TW201327638A - 擴散劑組成物、雜質擴散層之形成方法及太陽能電池 - Google Patents
擴散劑組成物、雜質擴散層之形成方法及太陽能電池 Download PDFInfo
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- TW201327638A TW201327638A TW101132979A TW101132979A TW201327638A TW 201327638 A TW201327638 A TW 201327638A TW 101132979 A TW101132979 A TW 101132979A TW 101132979 A TW101132979 A TW 101132979A TW 201327638 A TW201327638 A TW 201327638A
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Abstract
本發明之擴散劑組成物,係於半導體基板形成雜質擴散層時所使用之擴散劑組成物,其含有:硼酸酯(A)、下述通式(1)所表示之多元醇(B)、與烷氧矽烷化合物(C)。□[通式(1)中,k為0~3之整數。m為1以上之整數。R2及R3,分別獨立地為氫原子、羥基、碳原子數1~5之烷基、或碳原子數1~5之羥烷基。R2及R3當為複數時,複數之R2及R3可分別為相同或相異。又,當k為2以上時,複數之R2及R3必須含有一個以上之羥基或碳原子數1~5之羥烷基。R4及R5,分別獨立地為氫原子或碳原子數1~3之烷基。]
Description
本發明係關於一種擴散劑組成物、雜質擴散層之形成方法及太陽能電池。
於電晶體、二極體、IC等之製造,係使用具有硼擴散後之P型區域之矽半導體元件。以往,使硼於矽基板擴散的方法,主要係使用熱分解法、對向NB法、摻雜物主體法、塗布法等。該等之中,由於塗布法不需要高價之裝置、可均勻地擴散、且量產性優異,故採用其為佳。特別以將含有硼之塗布液以旋塗器等進行塗布之方法為佳。
以往,旋塗法等之擴散塗布法所使用之含硼之擴散劑組成物之聚硼膜(PBF)有各種提案(專利文獻1~6)。
然而,近年來,於半導體製造領域、特別是太陽能電池製造領域,要求低成本化、高通量化、減低環境負荷。具體而言,例如於製造矽系太陽能電池時,要求更減少擴散用塗布液的使用量、或以更少之步驟數於同一矽基板內局部地形成擴散載體、擴散濃度不同之區域、亦即局部擴散。於該情形,以往之旋塗法,每基板之塗布液的使用量多,高成本且廢液量亦多。又,局部擴散時,產生事先於矽基板形成擴散保護膜等之必要,故步驟數亦增多。由於如此之背景,近年來,開發以噴墨印刷法或網版印刷法等於矽基板局部地印刷塗布液以進行局部擴散之方法。
專利文獻1:日本特開平9-181010號公報
專利文獻2:日本特開平4-53127號公報
專利文獻3:日本特開平9-181009號公報
專利文獻4:日本專利第3519847號公報
專利文獻5:日本特開昭57-73931號公報
專利文獻6:日本特開2010-62223號公報
