TW201140659A - Composition for forming p-type diffusion layer, method for forming p-type diffusion layer, and method for producing photovoltaic cell - Google Patents
Composition for forming p-type diffusion layer, method for forming p-type diffusion layer, and method for producing photovoltaic cell Download PDFInfo
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- TW201140659A TW201140659A TW100102723A TW100102723A TW201140659A TW 201140659 A TW201140659 A TW 201140659A TW 100102723 A TW100102723 A TW 100102723A TW 100102723 A TW100102723 A TW 100102723A TW 201140659 A TW201140659 A TW 201140659A
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- Prior art keywords
- diffusion layer
- type diffusion
- glycol
- ether
- composition
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Description
201140659 37019pif 六、發明說明: 【發明所屬之技術領域】 本發明涉及一種用於形成光伏電池(photovoltaic cell) 的P型擴散層(p-type diffusion layer)的組合物,一種p 型擴散層的製造方法,和一種光伏電池的製造方法。更具 體地,本發明涉及一種用於形成卩型擴散層的技術,其能 夠減小用作半導體基板的石夕的内應力,從而可以抑制對晶 粒界(crystal grain boundary)的損害,並且可以抑制晶體 缺陷(crystal defects)的增加和抑制翹曲。 【先前技術】 以下描述矽光伏電池的習知製程。 一首為了通過促進光學侷限效應(confinement effec 來貝現南效率,製備其上形成有紋理結構的 型矽基板,並且隨後將該P型矽基板在三氯氧化巧 (P〇Cl3)、氮氣和氧氣的混合氣體氣氛下,在800至900。< 的溫度進行處顆十分鐘,從㈣勻形成η型擴散層。 據此習知技術方法,由於翻擴散使肢合氣體進行,g 此η里擴政層不僅形成在該表面上,而且形成在其側面矛 後表面上。由於這些原因,需要側侧(side etching) % 知來移除在側面上的n型擴散層。此外,需要將後表面^ η里擴政層轉d成p+型擴散層,因此,將紹膏印刷到後名 面的:擴政層上’然後燒結,以實現η型擴散層至p+座 擴散詹畴變朗時獲得歐姆觸接觸。 然而’料具有低的電導率’因此通常必須在燒結以 4 201140659 37019pif 後在整個後表面上形成約10至2〇μιη的厚鋁層,以減j 電阻(sheet resistance)。此外,鋁的熱膨脹係數與矽 膨脹係數顯著不同,因此這種差別導致在燒結和冷卻尚^、、 中在石夕基板中產生大的内應力,這促進了對晶粒界= 害,晶體缺陷的增加,以及趣曲。 貝 為了解決此問題,存在通過減少要塗布的膏狀組合 的量來降低後表面電極的厚度的方法。然而,當減少&狀 組合物的塗布量時,從P型矽基板的表面擴散到内部;分 的鋁的量不足。結果,沒有得到期望的BSF(背面電場 surface Field))效應(其中產生的載子(carrie〇的收集 (collection efficiency)歸因於p+型層的存在而增大^效 應),從而導致光伏電池性質降低的問題。 由於這些原因’例如,已經提出了—種包含鋁粉末、 有機媒劑(organic vehicle)和無機化合物粉末的膏狀組人 物’所述無機化合物粉末的熱膨脹係數低於鋁的熱膨脹^ 數’並且其熔融溫度、軟化溫度和分解溫度中的至少一項 低於鋁的熔融溫度(例如,參見日本專利公開(Jp_A) 2003-223813)。 【發明内容】 [本發明要解決的問題] 然而,存在著即使使用了記載於特開2003-223813號 公報的膏狀組成物亦無法充分地抑制趣曲的情況。 本發明是考慮到由背景技術提出的以上問題而進行 的,並且本發明的目的是提供一種形成p型擴散層的組合 201140659 37019pif 物’ P型擴散層的製造方法,以及一種光伏電池的製造方 法,其中該組合物在使用矽基板製備光伏電池的製程中能 夠形成P型擴散層,而不引起矽基板中的内應力和基板的 勉曲。 [用於解決問題的手段] 上述問題通過下列手段解決。 一種形成P型擴散層的組合物,所述組合物含有 含受體元素(acceptor element)的玻璃粉末和分散介質。 <2>如<1>所述的形成p型擴散層的組合物,其中所 述受體元素是選自硼(B)、鋁(A1)或鎵(Ga)中的至少一種受 體元素。 <3>如<1>或<2>所述的形成p型擴散層的組合物,其 中所述含受體元素的玻璃粉末含有選自B2〇3、Al2〇3、及 Ga2〇3中的至少一種含受體元素的材料,以及選自&〇2、 K20、Na20、Li20、BaO、SrO、CaO、Mg〇、BeO、ZnO、
