TW201405857A - 使用雷射照射製造一光伏打元件之方法 - Google Patents
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- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
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- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 230000035515 penetration Effects 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 description 14
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 14
- 238000000137 annealing Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 description 4
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
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- 238000002835 absorbance Methods 0.000 description 1
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Abstract
本發明係關於一種用於製造一光伏打元件之方法,其包括:a.製造一光伏打層堆疊,b.在雷射照射之前在該光伏打層堆疊之表面區域上提供一囊封層,c.選擇一雷射照射參數集合,d.使用該雷射照射參數集合同時照射該囊封層及該光伏打層堆疊,其特徵在於該囊封層係非犧牲性的且該照射參數集合包含在0.01 J/cm2與10 J/cm2之間的一光束能量密度。
Description
本發明係關於一種用於使用雷射照射製造一光伏打元件之方法。
在光伏打電池製造中,結晶矽、非晶矽、多晶矽等之熱退火通常用於獲得再結晶、摻雜劑活化、缺陷修復等。
在當前最佳技術光伏打元件製造中,越來越多地藉由雷射照射執行熱退火。藉由啟用一極快速熱處理及經加熱區域之淺深度,此技術提供優於標準較長持續時間迅速熱處理(RTP)或爐製程(其中並不總是易於避免至一非所要深度之熱擴散或一光伏打層堆疊中之損壞)之顯著優點。
然而,為維持經照射區域之尺寸穩定性、表面紋理及平坦性,在雷射照射之前在光伏打層堆疊之頂部上沈積一囊封層(通常亦稱作封蓋層)。US4751193中給出一實例,其中在非晶層或多晶矽層上方提供一保護性氮化矽層以在其被熔化之後及在再結晶期間維持該非晶層或多晶矽層之形狀。
以上方法之一大體缺點係此囊封層係犧牲性的:其唯一目的係在雷射照射期間保護光伏打層堆疊並在其被再次移除後旋即影響跨越該堆疊之溫度梯度,此導致額外製程步驟、材料之浪費及較高光伏打
元件成本。
考量以上缺陷,本發明之一第一目標係提供一種用於製造一光伏打元件之方法,其中不需要為獲得滿意熱退火結果而在熱退火步驟中引入額外製程步驟。
本發明之另一目標係提供一種其中可在不利用一額外犧牲層之情況下將一光伏打層堆疊曝露於一所要深入溫度量變曲線之方法。
本發明之一第二目標係提供一種用於製造一光伏打元件之方法,該光伏打元件使得光伏打層堆疊能夠曝露於特定雷射照射條件以控制彼等不同深度處之缺陷退火、材料再結晶、材料合金化或摻雜劑活化之位準。
作為另一目標,本發明提供一種具有工程設計光伏打層堆疊之電性質及達成跨越該層堆疊之一或多個層之電性質之任一受控深入梯度之能力之方法。
