TW200947729A - Semiconductor structure combination for thin-film solar cell and manufacture thereof - Google Patents

Semiconductor structure combination for thin-film solar cell and manufacture thereof Download PDF

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TW200947729A
TW200947729A TW097117665A TW97117665A TW200947729A TW 200947729 A TW200947729 A TW 200947729A TW 097117665 A TW097117665 A TW 097117665A TW 97117665 A TW97117665 A TW 97117665A TW 200947729 A TW200947729 A TW 200947729A
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layer
junction
deposition process
substrate
temperature
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TW097117665A
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TWI427811B (zh
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Miin-Jang Chen
Wen-Ching Hsu
Suz-Hua Ho
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Sino American Silicon Prod Inc
Miin-Jang Chen
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Priority to US12/465,087 priority patent/US20090283139A1/en
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
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    • 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 at least one potential-jump barrier or surface barrier
    • 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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
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    • 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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PIN type
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    • 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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PIN type
    • H01L31/076—Multiple junction or tandem solar cells
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Description

200947729 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種半導體結構組合及其製造方法，特別 是關於一種供一薄臈型太陽能電池用之半導體結構組合。 【先前技術】 太電池因為其將發自一光源(例如，太陽光)的能量 轉換成電力以供電給例如，計算機、電腦、加熱器…，等電 子裝置，所以太陽能電池已被廣泛地使用。 太％冑b電池的原理係光子進入石夕基材並且由該石夕基材吸 收^以轉移光子的能量給原為鍵結狀態（共價鍵)的電子，並 且藉此釋放原為鍵結狀態的電子成游離的電子。此種可移動 的電子，以及其所遺留下原在共價鍵處的電洞(此種電洞也是 可移動的），可以造成電流從該太陽能電池流出。為了貢獻該 電流，上述的電子以及電洞不可以重新結合，反而是由與矽 基材内p_n接合處之電場所分離。 ^ 眾所周知，於太陽能電池上形成表面鈍化層可以使由光 產生的載子(即電子與電洞)在表面發生結合的機率減低。 目莉太1¼電池係以砍為主要材料，並且依據發原子不同 的結晶方式，太陽電池可區分成單晶矽太陽電池、多晶矽太 陽電池及非晶矽(即薄膜型)太陽電池。 一般來說’非晶矽是以電漿式化學氣相沈積法(phsma enhanced chemical vapor deposition，PECVD)，在玻璃等基板 上成長厚度約1微米（#m)左右的非晶矽薄膜。因為非晶$對 光的吸收性比單晶矽來的高，所以對非晶矽而言只需要薄薄 6 200947729 就可以把光子的能量有效的吸收。非晶 基板，改採^格較 反3%3得製作大面積的鳩電池成為可能。相 也、、、口曰曰矽太IW能電池的面積則受限於矽晶圓的尺寸 能電、、im非轉太陽㈣絲說’同#需要於太陽 低。因此’ίΐ面鈍化層以使載子的在表面結合的機率減 能電=之iir之主要㈣在於提供—種供—薄膜型太陽 月匕電池用之+導體結構組合，以解決上述問題。 【發明内容】
健—細社陽能電池用 根據本發明之一具體實施例，該半導體結構組合包含一 基板(substrate)、—多層結構以及一純化層❻咖㈣⑽丨_)。 該基板具有一上表面。該多層結構係形成於該基板之該 上表面上。該多層結構包含一 p_n接面、一 p_i_n接面、一 n_ 1-P接面、一雙接面扣ndem junction)或一多重接面(聰出_ junction)。該鈍化層係藉由一原子層沈積製程及/或一電漿增 強原子層沈積製程(或一電漿辅助原子層沈積製程)形成於^ 多層結構之—最頂層(top-most layer)上。 根據本發明之另一具體實施例為一種製造供一薄膜型太 1%月電池用之半導體結構組合之方法。 該方法首先製備一基板，該基板具有一上表面。接著， 該方法形成一多層結構於該基板之該上表面上。該多層結構 包含一 p-n接面、一 p_i_n接面、一 n_i_p接面、一雙接面或 7 200947729 一多重接面。之後，藉由一原子層沈積製程及/或一電漿增強 原子層沈積製程(或一電漿輔助原子層沈積製程）’該方法形 成一鈍化層於該多層結構之一最頂層上。 相較於先前技術，根據本發明之適用於製造薄膜型太陽 能電池之半導體結構組合，藉由原子層沈積製程，以優異的 均勻度及三維包覆度，在矽薄膜上沉積形成高品質的表面鈍 化層，以消除空懸鍵(dangling bond)的影響。特別地，針對具 有微晶結構的石夕薄膜，更能夠藉由原子層沈積製程優異的三 維包覆度’深入砍薄膜底層的微晶結構的晶界扭血b〇undary) 之間形成純化層，藉此充份發揮純化層的功能。 關於本發明之優點與精神可以藉由以下的發明詳述及所 附圖式得到進一步的瞭解。 【實施方式】 請參閱圖一，圖一係繪示根據本發明之半導體結構組合 1之截面視圖。該半導體結構組合1可以供一薄膜型太陽能 電池之用，但不以此為限。 如圖一所示’該半導體結構組合1包含一基板1〇、一多 層結構12以及一鈍化層14。於實際應用中，該基板1〇可以 是一具有透光性質且不具導電性之基板1〇。舉例而言，該基 板10可以是一玻璃基板10，但不以此為限。該基板10具有 一上表面100。該多層結構12係形成於該基板1〇之該上表 面100之上。 於實際應用中，該多層結構12可以包含一 p_i_n接面(i 指的是沒有η型或p型掺雜之本質矽(intrinsic smc〇n))、一 n_ i-p接面、一雙接面(tandem junction)或一多重接面(multi· junction)。該鈍化層14可以形成於該多層結構12之一最頂 200947729 層上。 於實際應财，魏化層μ可崎由U層沈積製程 及/或-電強原子層沈積製程(或-電漿辅助原子層沈積製 程)形成於該多層結構12之該最頂層上。 清參晒—。