PbO ' CdO ' V2〇5、SnO、Zr02 及 Mo03 中的至少一種玻璃 成份材料。 <4> 一種p型擴散層的製造方法,所述方法包括: 在半導體基板上塗佈如前述<1;>至<3>中任一項所述 的形成P型擴散層的組合物的步驟;以及 進行熱擴散處理的步驟。 <5> —種光伏電池的製造方法,其中該光伏電池的製 造方法包括: 在半導體基板上塗佈如前述至<3〉中任一項所述 6 201140659 37019pif 的形成P型擴散層的組合物的步驟;以及 進行熱擴散處理以形成p型擴散層的步驟;以及 在所形成之p型擴散層上形成電極的步驟。 [發明效果] 本發明使得在使用石夕基板製備光伏電池的製程中能 夠形成p型擴散層,而不引起矽基板中的内應力和基板的 勉曲。 為讓本發明之上述特徵和優點能更明顯易懂,下文特 舉實施例,並配合所附圖式作詳細說明如下。 【實施方式】 百无 刑·?田地很像本發明的形成p型擴散層的組合 物,然後將描述使用所述形成p型擴散層的組合物的㈣ 擴散層的製造方法和光伏電池的製造方法。 在本說明書中「步驟(P聰SS)」的用語不僅包含獨 ’亦包含在無法與其他步驛區別的情況下,若該 步驟能達賴翻_帛,㈣純含於本畴巾。此外, 所表示的數值範圍代表包含被記載於 〜代表最小值與最大值的數值的範圍。 一根據本發明的形成p型擴散層的組合物至少包含含典 體兀素的玻璃粉末(以下,通f簡稱 1 介質’並且考慮到可塗布性等放 添加劑。 寻雌需要柯时有其他 如本文中所使用的“形成P型擴散層的組合物,,是指 這樣的一種材料:該材料含有含㈣元素的 7 201140659 J/uiypif ^^將該材料塗佈_基板上以後通過受體 的使用確保二= 接觸的步驟分開,從而拓展了對用於形成: 具有薄的膜厚度和低電阻的電,::電;;’可以得到 面卜心Ί 的電極匕外,不需要在整個表 =電因此可以部分地形成電極,例如梳狀電極。 、述,藉由形成薄的電極或如梳狀電極的部分電極, :私ί抑制矽基板中的内應力和基板翹曲的同時形成Ρ型 擴散灣。 因此’ §使用根據本發明的形成ρ型擴散層的組合物 時’抑制了在常規廣泛使用的方法中出現㈣基板中的内 應力和基板翹曲,所述常規廣泛使用的方法即為這樣的方 法:其中將銘膏塗佈到η型擴散層上,然後燒結以將η型 擴散層轉變成Ρ+型擴散層,同時還形成歐姆接觸。 再者,由於玻璃粉末中的受體成分在燒結中亦難以昇 華(sublimation) ’可抑制ρ型擴散層因昇華氣體的產生 而形成於期望的區域以外。下面將更詳細地描述根據本發 明的含受體元素的玻璃粉末。 如在本文中使用的“受體元素”是指能夠通過將其在 矽基板上掺雜而形成Ρ型擴散層的元素。作為受體元素, 可以使用週期表的帛xni族元素。受ϋ元素的實例包括 Β(删)、鋁(Α1)和鎵(Ga)。 201140659 37019pif 用於將受體元素引入到玻璃粉末中的含受體元素的 材料的實例包括B2〇3,Al2〇3和Ga203。優選使用選自 B2O3 ’ Al2〇3和Ga2〇3中的至少一種。 此外,必要時,可以通過調節組分比來控制含受體元 素的玻璃粉末的熔融溫度,軟化點,玻璃化點,化學耐久 性等。此外,優選含有以下所述玻璃組分物質(constituent matter) 〇 玻璃組分物質的實例包括Si〇2、K20、Na20、Li20、
BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、、V205、 SnO、Zr02、W03、Mo03、MnO、La203、Nb205、Ta205、 Y2O3、Ti〇2、Ge02、Te02和Lu2〇3。優選使用選自下列各 項中的至少一項:Si〇2、Κ20、Na20、Li20、BaO、SrO、 CaO、MgO、Be〇、Zn0、Pb〇、Cd〇、、V2〇5、Sn〇、