本發明之又一目標係提供一種可藉助於標準雷射退火裝置應用之方法,該標準雷射退火裝置最佳化PV線中之全球製造成本且因此在一$/瓦特峰值基礎上最佳化光伏打元件生產成本。
本發明之另一目標係提供具有經改良效率之光伏打元件。
本發明藉由提供一種用於製造一光伏打元件之方法而滿足以上目標,其中使用雷射照射且其中雷射照射參數包含在0.01 J/cm2與10 J/cm2之間的一光束能量密度以使得非犧牲層(亦即,存在於最終光伏打元件中之層)可用作囊封層。
本發明係關於一種用於製造一光伏打元件之方法,其包括:a. 製造一光伏打層堆疊,b. 在雷射照射之前在該光伏打層堆疊之表面區域上提供一囊封層,
c. 選擇一雷射照射參數集合,d. 使用該雷射照射參數集合同時照射該囊封層及該光伏打層堆疊,其特徵在於該囊封層係一非犧牲層且該照射參數集合包含在0.01 J/cm2與10 J/cm2之間的一光束能量密度。
在本發明之上下文中,一光伏打層堆疊應理解為由至少2個不同層(其中之一者視情況係一基板)建立之任何種類之堆疊,因此光伏打層堆疊可係一基板上之一個或複數個層。
在本發明之上下文中,一囊封層係將被雷射照射之一層之頂部上之一材料層,與不具有囊封層之照射相比,該囊封層經提供以改良雷射照射對下伏層之效應或結果。
根據本發明之一第一實施例,提供一種用於製造一光伏打元件之方法,其包括:a. 製造一光伏打層堆疊,b. 在雷射照射之前在該光伏打層堆疊之表面區域上提供一囊封層,c. 選擇一雷射照射參數集合,d. 使用該雷射照射參數集合同時照射該囊封層及該光伏打層堆疊,其特徵在於該囊封層係一非犧牲層且該照射參數集合包含在0.01 J/cm2與10 J/cm2之間的一光束能量密度。
藉由選擇適當雷射照射參數且提供一適當囊封層,該囊封層可係一非犧牲層,該非犧牲層在本發明之上下文中係全部、部分地維持
於最終光伏打元件中或者被圖案化、在雷射照射後未被改質或旋即被改質(部分或完全地)之一層,且其對最終光伏打元件效能係有益的。或換言之,藉由選擇適當雷射照射參數,作為一全部、部分或經圖案化層維持於最終光伏打元件中之一層(其可在雷射照射後未被改質或旋即被改質(部分或完全地)且其對最終光伏打元件效能係有益的)可用作囊封層以改良雷射照射對下伏層之效應或結果。
其一大體優點係不需要為獲得滿意熱退火結果而在光伏打元件製造中將額外製程步驟引入至熱退火步驟,從而產生較低光伏打元件成本。
另一優點係可在不利用一額外犧牲層之情況下將一光伏打層堆疊曝露於一所要深入溫度量變曲線。
為選擇一適當雷射照射參數集合,可判定將跨越光伏打層堆疊獲得之一目標深入溫度量變曲線。可將光束能量密度及/或脈衝長度以及甚至波長選擇為將跨過光伏打層堆疊獲得之目標深入溫度量變曲線之一函數。
可基於將在光伏打層堆疊中獲得之所要材料性質(諸如結晶度、摻雜劑活化或具有一給定厚度之金屬合金化、化學計量(或組合物)及結晶相(或結晶定向))判定將跨越該堆疊獲得之目標深入溫度量變曲線。。
選擇一適當雷射照射參數集合可進一步包括:計及非犧牲囊封層及/或光伏打層堆疊之吸收率及反射率。
另外,在選擇雷射照射參數集合及考量一給定層堆疊結構時,可預測光伏打層堆疊中之雷射照射之深入照射能量傳播及/或穿透深度。
在根據本發明之一實施例中,與光伏打層堆疊之表面區域相比,非犧牲囊封層可對雷射照射係至少部分抗反射的,或與光伏打層
堆疊之表面區域相比,可對雷射照射係更至少部分反射的。非犧牲囊封層之反射率將影響光伏打層堆疊曝露於其之深入溫度梯度。
在另一實施例中,舉例而言,在其中由於在封蓋有非犧牲囊封層之光伏打雷射堆疊中獲得之一較低熱預算而最小化熱損失之情形中,可在雷射照射期間將該囊封層與光伏打層堆疊熱絕緣,從而針對相同雷射能量產生較高裝置產量。