一般而言,以往之使用PBF之硼擴散,係將PBF溶液塗布於矽基板上後,於使硼擴散之前,使硼之黏結劑之含羥基之高分子化合物分解燃燒。因此,於硼之擴散時,硼化合物(B2O3)成為單獨形成被膜的狀態,硼容易由矽基板上之硼被膜朝被膜外部飛散。因此,當使用如此之PBF實施局部擴散時,容易引起硼擴散至相鄰之基板或PBF之未塗布區域的向外擴散(out diffusion),難以局部擴散。
又,不使用以往之PBF所含之聚乙烯醇等黏結劑,而將硼化合物(B2O3、硼酸等)溶解於有機溶劑之硼擴散劑組成物,當形成為被膜時,有硼化合物容易凝集、析出的傾向。然而,於擴散劑組成物,為了抑制所形成之雜質擴散層之電阻值的偏差或接面的混亂,要求不易引起所含之硼化合物之凝集、能高濃度且均勻之硼擴散。
本發明係有鑑於如此之狀況所完成者,其之目的在於
提供一種能抑制向外擴散之發生、與所含之硼化合物之凝集的擴散劑組成物、使用前述擴散劑組成物之雜質擴散層的形成方法、及太陽能電池。
為了解決上述課題,本發明之一樣態為擴散劑組成物。前述擴散劑組成物,係於半導體基板形成雜質擴散層時所使用之擴散劑組成物,其特徵係含有:硼酸酯(A)、下述通式(1)所表示之多元醇(B)、與烷氧矽烷化合物(C)。
[通式(1)中,k為0~3之整數。m為1以上之整數。R2及R3,分別獨立地為氫原子、羥基、碳原子數1~5之烷基、或碳原子數1~5之羥烷基。當R2及R3為複數時,複數之R2及R3可分別為相同或相異。又,當k為2以上時,複數之R2及R3必須含有一個以上之羥基或碳原子數1~5之羥烷基。R4及R5,分別獨立地為氫原子或碳原子數1~3之烷基。]
藉由該樣態,可抑制向外擴散之發生、與所含之硼化合物之凝集。
本發明之其他樣態為雜質擴散層之形成方法。該雜質擴散層之形成方法,其特徵係含有:於半導體基板,將上
述樣態之擴散劑組成物選擇性地塗布以形成既定圖型之雜質擴散層的圖型形成步驟;與使擴散劑組成物所含之硼酸酯(A)之硼,擴散於半導體基板的擴散步驟。
藉由該樣態,能以更高精度形成雜質擴散層。
本發明之再一樣態為太陽能電池。該太陽能電池,其特徵係,具備以上述之雜質擴散層之形成方法所形成有雜質擴散層之半導體基板。
藉由該樣態,可得可靠性更高之太陽能電池。
藉由本發明,可提供一種能抑制向外擴散之發生、與所含之硼化合物之凝集的擴散劑組成物、使用前述擴散劑組成物之雜質擴散層的形成方法、及太陽能電池。
以下,以較佳之實施形態說明本發明。實施形態係僅用以例示者並不限定發明,而實施形態所記述之所有特徵或其之組合,並不一定為發明之本質者。
本實施形態之擴散劑組成物,係於半導體基板形成雜質擴散層時所使用之擴散劑組成物,特別是,於藉選擇性地塗布以形成既定圖型之雜質擴散層時所使用之較佳之擴散劑組成物。本實施形態之擴散劑組成物,含有:硼酸酯(A)、多元醇(B)、與烷氧矽烷化合物(C)。又,擴散劑組成物,含有作為任意成分之有機溶劑(D)。以下,詳細說
明本實施形態之擴散劑組成物之各成分。
硼酸酯(A),係作為摻雜劑使用於太陽能電池之製造之化合物。硼酸酯(A),為III族(13族)元素之化合物,含有P型之雜質擴散成分之硼。硼酸酯(A),可於半導體基板內形成P型之雜質擴散層(雜質擴散區域)。更具體而言,硼酸酯(A),可於N型之半導體基板內形成P型之雜質擴散層,可於P型之半導體基板內形成P+型(高濃度P型)之雜質擴散層。