Zr02 以及、、M〇〇3。 人含受體元素的玻璃粉末的具體實例可列舉包含前述 含受體元素的物質以及前述玻璃組成物f兩者,含受體元 璃粉末可列舉秘3_81〇2系(以含受體元素的物質_ 物質的順序記載,以下相W、B2(vzh =、秘3單㈣料包含料含"元素的 的t Γί 2系等的包含作為含受料素的_ =Ga2CVSi〇2系等的包含作為含受體元素的Ga細 此外,如同 ai2o3-b2〇3 系、Ga η Ώ ^ ^ 璃 扒古h、a 2〇r Β2〇3系等般,玻 b末也可以包含兩種類以上的含受體元素。 201140659 37019pif /管__在以上示出了含有一種或兩種組分的複合玻 璃’含有三種以上的物質的玻璃粉末如B203_Si〇rNa2〇等 也是可以的。 玻璃組分材料在玻璃粉末中的含量優選考慮烙融溫 度、軟化點、朗化點和化學耐久性而適當地設置。通常, 玻璃組分材料的含量優選為G.1質量%以上至95質量%以 下並且更優選為〇.5質量%以上至90質量%以下。 考慮到在擴散處理過程中的擴散性以及滴落 (dripping) ’破璃粉末的軟化點優選在2⑻。c〜i〇〇〇〇c 的範圍内,並且更優選在300〇C〜900〇C的範圍内。 作為朗粉末的雜’可列舉賴上雜,爲平狀, μ板狀’以及鱗片狀等,基於作為形成n型擴散層的 二“的情況下對基板的塗佈性以及擴散性的點來考量, 較佳為大體上球狀,扁平狀,或板狀。 玻璃粉末的粒徑優選為50 μηι以下。當使用粒徑為5〇 的玻璃粉末時’可以容易地得到平滑的塗膜。此 卜玻璃粉末的粒徑更優選為1〇μιη以下。又下限並無 特別的限制’較佳為0.01 μηι以上。 . =處’玻璃的粒徑是表示平均粒徑,可藉由雷射散射 射法(laser scattering diffracti〇n 咖比⑽)粒徑分布 C parole size distributi〇n )的測定裝置來進行測定。 含受體元素的玻璃粉末根據下列步驟製備。 处首先將原料稱重並且放入掛禍中。掛禍可以由始, 、白务銥,氧化銘,石英’碳或類似物製成,其考慮到熔 201140659 37019pif 融孤度三氣氛,與熔融材料的反應性等而適當地選擇。 /接著~將原料加熱到對應於電爐中的玻璃組合物的溫 又從而製備炫化液。此時,優選施加授拌以使炼化液變 得均勻。 、Ik後’使賴得祕嫌在氧储絲或碳基板等上 流動以致使溶化液的玻璃固化。 最後,將玻璃粉碎成粉末。所述粉碎可以通過使用已 知方法例如噴射磨、珠磨或球磨進行。 含受體元素的玻璃粉末在所述形成1)型擴散層的組合 :中的ί量考慮到可塗佈性'受體元素的擴散性等而; 定二通常’玻璃粉末在所述形成Ρ型擴散層的組合物中的 含量優選為0.1質量%以上至95質量%以下,並且更優選 為1質量%以上至90質量%以下。進一步優選為哲旦 %以上至85質量%以下’並且最優選為2質量%以上至8〇 質量%以下。 以下’將描述分散介質。 分散介質是將玻璃粉末分散在組合物中的介質。具體 地’將粘合劑、溶劑等用作分散介質。 八 例如,粘合劑可以適當地選自:聚乙烯醇,聚丙烯醯 胺類,聚乙烯基醯胺類,聚乙烯基吡咯烷酮,聚環氧乙烷 類,聚續酸,丙烯酿胺烧基續酸,纖維素_類,纖維素衍 生物,羧曱基纖維素,羥乙基纖維素,乙基纖維素,明'膠Μ 澱粉和澱粉衍生物,藻酸鈉類,蒼耳烷,瓜耳膠和瓜耳膠 衍生物,硬葡聚糖,黃蓍膠或糊精衍生物,(甲基)丙烯^ 11 201140659 J /Ul^pif ’(曱基)丙烯酸酯類樹脂(例如烷基(曱基)丙烯 、二曱基胺基乙基(曱基)丙烯酸樹脂等),丁二烯 巧樹脂,笨乙烯類樹脂及它們的共聚物,矽氧烷樹脂等。 這些化合物可以單獨使用或以它們的兩種以上的組合使 用。 粘合劑的分子量不受特別限制並且優選考慮到所述 組合物的所需粘度而適當地調節。 溶劑的實例包括:例如丙酮、曱基乙基酮、曱基正丙 基酮、甲基_異丙基酮、曱基-正丁基酮、曱基-異丁基酮、 甲基-正戊基酮、曱基_正己基酮、二乙基酮、二丙基酮、 二-異丁基酮、三曱基壬酮、環己酮、環戊酮、甲基環己酮、 2 4·.戍二㈣、丙喊丙_、γ_了㈣和戊内自旨等嗣系溶 1,=如二乙基醚、曱基乙基醚、甲基-正丙基峻 与土 ί n_Pn)Pyl ether)、二-異丙基醚、四氫呋喃、曱基四 氫吱喃、二口惡烧(di〇xane)、二甲基二魏、乙二醇 基輕、乙二醇二乙細、乙二醇二正丙細、乙二醇二丁 細、二甘細、二謂二乙細、二甘醇^乙 基趟、二甘醇甲基正丙基⑽'二甘醇甲基正丁基越、二甘
醇:=:+二甘醇二正丁跡二甘醇甲基正己基I IS;: 甘醇二乙細、三甘醇甲基乙基驗、 二甘和甲基正丁基⑽、三甘醇二正了基驗、三甘 正 己細、四甘醇二甲細、四甘醇二乙細、四二^ (嫩dieth細e glycol)甲基乙麵、四甘醇甲基正丁^和 一甘酵一正丁細、四甘醇甲基正己基㈣、四甘醇二正丁 12 201140659 37019pif 基醚、丙二醇二曱基醚、丙二醇二乙基醚、丙二醇二正丙 基醚、丙二醇二丁基醚、一縮二丙二醇二曱基醚、一縮二 丙二醇二乙基醚、一縮二丙二醇曱基乙基醚(dipr〇pylene glycol methyl ethyl ether)、一縮二丙二醇曱基正丁基醚、 一縮二丙二醇二正丙基醚、一縮二丙二醇二正丁基醚、一 縮二丙二醇曱基正己基醚、三丙二醇二曱基醚、三丙二醇 二乙基醚、二丙二醇甲基乙基醚、三丙二醇甲基正丁基醚、 三丙二醇二正丁基醚、三丙二醇甲基正己基醚、四丙二醇 二曱基醚、四丙二醇二乙基峻、四二丙二醇(tetradipiOpy匕狀 glycol)甲基乙基醚、四丙二醇曱基正丁基醚、一縮二丙二 醇二正丁基醚、四丙二醇曱基正己基醚和四丙二醇二正丁 基輕等的醚系溶劑;例如乙酸曱、乙酸乙醋、乙酸正丙 醋、乙酸異丙醋、乙酸正丁醋、乙酸異丁酯、乙酸仲丁醋、 乙酸正戊酯、乙酸仲戊酯、乙酸3砰氧基丁酯、乙酸甲基 戊醋、乙酸2_乙基丁@旨、乙酸2_乙基己錯、乙酸2·(2_丁氧 基乙氧基)乙醋、乙酸节g旨、乙酸環己醋、乙酸甲基環己醋、 