在又一實施例中,囊封層可係與存在於光伏打層堆疊中之經圖案化下伏層組合或不組合之一經圖案化層,此產生局部不同之深入溫度量變曲線以便在曝露於相同雷射能量後旋即達成局部不同之材料性質。
在又一實施例中,非犧牲囊封層可防止光伏打層堆疊之表面區域之污染。更具體而言,在熱退火期間,非犧牲層可係抵抗存在於周圍大氣中之污染之一化學障壁。
在又一實施例中,非犧牲囊封層可防止自光伏打層堆疊向外擴散。更具體而言,非犧牲層可係在雷射照射期間抵抗特定化學組份(諸如存在於層堆疊中之揮發性組份)之向外擴散之一化學障壁,從而保存材料完整性及光伏打元件效能。
非犧牲囊封層可包括適合於供在光伏打元件中使用及適合於在雷射照射期間囊封一光伏打層之任何材料。較佳地,囊封層可係一金屬層、一金屬氧化物層、一金屬硫化物層、一介電層、一經摻雜或未經摻雜半導體層或其一組合。
在一最終光伏打元件中,非犧牲囊封層可具有任何功能,舉例而言,抗反射塗層(ARC)、鈍化層、透明導電氧化物(TCO)、p型或n型半導體接面層、觸點或一觸點之部分或者其一組合。
在根據本發明之一實施例中,提供一種包括將囊封層與下方之光伏打層堆疊之表面區域之間的界面改質之方法。舉例而言,在囊封
層係一金屬且光伏打層堆疊之表面區域係矽之情形中,可在界面處形成金屬矽化物。
在其他實施例中,可將囊封層及光伏打層堆疊(其一個或複數個層)同時在深度上改質。
為影響跨過光伏打層堆疊之深入溫度梯度,可將非犧牲囊封層之厚度調整為所要深入溫度梯度之一函數。
在本發明之上下文中,雷射源可係其波長、能量及脈衝持續時間適於製程之任何雷射源,諸如固態雷射、二極體雷射或準分子雷射。較佳地,雷射源可係一準分子層,更較佳地係一種氯化氙準分子雷射。
雷射源之波長可由於矽在彼等波長處之高能量吸收而在介於100 nm至900 nm、190 nm至600 nm、190 nm至550 nm或較佳地190 nm至480 nm之範圍中。
照射能量可在介於1焦耳至25焦耳之範圍中。為達成此等能量,通常將雷射放電量最佳化為10 cm(電極間間距)×7 cm至10 cm(放電寬度)×100 cm至200 cm(放電長度)。
在本發明之一實施例中,雷射源可經調適以產生具有在0.01 J/cm2與10 J/cm2之間、較佳地在0.01 J/cm2與5 J/cm2之間、最佳地在0.01焦耳/cm2至1焦耳/cm2之間的一光束能量密度之一照射光束。雷射能量密度可經調適以匹配光伏打層堆疊中之所要溫度梯度。
在一較佳實施例中,雷射可係經調適以產生多於60 cm2、多於80 cm2、較佳地為100 cm2之一大面積輸出光束之一準分子雷射,該大面積輸出光束具有通常為至少1 cm2、至少5 cm2及高達100 cm2之一經投射光束點,該經投射光束點具有在0.01 J/cm2與10 J/cm2之間的一能量密度。
在根據本發明之一特定實施例中,對於每一脈衝,至少1 cm2、
至少5 cm2、至少10 cm2或至少100 cm2之一部分可被照射,此使本發明適合於以高產量工業製造光伏打電池。
另一選擇係,雷射照射可包括用具有等於或(稍微)超過所使用之基板或最終光伏打元件面積之一個尺寸之一線長度的一線光束掃描非犧牲囊封層,此使本發明尤其適合於以高產量工業製造薄膜光伏打電池。舉例而言,藉由使一大基板以一掃描速度(數毫米/秒)沿垂直於線光束之一方向連續流動,連貫脈衝式雷射發射將啟用整個區之連續退火。
照射光束可係連續的或脈衝式的,其較佳地具有在介於100 ns至1000 ns之範圍中或在100 ns與300 ns之間或者較佳地在100奈秒與200奈秒之間的一脈衝持續時間。
在本發明之一較佳實施例中,雷射源可係具有308 nm之一波長、在100奈秒與200奈秒之間的一脈衝持續時間及在0.01 J/cm2與1 J/cm2之間的一經投射照射光束能量密度之一準分子雷射。
