及 形成該第二金屬膜於該第一金屬膜上。 21.根據請求項13之太陽能電池元件結構之製造方法，其中形 成該金屬層係利用濺鍍。 22·根據請求項13之太陽能電池元件結構之製造方法，其中形 成該p型半導體層係利用元素源共同蒸錢、金屬前驅物石西 化、化合物源蒸鍍、化學氣相沉積、封閉空間氣相傳輸、 噴霧熱解、電鍍、前驅物低溫液相沉積或粒狀前驅物黃銅 晶化。 23·根據請求項13之太陽能電池元件結構之製造方法，其中形 成透明導電層於該η型半導體層上之前另包含形成一载子 阻障層之步驟’使得該載子阻障層形成於該η型半導體層 -15· 1377685 及透明導電層之間。
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