乙酸壬酿、乙醯乙酸曱®旨、乙酿乙酸乙醋、二甘醇單曱基 喊乙義、二甘醇單乙_乙_、二甘醇單正丁細乙 酸酉旨、-縮二丙二醇單曱細乙酸§|、—縮二丙二醇單乙 基鱗乙酸S旨、乙二醇二乙酸、曱氧基三甘醇乙酸醋、丙 酸乙酯、丙酸正丁酉旨、丙酸異戊酿、草酸二乙醋、草酸二_ ^丁醋、乳酸曱酉旨、乳酸乙醋、乳酸正丁醋、乳酸正戍酉旨 專的醋糸溶劑:例如乙二醇曱基㈣酸§|、乙二醇乙基鍵 丙酸醋、乙二醇曱細乙目❹旨、乙二醇乙基㈣酸醋、二 13 201140659 3/uiypif 甘醇曱基⑽乙酸g旨、二甘醇乙基趟乙酸醋、二甘醇-正丁基 謎乙酸醋、丙二醇甲基喊乙酸醋、丙二醇乙基•酸醋、 丙二醇丙基驗乙酸g旨、-縮二丙二醇曱基趟乙酸醋和一縮 二丙二醇乙基旨料乙酸@|系溶劑;例如乙猜、n_ 曱基吡咯烷酮、N-乙基吡咯烷酮、N_丙基吡咯烷酮、N•丁 基吡咯烷酮、N-己基吡咯烷酮、N_環己基吡咯烷酮、n,n_ 二甲基甲_、N,N-二曱基乙醯胺、N,N•二甲亞石風等非質 子(proton)性極性溶劑;例如曱醇、乙醇、正丙 丙醇、正丁醇、異丁醇、仲丁醇、叔丁醇、正戊醇、異^ 醇、2-曱基丁醇、仲戊醇、叔戊醇、3_甲氧基丁醇、正己 醇、2-曱基戊醇、仲己醇'2_乙基丁醇、仲庚醇、正辛 2-乙基己醇、仲辛醇、正壬醇、正癸醇、仲十—燒醇、三 甲基壬醇、仲十四燒醇、仲十七烧醇、苯盼、環己醇、^ 基環己醇、节醇、乙二醇、以丙二醇、丁二醇二: 醇、-縮二丙二醇、三甘醇和三丙二料醇系溶 細、乙二醇乙基醚、乙二醇單苯細、二: η、、二甘醇單乙_、二甘醇單正丁基醚、二甘Ξ 醚一乙氧基二甘醇、四甘醇單正丁基醚、丙二醇 早曱細、-縮二丙二醇單曱細、—縮二丙二 醚、和三丙二料甲基鱗骑單 品烯、《 —萜品醇、 ^ 萜 烯蔽、夕-b! *才〜卜又·、 一烯获1-- (〇—、水序稀等JerP画1、香旱芽酮、蘿勒祐 坪專萜(terpene)糸溶劑;水等。這此 201140659 37019pif 材料可以單獨使用或以它們的兩種以上的組合使用。 曰分散介質在所述形成p型擴散層的組合物中的構成及 含量考慮到可塗布性和受體濃度而確定。 以下,將描述根據本發明的用於製備?型擴散層 伏電池的方法。 首,,將驗性溶液塗佈於作為P型半導體基板的石夕基 板上’藉此移除受損(damage)層,並且通賴刻得到紋 理結構。 具體地,在從錠料切下時所致的矽表面的受損層通過 使用20質量%的苛性鈉移除。然後,通過用1質量%的苛 性鋼與1G質量%的異丙醇的混合物進行㈣以形成紋理 結構。通過在受細(表面)上形成紋理結構以促進光學偈 限效應,從而光伏電池獲得高的效率。 尸接著’通過在三氣氧化磷(P〇cl3)、氮氣和氧氣的混合 ,體氣氛下,在8GG至_°C的溫度進行處理幾十分鐘, 從而形成η贿散層。此時’根據使用三氣氧化翻方法, 由於碟的擴散是側面及後面,因此η型擴散層不僅形成在 表面上,而且還形成在側面和後表面上。由於這些原因, 需要實施侧蝕刻製程來移除側面的η型擴散層。 此外,將形成ρ型擴散層的組合物塗佈在形成於後表 面即非光接受表面上的η型擴散層上。在本發明中,儘管 對塗佈方法沒有限制,但是例如可以使用印刷法,旋塗法, 刷塗,喷塗,刮刀法,輥塗機法,喷墨法等。 作為剷述形成Ρ型擴散層的組成物的塗佈量並無特別 15 201140659 3701 ypif 的限制’例如基於玻璃粉末量,可以為0 01g/m2〜100g/m2, 較佳為 O.lg/m2〜10g/m2。 此外,取決於形成P型擴散層的組合物的組成,必要 時在其塗佈以後,可能需要使組合物中含有的溶劑揮發 的乾燥製程。在此情況下,乾燥在8〇T〜3⑻。c的溫度進 行’當使用電熱板時’進行i至10分鐘,或當使用乾燥 器或類似裝置時,進行10至30分鐘。由於這些乾燥條件 取決於形成P型擴散層的組合物的溶劑組成,因此本發明 不特別限於上述條件。 對塗佈了形成p型擴散層的組合物的半導體基板在 600至1200°C的溫度進行熱處理。此熱處理導致受體元素 向半導體基板中的擴散,從而形成p+型擴散層。熱處理可 以使用已知的連續爐、間歇爐或類似裝置進行。 由於在p+型擴散層的表面上形成了由麟酸玻璃或類 似物構成的玻璃層,因此通過姓刻移除構酸玻璃。姓刻可 以通過使用已知方法進行,所述已知方法包括將目標物浸 入到酸如氮氣知中的方法,將目標物浸入到驗如苛性納中 的方法等。 在令規製備方去中,將紹膏塗佈到後表面上,然後燒 結,從而將η型擴散層轉變成p+型擴散層,同時還形成歐 姆接觸。然而’由於鋁膏具有低的電導率,因此為了降低 片電阻’通常必須在整個後表面上形成在燒結以後為約1〇 至20 μιη的厚銘層。而且,紹的熱膨脹係數與石夕的熱膨脹 係數顯著不同’因此這種差別導致在燒結和冷卻製程中在 16 201140659 j/uiypif 石夕基板中產生大的内應力,這促進了矽基板的翹曲。 内應力導致對晶粒界的損害問題,從而導致功率損失 增加。麵曲使得光伏電池易於在模組化處理中的電池的運 輸過程中損壞’或在與稱為分支線路(tub Une)的銅線連接 過程中損壞。最近,歸因於切割技術的進步,持續使得矽 基板的厚度變更薄,從而電池更容易破裂。 