硼酸酯(A)之濃度,可因應半導體基板所形成之雜質擴散層之層厚等適當地加以調整。例如,硼酸酯(A),相對於擴散劑組成物之總質量以含有0.1質量%以上為佳,以含有1.0質量%以上為更佳。又,硼酸酯(A),相對於擴散劑組成物之總質量以含有50質量%以下為佳。又,硼酸酯(A)中之硼原子,相對於擴散劑組成物之總質量,較佳為以0.01~10質量%之範圍含有、更佳為以0.1~3質量%之範圍含有。
於本實施形態,硼酸酯(A),具有下述通式(2)所表示之構造。
B(OR1)3 (2)
[通式(2)中,R1分別獨立地為碳原子數1~10之烷基
、或碳原子數6~10之芳基。3個R1可為相同或相異。]
當R1為烷基時,以碳數1~4之直鏈狀或分支鏈狀之烷基為更佳。芳基,例如苯基、萘基等。又,烷基及芳基,亦可具有取代基。
硼酸酯(A)之具體例,可舉例如硼酸三甲酯、硼酸三乙酯、硼酸三丙酯、硼酸三丁酯、硼酸三戊酯、硼酸三己酯、硼酸三辛酯、硼酸三苯酯等。該等硼酸酯(A)之中,由更容易發揮凝集、析出之抑制效果的觀點,以硼酸三甲酯、硼酸三乙酯為佳。該等之硼酸酯(A),可單獨使用、亦可組合2種以上。
多元醇(B),係以下述通式(1)表示。
[通式(1)中,k為0~3之整數。m為1以上之整數。R2及R3,分別獨立地為氫原子、羥基、碳原子數1~5之烷基、或碳原子數1~5之羥烷基。R2及R3當為複數時,複數之R2及R3可分別為相同或相異。又,當k為2以上時,複數之R2及R3必須含有一個以上之羥基或碳原子數1~5之羥烷基。R4及R5,分別獨立地為氫原子或碳原子數1~3之烷基。]
多元醇(B)之具體例,可舉例如乙二醇、丙二醇、1,3-丁二醇、三羥甲基丙烷、3-甲基戊烷-1,3,5-三醇、甘露醇等。該等多元醇,可單獨使用、亦可組合2種以上使用。
藉由使P型之雜質擴散成分以硼酸酯(A)之形式含於擴散劑組成物、並且使擴散劑組成物含有特定構造之多元醇(B),於擴散劑組成物中多元醇(B)與硼酸酯(A)會有效率地形成錯合物,藉此可抑制硼酸酯(A)之水解,並抑制硼化合物之凝集及析出。又,由於可抑制硼化合物之凝集及析出,故可抑制硼由塗布於半導體基板等之擴散劑組成物之被膜朝被膜外部飛散,而附著於相鄰之基板或擴散劑組成物之未塗布區域而產生向外擴散的發生。
擴散劑組成物中之硼酸酯(A)及多元醇(B)之含有比,以硼酸酯(A)之含量為多元醇(B)之含量的5倍莫耳以下為佳、2倍莫耳以下為更佳。又,由硼酸酯(A)可有效地形成錯合物的觀點考量,更佳為,多元醇(B)之含量較硼酸酯(A)之含量為多、亦即硼酸酯(A)之含量未達多元醇(B)之含量之1倍莫耳。
烷氧矽烷化合物(C),含有下述通式(3)所表示之烷氧矽烷水解所得之反應生成物。
R6 nSi(OR7)4-n (3)
[通式(3)中,R6為氫原子或有機基。R7為有機基。n為0、1、或2之整數。當R6為複數時,複數之R6可為相同或相異,當(OR7)為複數時,複數之(OR7)可為相同或相異。]