光伏打層堆疊可包括適合於光伏打應用之任何材料,諸如但不限於結晶矽、未經摻雜之矽或經摻雜矽、多晶矽、經植入矽、非晶矽、矽鍺、III-V化合物半導體(諸如砷化鎵、砷化鎵鋁、氮化鎵及諸如此類,二硒化銅銦(CuInSe2)或二硒化銅銦鎵(Cu(In,Ga)Se2)、CZTS(Cu2ZnSnS4)及諸如此類,碲化鎘(CdTe)及諸如此類)或在任何有機光伏打元件或染料敏化太陽能電池元件中發現之層。
使用一薄金屬非犧牲囊封層及雷射照射透過在充分活性矽上形成一金屬矽化物層來使得一經改良金屬接觸方案能夠實現。所得光伏打元件展示經改良效能:使用在0.55 J/cm2下之雷射退火對迅速熱退火(RTA)之+0.6%絕對效率。
透過一Al2O3囊封層(在最終PV元件中充當一電鈍化層)將PV元件之背側處之矽層再結晶以便將矽中之摻雜劑活化且局部形成某種所要背表面場效應。
使用5 nm Al2O3囊封層,下伏矽開始在1.9 J/cm2下熔化。在2 J/cm2下之熔化深度係0.17 μm。
使用30 nm Al2O3囊封層,下伏矽開始在0.8 J/cm2下熔化。在2 J/cm2下之經熔化深度係1.8 μm。
在不使用任何Al2O3囊封層之情況下,在0.035 μm處計算c-Si在2 J/cm2下之經熔化深度。
針對塗佈有5 nm Al2O3之c-Si對裸c-Si觀察稍微較大熔化時間,但
針對塗佈有30 nm Al2O3之c-Si量測3倍大熔化時間。
透過一CdS囊封層(緩衝層)或透過一TCO/CdS堆疊將一CIGS層退火以便改良CdS/CIGS界面及PV元件效能。該情形亦適用於TCO/CdS界面之改良。因此,改良了CdS囊封層1與CIGS層2之間的界面且亦改良了CdS緩衝區之結晶度。此外,在雷射退火期間,CdS囊封層充當抵抗Se向外擴散之障壁層。
透過一TCO層將一非晶層退火且藉由減少接觸電阻改良TCO/a-Si界面。此外,非晶矽可在與TCO之界面處部分地結晶同時在與塊體矽之界面處維持其非晶性質。因此,減少了光吸收及電損失,從而促成太陽能電池效能之一大體改良。
Claims (12)
- 一種用於製造一光伏打元件之方法,其包括:a. 製造一光伏打層堆疊,b. 在雷射照射之前在該光伏打層堆疊之表面區域上提供一囊封層,c. 選擇一雷射照射參數集合,d. 使用該雷射照射參數集合同時照射該囊封層及該光伏打層堆疊,其特徵在於該囊封層係一非犧牲層且該照射參數集合包含在0.01 J/cm2與10 J/cm2之間的一光束能量密度。
- 如請求項1之方法,其中判定將跨過該光伏打層堆疊獲得之一目標深入溫度量變曲線。
- 如請求項1或2之方法,其中與該光伏打層堆疊之該表面區域相比,該囊封層對該雷射照射係至少部分抗反射的。
- 如請求項1或2之方法,其中與該光伏打層堆疊之該表面區域相比,該囊封層對該雷射照射係至少部分反射的。
- 如請求項1或2之方法,其中該囊封層與該光伏打層堆疊熱絕緣。
- 如請求項1或2之方法,其中該囊封層係與存在於該光伏打層堆疊中之經圖案化下伏層組合或不組合之一經圖案化層。
- 如請求項1或2之方法,其中該囊封層包括一金屬層、一金屬氧化物層、一金屬硫化物層、一介電層、一經摻雜或未經摻雜半導體層或其一組合。
- 如請求項1或2之方法,其中該囊封層係一抗反射塗層、一鈍化層、一透明導電氧化物、p型或n型半導體接面層、一觸點或一 觸點之部分或者其一組合。
- 如請求項1或2之方法,其包括將該囊封層與該光伏打層堆疊之該表面區域之界面改質。
- 如請求項1或2之方法,其包括將該囊封層及該光伏打層堆疊同時改質。
- 如請求項1或2之方法,其中基於該光伏打層堆疊中之深入照射能量傳播及/或穿透深度而選擇該雷射照射參數集合。
- 如請求項1或2之方法,其使用一準分子雷射照射源。
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