然而,根據本發明的製備方法,採用形成p型擴散層 的組合物將η型擴散層轉變成p+型擴散層,然後另外在p+ 型擴散層上製備電極。因此,用於後表面的材料不限於銘。 例如,還可以使用Ag (銀),Cu (銅)或類似物,從而後表 面的電極的厚度可以相對於現有技術進一步減小,並且另 外,不需要在整個後表面上形成電極。結果,可以抑制在 燒結和冷卻過程中在矽基板中形成内應力以及翹曲。 在η型擴散層上形成抗反射膜。抗反射膜通過使用已 知技術形成。例如,當抗反射膜是氮化矽膜時,抗反射膜 通過使用SiH4和NHS的混合氣體作為原料的等電漿 (plasma)CVD方法形成。在此情況下,氫擴散到晶體中, 和擴散到沒有貢獻於矽原子的結合的轨道中,即懸鍵 (dangling bond)與氫結合,這使得缺陷不活潑(氫鈍化)。 更具體地,抗反射膜在下列條件下形成:混合氣體 NiVSiH4流量比為〇.〇5〜1.0,反應室壓力為〇丨托(t〇rr) 至2托,成膜溫度為300°C至550。(:,和電聚放雪的赌鱼 為100 kHz以上。 通過絲網印刷法將用於表面電極的金屬膏印刷並涂 17 201140659 佈在表面(受光側)的抗反射膜上,隨後通過乾燥以形成 面電極。用於表面電極的金屬膏含有金屬粒子和破螭粒子 ^為主要組分’並且必要時含有樹職合劑、其他添加劑 然後,在p+型擴散層上也形成後表面電極。如之前所 述,後表面電極的構造材料和形成方法在本發明中並沒有 特別限制。例如,後表面電極還可以通過下列方法形成: 塗佈含有金屬如鋁、銀或銅的後表面電極膏,隨後^燥: 在此情況下,後表面的一部分還可以提供有用於形成銀電 極的銀膏,用於在模組化處理中電池之間的連接。 將電極燒結以完成光伏電池當燒結在〜 的溫度進行若干秒至若干分鐘時,表面側經歷作為絕緣膜 的抗反射膜的熔融,這歸因於在電極形成金屬膏中含有的 玻璃粒子,並且矽表面也部分熔融,由此所述膏中的金屬 粒子(例如,銀粒子)形成與矽基板的接觸,隨後固化。以 此方式,在形成的表面電極和矽基板之間形成電傳導。這 種製程稱為燒透(fire_through)。 以下,描述表面電極的形狀。表面電極由匯流條電極 和與所述匯流條電極交又的指狀電極(finger electr〇de)構 成。 表面電極可以例如通過下列方法形成:上述的金屬膏 的絲網印刷,或電極材料的鍍敷,在高真空下電極材料通 過電子束加熱的沉積,或類似方法^由匯流條電極和指狀 电極構成的表面電極是眾所周知的’因為它被典型用作光 18 201140659 j/uiypif 接受表面__,並且可喊 的匯流條電極和指狀電極的已知方法4就接又表面側 在用於製備?型擴散層和光伏 了在用作p型半導轉其扣心L 7的以上万击中為 氯氧化雜。C1、導5板场成n型擴散層,使用三 用於开π、氮乳和氧氣的混合氣體。然而,可以將 的組合物含有週期表的第二元二 雜)’録(sb)或純元素作為⑽it素。 在使用用於形成η型擴散層的组合物的方法中,為了 5擴政層’首先,制於形成η型紐層的組合物 k佈在作為光接受表面的卩型半導體基板的前表面上,將 形成P。型擴散相組合㈣佈在後表面上,雜在6〇〇〇c 二12〇0 C進行熱處理。此熱處理導致給體元素擴散到p型 半導體基㈣前表面巾㈣成㈣擴散層,並料致受體 元素擴散到p型半導體基板的後表面中以形成P+型擴散 層。除這些方法以外,根據與上述方法中相同的方法製備 光伏電池。 曰本申請案2010-022462號以及曰本申請案 2011 -005312號所揭示的所有内容是作為參照而被引用於 本說明書中。 本說明書中所記載的全部文獻、日本專利申請案、以 及技術規格是以與具體地且個別地記載以參照的形式引用 各個文獻、日本專利申請案、以及技術規格時相同的程度, 作為參照而被引用於本說明書中。 201140659 3701 ypif [實施例] 以下,將更詳細地描述根據本發明的實施例,但是本 發明不限於所述實施例。除非具體指出,否則所使用的化 學品全部是試劑級的。除非具體指出,否則“%,,是指“質量 %”。 [實施例1] 將20 g的粒子形狀呈大體上球狀、平均粒徑為4 9 μιη 且軟化點為 5610C 的 B203-Si〇2_R2〇 (r : Na,Κ,Li)系玻 璃粉末(商品名稱:TMX-404 ’ 由 Tokan Material Technology C〇.,Ltd.生產)’ 0·5 g乙基纖維素和i〇 g乙酸2_(2_丁氧基 乙氧基)乙酯利用自動研蛛(mortar)捏合裝置(kneading machine)混合並製成膏狀物,以製備形成p型擴散層的組 合物。 玻璃粒子的形狀是使用(公司)曰立高科技 (HIGHTECHNOLOGIES)製造的TM-1000型掃描式電子 顯微鏡觀察來觀察而判定的。玻璃的平均粒子徑是使用 BECKMAN COULTER (公司)製造的LS 13 320型雷射散 射繞射法(laser scattering diffraction method)粒徑分布測 疋裝置(測疋波長.632nm )而計算出來的。玻璃軟化點 是使用(公司)島津製作所製造之DTG—60AH熱示差· 熱重同時測定裝置,根據示差熱分析(DTA)曲線而求出 的。 