R6及R7之有機基,可舉例如烷基、芳基、烯丙基、甘胺醯基等。該等之中,以烷基及芳基為佳。R6之有機基,例如以碳數1~20之直鏈狀或分支鏈狀之烷基為更佳,由反應性之觀點,以碳數1~4之直鏈狀或分支鏈狀之烷基又更佳。較佳為,R6之中至少1個為烷基或芳基。芳基,例如以碳數6~20者為佳,可舉例如苯基、萘基等。
R7之有機基,例如以碳數1~5之直鏈狀或分支鏈狀之烷基為佳,由反應性之觀點,以碳數1~3之直鏈狀或分支鏈狀之烷基為更佳。芳基,例如以碳數6~20者為佳,可舉例如苯基、萘基等。
上述通式(3)中之n為0時之烷氧矽烷(i),例如可以下述通式(4)表示。
Si(OR21)a(OR22)b(OR23)c(OR24)d (4)
[通式(4)中,R21、R22、R23及R24,分別獨立地表示與上述R7同樣之有機基。a、b、c及d,為滿足0≦a≦4、0≦b≦4、0≦c≦4、0≦d≦4、且a+b+c+d=4之條件的整數。]
烷氧矽烷(i)之具體例,可舉例如四甲氧矽烷、四乙氧
矽烷、四丙氧矽烷、四丁氧矽烷、四戊氧矽烷、四苯氧矽烷、三甲氧基單乙氧矽烷、二甲氧基二乙氧矽烷、三乙氧基單甲氧矽烷、三甲氧基單丙氧矽烷、單甲氧基三丁氧矽烷、單甲氧基三戊氧矽烷、單甲氧基三苯氧矽烷、二甲氧基二丙氧矽烷、三丙氧基單甲氧矽烷、三甲氧基單丁氧矽烷、二甲氧基二丁氧矽烷、三乙氧基單丙氧矽烷、二乙氧基二丙氧矽烷、三丁氧基單丙氧矽烷、二甲氧基單乙氧基單丁氧矽烷、二乙氧基單甲氧基單丁氧矽烷、二乙氧基單丙氧基單丁氧矽烷、二丙氧基單甲氧基單乙氧矽烷、二丙氧基單甲氧基單丁氧矽烷、二丙氧基單乙氧基單丁氧矽烷、二丁氧基單甲氧基單乙氧矽烷、二丁氧基單乙氧基單丙氧矽烷、單甲氧基單乙氧基單丙氧基單丁氧矽烷等四烷氧矽烷,其中,以反應性的觀點考量以四甲氧矽烷、四乙氧矽烷為佳。
當上述通式(3)中之n為1時之烷氧矽烷(ii),例如係以下述通式(5)所表示。
R31Si(OR32)e(OR33)f(OR34)g (5)
[通式(5)中,R31與上述R6同樣地表示氫原子或有機基。R32、R33及R34,分別獨立地表示與上述R7同樣之有機基。e、f及g,為滿足0≦e≦3、0≦f≦3、0≦g≦3、且e+f+g=3之條件的整數。]
烷氧矽烷(ii)之具體例,可舉例如甲基三甲氧矽烷、
甲基三乙氧矽烷、甲基三丙氧矽烷、甲基三戊氧矽烷、乙基三甲氧矽烷、乙基三丙氧矽烷、乙基三戊氧矽烷、乙基三苯氧矽烷、丙基三甲氧矽烷、丙基三乙氧矽烷、丙基三戊氧矽烷、丙基三苯氧矽烷、丁基三甲氧矽烷、丁基三乙氧矽烷、丁基三丙氧矽烷、丁基三戊氧矽烷、丁基三苯氧矽烷、甲基單甲氧基二乙氧矽烷、乙基單甲氧基二乙氧矽烷、丙基單甲氧基二乙氧矽烷、丁基單甲氧基二乙氧矽烷、甲基單甲氧基二丙氧矽烷、甲基單甲氧基二戊氧矽烷、甲基單甲氧基二苯氧矽烷、乙基單甲氧基二丙氧矽烷、乙基單甲氧基二戊氧矽烷、乙基單甲氧基二苯氧矽烷、丙基單甲氧基二丙氧矽烷、丙基單甲氧基二戊氧矽烷、丙基單甲氧基二苯氧矽烷、丁基單甲氧基二丙氧矽烷、丁基單甲氧基二戊氧矽烷、丁基單甲氧基二苯氧矽烷、甲基甲氧基乙氧基丙氧矽烷、丙基甲氧基乙氧基丙氧矽烷、丁基甲氧基乙氧基丙氧矽烷、甲基單甲氧基單乙氧基單丁氧矽烷、乙基單甲氧基單乙氧基單丁氧矽烷、丙基單甲氧基單乙氧基單丁氧矽烷、丁基單甲氧基單乙氧基單丁氧矽烷等,其中,由反應性的觀點,較佳為甲基三烷氧矽烷、特佳為甲基三甲氧矽烷、甲基三乙氧矽烷。