係娜該編⑽丨4之纟域及其反應原 料(precursor)之對照表。如圖二所示，於實際應用中，該鈍化 層 14 可以是 Al2〇3、AIN、Hf02、Hf3N4、Si3N4、Si02、 Ta205、Ti02、TiN、ZnO、Zr02、Zr3N4 或其他類似化合物， ❹ 或為上述化合物之混合物(mixture)，但不以此為限。 於厂具體實施例中，若該鈍化層14係Al2〇3薄膜，該 Al2〇1薄膜的反應原料可以採用一 Trimethyiaiumin· (A1(CH1)1, TMA)先驅物(precursor)與一 h2〇先驅物所形成， 其中TMA即為A1的來源，H2〇為〇的來源。 以沈積Al2〇1鈍化層14為例，在一個原子層沈積的週期 内的反應步驟可分成四個部分： 1. 利用載送氣體將EtO分子導入反應腔體，h2〇分子在 進入腔體後會吸附於基材表面，在基材表面形成單一層〇H 基’其曝氣時間為0.1秒。 2. 通入載送氣體將多餘未吸附於基材的H20分子抽走， 其吹氣時間為5秒。 9 1 利用載送氣體將TMA分子導入反應腔體中，與原本吸 附在基材表面的單一層0H基，在基材上反應形成單一層的 A12〇3 ’副產物為有機分子，其曝氣時間為0.1秒。 4. 通入載送氣體，帶走多餘的TMA分子以及反應產生的 200947729 5秒 有機分子副產物，其吹氣時間為 ΐί，，可以採用高純度的氬氣或氮氣。 以上四個 期層=的週期可 锱盔w / 風長早—原子層厚度的薄膜 利用
，結來說，本發騎_的原子層沈積製減有以下優 .、'、.⑴可在原子等級控制材料的形成；（2)可更精準地控制薄 巧厚度；⑺可大面積量產；⑷有優異的均句度 (umfonmty) ; (5)有優異的三維包覆性(c〇nf〇rm卿）；⑹無孔 洞結構，⑺缺陷密度小；以及⑻沈積溫度較低…，等製程優 點0
該純化層14之形成可以於一溫度範圍介於室溫至6〇〇。〇 之製程溫度下執行。於該鈍化層14形成後，該純化層14可 以進一步於一退火溫度介於3〇〇°c至12〇〇°C之退火溫度下執 行退火以提昇該鈍化層14之品質。於實際應用中，該鈍化層 14可以具有範圍介於lnm〜ΙΟΟηιη之一厚度。 為充分表示本發明之構想’以下將列舉三個具體實施例 來說明。請參閱圖三。圖三係緣示根據本發明之第一具體實 施例之薄膜型太陽能電池2之示意圖。圖三中之太陽能電池 2為一種n-i-p單接面(single-junction)之薄膜型太陽能電池。 如圖三所示，太陽能電池2包含基板(substrate)20、金屬 層22、透明導電層24、n-i-p非晶矽結構層26、鈍化層28以 及透明導電層29，分別依圖三中之順序形成。需注意的是， 200947729 在n-i-p非晶矽層結構26沉積之後，鈍化層％可以藉由原 層沈積製程形成於n-i-p非晶矽結構層26上。 、 *請參閲圖四。圖四係繪示根據本發明之第二具體實施 ^薄膜型太陽能電池3之示意圖。圖三中之太陽能電池 為一種p-i-n單接面之薄膜型太陽能電池。 示.，，能電池3包含基板(哪贈_0、透 f導電層32、ρ+η非晶矽結構層34、鈍化層％、 ❹ ❹ ΐ 38/X及金屬層39，分別依圖四中之順序形成。需注意^ =，在p-i-n非晶矽結構層34沉積之後，鈍化層％可▲ 原子層沈積製程形成於p_i_n非晶雜構層34上 ^ 太陽能電池3_置使用，卿人射光由基板3()射入務， 請參閱圖五。圖五係$會示根據本發明 之缚膜型太陽能電池4之示意圖。圖五中之太陽能 一種双接面型之薄膜型太陽能電池(tandemeell) 為 如圖五所示，太陽能電池4包含透導 42 . ^ 44 ；〇 ； 層48，分別依圖五中之順序形成。需注意的是，及金， 晶矽/微晶秒結構層42沉積之後，鈍化層44可Ρ ^非 沈積製程形成於p_i_n非晶石夕/微晶石夕結構層42上。β原子層 發非社稍财的具體ΐ 楚描:ίί明；=實係希望能更加清 _六Α至圖六C並配合參閱圖— C係繪不用以描述根據本發明之製 |圖六 方法之截面視圖。 衣4 +导體'、、《構組合i之 11 200947729 首先’如圖六Α所示’該方法製備一基板10，該基板 10具有一上表面1〇〇。 接著，如圖六Β所示，該方法形成一多層結構12於該 基板10之該上表面1〇〇上。該多層結構12包含一 ρ_η接 面、一 p-i-n接面、一 n-i-p接面、一雙接面或一多重接面。 之後，如圖六C所示，藉由一原子層沈積製程及/或一電 漿增強原子層沈積製程(或一電漿輔助原子層沈積製程），該 方法形成一鈍化層14於該多層結構12之一最頂層上。