接著,通過絲網印刷,將所製備的膏狀物塗佈到其上 形成有η-型層的p型矽基板表面上,並且在電熱板上在 201140659 i/uiypif 150 C乾無5分鐘。隨後’在設定為ι〇〇〇τ的電爐中進行 熱擴散處理30分鐘。然後’將基板浸入氫氟酸中5分鐘, 以移除玻璃層,進行流水洗滌、乾燥。 在塗佈了形成p型擴散層的組合物的那一側的表面表 現出190 Ω/□的片電阻和通過B(硼)的擴散形成p型擴散 層。 且’片電阻是使用三菱化學(公司)製的 Loresta-EPMCP-T3 60型的低電阻率計藉由四探針法所測 定。 [實施例2] 除了將玻璃粉末改變為粒子形狀呈大體上球狀、平均 粒徑為 3.2μιη 且軟化點為 8150C 的 B203-Si02-R〇(;R:]V[g, Ca,Sr,Ba)系玻璃粉末(商品名稱:TMX-603,由Tokan Material Technology Co.,Ltd.生產)作為p型擴散層組成物 之外,以與實施例1中相同的方式形成p型擴散層。在塗 佈了形成P型擴散層的組合物的那一側的表面表現出35 Ω/□的片電阻和通過B(硼)的擴散形成p型擴散層。 [實施例3] 除了將玻璃粉末改變為粒子形狀呈大體上球狀、平均 粒徑為 5.1μιη 且軟化點為 808。(:的 B203-Si02-R〇(R:Mg, Ca,Sr,Ba)系玻璃粉末(商品名稱:TMX-403,由Tokan Material Technology Co.,Ltd.生產)作為p型擴散層組成 物’以與實施例1中相同的方式形成p型擴散層。在塗佈 了形成P型擴散層的組合物的那一侧的表面表現出45 Ω/口 21 201140659 J f\Ji ^pif 的片電阻和通過B(棚)的擴散形成P型擴散層。 [實施例4] 將20 g的粒子形狀呈大體上球狀、平均粒徑為3.Ιμιη 且軟化點為 416°C 的 P2〇5-ZnOrR2〇 (R : Na,Κ, Li)系玻璃粉末(商品名稱.TMX-203 ’由Tokan Material Technology Co.,Ltd.生產)’ 0.3 g乙基纖維素和7g乙酸 2-(2-丁氧基乙氧基)乙醋利用自動研体捏合裝置混合並製 成膏狀物,以製備用於形成η型擴散層的組合物。將所製 備的膏狀物塗佈到Ρ型碎基板表面上。 隨後,將 20 g 的 B2〇3-Si〇2-RO (R : Mg,Ca,Sr,Ba) 糸玻璃粉末(商品名稱.TMX-603,由Tokan Material Technology Co.,Ltd.生產),0.5 g乙基纖維素和10 g乙 1 2-(2-丁氧基乙氧基)乙醋同樣地混合並製成膏狀物,以 製備形成p型擴散層的組合物。將所製備的膏狀物通過絲 網印刷塗佈到沒有印刷用於形成n型擴散層的組合物的p 型矽基板表面上,並且在電熱板上在150〇c乾燥5分鐘。 接著,在設定為1〇〇〇。〇的電爐中進行熱擴散處理1〇 分鐘。然後,將基板浸入氫氟酸中5分鐘,以移除玻璃層, k後用進行流水洗條、乾燥。 在塗佈了用於形成n型擴散層的組合物的那一側的表 ,表現出35 Ω/□的片電阻和通過ρ(磷)的擴散形成η型擴 政層。在塗佈了形成ρ型擴散層的組合物的那一侧的表面 表現出47 Ω/□的片電阻和通過Β(硼)的擴散形成Ρ型擴散 層0 22 201140659 3/Uiypif 雖然本發明已以實施例揭露如上,然其 本發明,任何所屬技術領域中具有通常知二用以限定 本U之精神和範_,當 ,在不脫離 發明夕徂嘈, ,F —°卞I更勤與潤飾,故太 =錄圍當視後附之申請專利範圍所界定者 【圖式簡單說明】 無 【主要元件符號說明】 無 23
Claims (1)
- 201140659 37019pif 七、申請專利範固: < L 一種形成p型擴散層的組合物,其中該組合物含有 含受體元素的破螭粉末以及分散介質。 2. 如申請專利範圍第1項所述之形成P型擴散層的組 合物,其中該受體元素是選自硼(B)、鋁(A1)及鎵(Ga)中的 至少一種受體元素。 3. 如申請專利範圍第1項所述之形成p型擴散層的組 合物,其中該含受體元素的玻璃粉末含有: 選自Β2〇3、Α12〇3及Ga2〇3中的至少一種含受體元素 的材料;以及 選自 Si〇2、K20、Na20、Li2〇、BaO、SrO、CaO、 MgO、BeO、ZnO、PbO、CdO、V2〇5,SnO,Zr02 及 Mo03 中的至少一種玻璃成分材料。 4. 一種p型擴散層的製造方法,包括: 在半導體基板上塗佈如申請專利範圍第1項至第3項 中任一項所述的形成p型擴散層的組合物的步驟;以及 進行熱擴散處理的步驟。 5. —種光伏電池的製造方法,包括: 在半導體基板上塗佈如申請專利範圍第1項至第3項 中任一項所述的形成P型擴散層的組合物的步驟;以及 對該基板進行熱擴散處理以形成p型擴散層的步驟; 以及 在所形成之P型擴散層上形成電極的步驟。 24 201140659 37019pif 四、指定代表圖: (一) 本案之指定代表圖:無。 (二) 本代表圖之元件符號簡單說明: 無0 五、本案若有化學式時,請揭示最能顯示發明特徵 的化學式: 無 201140659 37019pifl 爲第100102723號中文說明書無劃線修正頁 /;· ,「 修正b嫌100華3 \ ΐίΠ/ Ο 基醚、丙二醇二曱基醚、丙二醇二乙基醚、丙二醇二正丙 基醚、丙二醇二丁基鰱、一縮二丙二醇二曱基喊、一縮二 丙二醇二乙基醚、一縮二丙二醇甲基乙基醚(dipr〇pylene glycol methyl ethyl ether)、一縮二丙二醇甲基正丁基醚、 一縮·一.丙一醇二正丙基鍵、一縮二丙二醇二正丁基謎、一 縮二丙二醇甲基正己基醚、三丙二醇二曱基醚、三丙二醇 二乙基醚、三丙二醇曱基乙基醚、三丙二醇曱基正丁基醚、 二丙二醇二正丁基醚、三丙二醇甲基正己基醚、四丙二醇 二甲基趟、四丙二醇二乙基醚、四二丙二醇(tetradipr〇pylene glycol)曱基乙基醚、四丙二醇曱基正丁基醚、一縮二丙二 醇二正丁基醚、四丙二醇曱基正己基醚和四丙二醇二正丁 基醚等的醚系溶劑;例如乙酸曱§旨、乙酸乙醋、乙酸正丙 酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸仲丁酯、 乙酸正戊酯、乙酸仲戊酯、乙酸3_曱氧基丁酯、乙酸曱基 戊醋、乙酸2-乙基丁g旨、乙酸2_乙基己醋、乙酸丁& 基乙氧基)乙醋 '乙酸节醋、乙酸環已酿、乙酸甲基環己醋、 乙酸壬酯、乙醯乙sit曱醋、乙酿乙酸乙_、二甘 醚乙酸乙細乙_旨、 ^ 酸醋、-縮二丙二醇單甲基醚乙酸醋、一縮: 基醚乙酸酯、乙二醇二乙旨、¥ _ ^ H 日甲氣基三甘醇乙酸酯、丙 I乙酉日、丙酸正TS旨、_異如旨、草酸二乙酯、草酸二 正丁醋、乳酸曱醋、乳酸乙酉旨、乳酸正丁 g 等的醋系溶劑;例如乙二醇曱基__旨、乙二醇乙t 丙酸醋、乙二醇甲基醚乙_旨、乙二醇乙_乙酸酯^ 13 201140659 37019pifl 修正日期:100年3月18日 爲第100102723號中文說明書無劃線修正頁 甘醇甲基醚乙酸酯、二倾乙基私_旨、二倾·正丁基 鍵乙酸醋、丙二醇甲基私酸S旨、㊉二醇乙基醚乙酸酉旨, 丙二醇丙細乙_、—縮二丙二醇曱細乙_和一缩 -丙-醇乙基醚乙酸自旨等_乙_旨系溶劑;例如乙猜、& 甲基吼魏酮、Ν·乙基轉_、一基轉_、时 基0比咯烧_、N-己基η比略烧酮、n ja :j « _ 扯基轉細、N,N_ 二基甲醯月女、N,N-二甲基乙醯胺、叫二甲亞石風 子b她η)性極性溶劑;例如甲醇、乙醇、正丙醇、異 Ξ醇2、異:Γ、仲丁醇、叔丁醇、正戊醇、異戊 ί叔戊醇、”氧基丁醇、正己 mt l醇、2_乙基丁醇、仲庚醇、正辛醇、 曱美二薛醇、正壬醇、正癸醇、仲十一烧醇、三 m四燒醇、仲十七燒醇、苯紛、環己醇、曱 =醇、卞醇、乙二醇、u_丙二醇、以丁二醇、二: r :、ΐ=二醇、三甘醇和三丙二醇等醇系溶劑;例如 單甲基醚、二甘醇單單苯基謎、二甘醇 單正己基醚、乙氧基:^ 早正丁基醚、二甘醇 單曱基鍵、-縮二;=二醇單:丁基醚、丙二醇 奸早甲暴喊、一縮二丙二醇單匕其 1 和一丙—醇^甲基喊等甘醇單喊系溶劑;例如 口口稀、α —萜品醇、 U1〇-_ene)、檸檬綠、月鏤=坪、醯㈣羅勒稀 烯蒎、萜品醇(terpine〇1)夭曰斧一烯蒎、冷—一 水麵綠二^ 糸丨,水等。這些材料可以單獨 14 201140659 • 37019pifl • 爲第1⑻而23號中文酬賴麵駐頁 修正_:1_月18日 , 使用或以它們的兩種以上的組合使用。 分散介質在所述形成P型擴散層的組合物中的構成及 含量考慮到可塗布性和受體濃度而確定。 以下,將描述根據本發明的用於製備p型擴散層和光 伏電池的方法。 ΐ先,躲性溶佈於作為p解導縣板的石夕基 板上’藉此移除受損(damage)層,並且通過钮刻得到紋 0 理結構。 具體地,在從錠料切下時所致的石夕表面的受損層通過 使用20質量%的苛性鈉移除。然後’通過用1質量% =與1G質量%的異丙醇的混合物進行㈣以形成紋理 、、’。冓。通過在受細(表面)±形成紋理結_促進光學倡 限效應,從而光伏電池獲得高的效率。 接著’通過在三氯氧化磷(p〇cl3)、氮氣和氧氣的混合 =體喊下’在_至9WC的溫度進行處理幾十分鐘, 散層。此時,根據使用三氯氧化鱗的方法, 表而μ'、擴散ΐ㈣及後面,· n型擴散層不僅形成在 步i每*且還形成在側面和後表面上。由於這些原因, 茜要實施侧钱刻製程來移除侧面的η型擴散層。一 面即^接Ρ _散層的組合物塗佈在形成於後表 對塗備方本上的η型擴散層上。在本發明中,儘管 刷塗,噴塗例如可以使用印刷法,旋塗法’ 、、‘、、刀法,輥塗機法,喷墨法等。 二、述形成P型擴散層的組成物的塗佈量並無特別 15 201140659 37019pifl 爲第100102723號中文說明書無劃線修正頁 修正日期:1〇〇年3月18日 的限制’例如基於玻璃粉末量,可以為0.01g/m2〜100g/m2, 較佳為 〇.lg/m2〜l〇g/m2。 此外’取決於形成p型擴散層的組合物的組成,必要 時’在其塗佈以後’可能需要使組合物中含有的溶劑揮發 的乾燥製程。在此情況下,乾燥在8〇°c〜300°C的溫度進 行,當使用電熱板時,進行1至10分鐘,或當使用乾燥 器或類似裝置時,進行1〇至3〇分鐘。