當上述通式(3)中之n為2時之烷氧矽烷(iii),例如係以下述通式(6)所表示。
R41R42(OR43)h(OR44)i (6)
[通式(6)中,R41及R42,與上述R6同樣地表示氫原子或有機基。R43及R44,分別獨立地表示與上述R7同樣之有機基。h及i,為滿足0≦h≦2、0≦i≦2、且h+i=2之條件的整數。]
烷氧矽烷(iii)之具體例,可舉例如甲基二甲氧矽烷、甲基甲氧基乙氧矽烷、甲基二乙氧矽烷、甲基甲氧基丙氧矽烷、甲基甲氧基戊氧矽烷、甲基甲氧基苯氧矽烷、乙基二丙氧矽烷、乙基甲氧基丙氧矽烷、乙基二戊氧矽烷、乙基二苯氧矽烷、丙基二甲氧矽烷、丙基甲氧基乙氧矽烷、丙基乙氧基丙氧矽烷、丙基二乙氧矽烷、丙基二戊氧矽烷、丙基二苯氧矽烷、丁基二甲氧矽烷、丁基甲氧基乙氧矽烷、丁基二乙氧矽烷、丁基乙氧基丙氧矽烷、丁基二丙氧矽烷、丁基甲基二戊氧矽烷、丁基甲基二苯氧矽烷、二甲基二甲氧矽烷、二甲基甲氧基乙氧矽烷、二甲基二乙氧矽烷、二甲基二戊氧矽烷、二甲基二苯氧矽烷、二甲基乙氧基丙氧矽烷、二甲基二丙氧矽烷、二乙基二甲氧矽烷、二乙基甲氧基丙氧矽烷、二乙基二乙氧矽烷、二乙基乙氧基丙氧矽烷、二丙基二甲氧矽烷、二丙基二乙氧矽烷、二丙基二戊氧矽烷、二丙基二苯氧矽烷、二丁基二甲氧矽烷、二丁基二乙氧矽烷、二丁基二丙氧矽烷、二丁基甲氧基戊氧矽烷、二丁基甲氧基苯氧矽烷、甲基乙基二甲氧矽烷、甲基乙基二乙氧矽烷、甲基乙基二丙氧矽烷、甲基乙基二戊氧矽烷、甲基乙基二苯氧矽烷、甲基丙基二甲氧矽烷、甲基丙基二乙氧矽烷、甲基丁基二甲氧矽烷、甲基丁基二
乙氧矽烷、甲基丁基二丙氧矽烷、甲基乙基乙氧基丙氧矽烷、乙基丙基二甲氧矽烷、乙基丙基甲氧基乙氧矽烷、二丙基二甲氧矽烷、二丙基甲氧基乙氧矽烷、丙基丁基二甲氧矽烷、丙基丁基二乙氧矽烷、二丁基甲氧基乙氧矽烷、二丁基甲氧基丙氧矽烷、二丁基乙氧基丙氧矽烷等,其中,以甲基二甲氧矽烷、甲基二乙氧矽烷為佳。
烷氧矽烷化合物(C),例如,可藉由下述方法調製:將選自上述烷氧矽烷(i)~(iii)之中之1種或2種以上,於酸觸媒、水、有機溶劑的存在下水解之方法。
如上述,雖於烷氧矽烷之水解反應中使用水,但於本實施形態之擴散劑組成物,以組成物整體為基準之水的含量以1質量%以下為佳、0.5質量%以下為更佳,以實質上不含有水為更佳。藉此,可更提高擴散劑組成物之保存安定性。
酸觸媒,可使用有機酸、無機酸之任一者。無機酸,可使用硫酸、磷酸、硝酸、鹽酸等,其中,以磷酸、硝酸為佳。有機酸,可使用甲酸、草酸、富馬酸、馬來酸、冰醋酸、乙酸酐、丙酸、正丁酸等羧酸、及具有含硫酸殘基之有機酸。具有含硫酸殘基之有機酸,可舉例如有機磺酸等,該等之酯化物,可舉例如有機硫酸酯、有機亞硫酸酯等。該等之中,特別以有機磺酸、例如以下述通式(7)所表示之化合物為佳。
R13-X (7)
[通式(7)中,R13為亦可具有取代基之烴基,X為磺酸基。]