於實際應用中，該鈍化層14可以是a12〇3、A1N、 励2、Hf3N4、Si3N4、Si02、Ta205、Ti〇2、TiN、Zn0、
Zr〇2、ZrsN4或其他類似化合物，或為上述化合物之混合物， 但不以此為限。此外，該鈍化層14可以具有範圍介於lnm〜 100nm之一厚度。 相較於先4技術，根據本發明之適用於製造薄膜型太陽 能電池之f導縣構組合，藉由原子層沈積製程，以優異的 均勻度及=維包覆度，树細上沉積形成高品質的表面鈍 以雜空騎的影響。_地，針對具有微晶結構的 石夕薄膜，更能_由原子層沈積製程優異的三維包覆度，深 入石夕薄膜底層的微晶結構的晶界(抑匕bounds)之間开)成純 化層，藉此充份發揮鈍化層的功能。 藉由以上較佳具體實施例之詳述，係希 施1列ί對本發明之範傳加以限制。相反地，其二 涵盍各種改敎具鱗性峡·本發 。因此’本發明所申請之專利範圍以= 據上述的制作最寬廣的轉，讀使其涵蓋所有可 200947729 變以及具相等性的安排。
13 200947729 【圖式簡單說明】
能電犯&不恩園。 〇 能電池之示意圖。 圖四係緣示根據本發明之第二 具體實施例之薄膜型太陽 圖五係繪示根據本發明之第三 能電池之示意圖。 二具體實施例之薄膜型太陽 圖六A至圖六C係繪示用以描述根據本發明之另一具體 實施例之製造一半導體結構、纟且合之方法之截面視圖。 【主要元件符號說明】 10 :基板 14 :鈍化層 1:半導體結構組合 U :多層結構 2、3、4 :太陽能電池 20、30 :基板 24、29、32、38、40、46:透明導電層 22、39、48:金屬層 26 : n-i-p非晶矽層結構 34 : p-i-n非晶矽結構層 42 : p-i-n非晶石夕/微晶;δ夕結構層 14 200947729 28、36、44 :純化層 100 :上表面
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Claims (1)

  1. 200947729 十、申請專利範圍： 1、 一種供一薄膜型太陽能電池用之半導體結構組合，該半導體 結構組合包含： —基板’該基板具有一上表面； 一多層結構，該多層結構係形成於該基板之該上表面 上，該多層結構包含由一P-η接面、一p-i-n接面、—n_i_ p接面、一雙接面及一多重接面所組成之一群組中之其 一；以及 —鈍化層，該鈍化層係藉由一原子層沈積製程及/或一電 漿增強原子層沈積製程(或一電槳輔助原子層沈積製程) 形成於該多層結構之一最頂層上。 2、 如申請專利範圍第1項所述之半導體結構組合，其中該純化 層係由選自由 Al2〇3、AIN、Hf02、Hf3N4、Si3N4、si02、 Α〇5、Ti〇2、TiN、ZnO、Zr〇2及ZqN4所組成之一群組中之 其一所製成。 3、 如申請專利範圍第2項所述之半導體結構組合，其中該純化 層之形成係於一溫度範圍介於室溫至6〇〇t之製程溫度下執 行。 、如申請專利範圍第3項所述之半導體結構組合，其中該鈍化 層於形成後，係進一步於一溫度介於3〇〇。(：至12〇〇。(：之退火 16 200947729 溫度下執行退火。 5、 如申凊專利範圍第1項所述之半導體結構組合，其中梦純化 層具有範圍介於lnm〜l〇〇nm之一厚度。 6、 一種製造供一薄膜型太陽能電池用之半導體結構組合之 法’該方法包含下列步驟： 方 製備一基板，該基板具有一上表面；
    形成多層結構於該基板之該上表面上，該多層结構勺 含由一P-n接面、一P-i-n接面、一n-i-p接面、—雙接^ 及一多重接面所組成之一群組中之其一；以及 藉由一原子層沈積製程及/或一電漿增強原子層沈積製。 (或-電聚辅助原子層沈積製程），形成一純化 ， 層結構之一最頂層上。 θ、以夕 7、 如申請專利範圍第6項所述之方法，其中該鈍化層係由 由 Al2〇3、AIN、Hf02、Hf3N4、Si3N4、Si〇2、Ta2〇5、Ti$、 TiN ZnO、Zr〇2及Zi^N4所組成之一群組中之其—所製成。 8、 如申請專利範圍第7項所述之方法，其中該純化層之形成係 於-溫度範於室溫至之製程溫度下執行。 ' 9、 如申請專利範圍第8項所述之方法，其中該鈍化層於形成 後，係進一步於一退火溫度介於3⑻。[至12〇〇。〇之溫度下執 行退火。 17 200947729 10、如申請專利範圍第6項所述之方法，其中該純化層具有範圍 介於lnm〜100nm之一厚度。
    18
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