由於這些乾燥條件取決於形成p型擴散層的組合物的溶劑組成,因此本發明 不特別限於上述條件。 對塗佈了形成p型擴散層的組合物的半導體基板在 600至120CPC的溫度進行熱處理。此熱處理導致受體元素 向半導體基板中的擴散,從而形成〆型擴散層。熱處理可 以使用已知的連續爐、間歇爐或類似裝置進行。由於在p型擴散層的表面上形成了由磷酸玻璃或類 似物構成的玻璃層,因此通過蝕刻移除磷酸玻璃。蝕刻可 以通過使用已知方法進行,所述已知方法包括將目標物产 入到酸如氫_中的方法,將目標物浸人顺如苛性納$ 在常規製傷方法中,將铭膏塗佈到後表面上 結’從而將n型擴散層轉變成P+型擴散層,同時還升 姆接觸。然而,由於鋁膏具有低的電導率,因^ 片電阻’通常必彡貞在整佩表社形成錢纟I牛氏 而且,的熱_係數與::熱: 係數顯者抑,因此這種差別導致錢結和冷卻製程中: 16
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2011
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- 2011-01-25 EP EP13178174.2A patent/EP2662883B1/en not_active Not-in-force
- 2011-01-25 CN CN201510193767.5A patent/CN104835724B/zh not_active Expired - Fee Related
- 2011-01-25 EP EP17162541.1A patent/EP3203500A1/en not_active Withdrawn
- 2011-01-25 TW TW105126461A patent/TW201642321A/zh unknown
- 2011-01-25 CN CN201610524236.4A patent/CN105977143B/zh not_active Expired - Fee Related
- 2011-01-25 WO PCT/JP2011/051365 patent/WO2011096301A1/ja active Application Filing
- 2011-01-25 EP EP16164209.5A patent/EP3062336A1/en not_active Withdrawn
- 2011-01-25 KR KR1020110007215A patent/KR20110090780A/ko not_active IP Right Cessation
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- 2011-01-25 TW TW103103033A patent/TWI667695B/zh not_active IP Right Cessation
- 2011-01-25 EP EP11151993.0A patent/EP2355137B1/en not_active Not-in-force
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CN105977143A (zh) | 2016-09-28 |
TWI482207B (zh) | 2015-04-21 |
KR20110090780A (ko) | 2011-08-10 |
EP2355137A1 (en) | 2011-08-10 |
JP5447397B2 (ja) | 2014-03-19 |
CN105977143B (zh) | 2018-03-30 |
TW201642321A (zh) | 2016-12-01 |
CN102169738B (zh) | 2017-06-13 |
TW201419385A (zh) | 2014-05-16 |
EP2355137B1 (en) | 2016-05-25 |
WO2011096301A1 (ja) | 2011-08-11 |
CN104835723A (zh) | 2015-08-12 |
CN104835724A (zh) | 2015-08-12 |
CN104835723B (zh) | 2018-04-10 |
CN104835724B (zh) | 2019-01-04 |
KR20170045744A (ko) | 2017-04-27 |
EP2662883B1 (en) | 2017-09-27 |
EP3203500A1 (en) | 2017-08-09 |
EP3062336A1 (en) | 2016-08-31 |
JP2011181901A (ja) | 2011-09-15 |
CN102169738A (zh) | 2011-08-31 |
TWI667695B (zh) | 2019-08-01 |
EP2662883A1 (en) | 2013-11-13 |
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