上述通式(7)中,R13之烴基,以碳數1~20之烴基為佳。該烴基,可為飽和或不飽和,可為直鏈狀、具支鏈狀、環狀之任一者。當R13之烴基為環狀時,例如以苯基、萘基、蒽基等之芳香族烴基為佳,其中以苯基為佳。於該芳香族烴基中之芳香環,以可鍵結1個或複數個作為取代基之碳數1~20之烴基。該芳香環上之取代基之烴基,可為飽和或不飽和,可為直鏈狀、具支鏈狀、環狀之任一者。又,R13之烴基,亦可具有1個或複數個之取代基,該取代基,可舉例如氟原子等鹵素原子、磺酸基、羧基、羥基、胺基、氰基等。
上述酸觸媒,係於水的存在下將烷氧矽烷水解之際作為觸媒作用,所使用之酸觸媒之量,較佳為調製成水解反應之反應系中之濃度為1~1000ppm、特別是5~800ppm之範圍。水之添加量,由於藉此會使聚矽氧烷聚合物之水解率改變,故係視欲得之水解率來決定。
水解反應之反應系中之有機溶劑,可舉例如甲醇、乙醇、丙醇、異丙醇(IPA)、正丁醇等之一價醇、甲基-3-甲氧基丙酸酯、乙基-3-乙氧基丙酸酯等烷基羧酸酯、乙二醇、二乙二醇、丙二醇、甘油、三羥甲基丙烷、己烷三醇等多元醇、乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇
單乙醚、丙二醇單丙醚、丙二醇單丁醚等多元醇之單醚類或該等之單乙酸酯類、乙酸甲酯、乙酸乙酯、乙酸丁酯等之酯類、丙酮、甲乙酮、甲基異戊基酮之酮類、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丙醚、乙二醇二丁醚、丙二醇二甲醚、丙二醇二乙醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙醚等之將多元醇之羥基全部烷基醚化之多元醇醚類等。該等有機溶劑可單獨使用、亦可組合2種以上使用。
藉由於如此之反應系使烷氧矽烷進行水解反應,可得烷氧矽烷化合物(C)。該水解反應,通常係進行1~100小時左右,而為了縮短反應時間,較佳為以不超過80℃之溫度範圍進行加熱。
反應結束後,可得合成之烷氧矽烷化合物(C)、與含有反應所使用之有機溶劑的反應溶液。烷氧矽烷化合物(C),可藉習知之方法與有機溶劑分離,以乾燥之固體狀態、或若需要時取代溶劑之溶液狀態,以上述方法製得。
本實施形態之擴散劑組成物,含有任意成分之有機溶劑(D)。有機溶劑(D),係多元醇(B)以外之有機溶劑。有機溶劑(D),可舉例如甲醇、乙醇、異丙醇、丁醇等醇類、丙酮、二乙基酮、甲乙酮等酮類、乙酸甲酯、乙酸乙酯、乙酸丁酯等酯類、丙二醇、甘油、二丙二醇等多元醇、二丙二醇二甲醚、乙二醇二甲醚、乙二醇二乙醚、丙二醇
二甲醚、丙二醇二乙醚等醚類、乙二醇單甲醚、乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、二丙二醇單甲醚等單醚系二醇類、四氫呋喃、二噁烷等環狀醚類、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯等醚系酯類。
本實施形態之擴散劑組成物,亦可含有其他成分之一般的界面活性劑或消泡劑等。例如,藉由含有界面活性劑,可提升塗布性、平坦化性、展開性,可減少塗布後所形之擴散劑組成物層之塗布偏差的產生。如此之界面活性劑,可使用習知者,而以聚矽氧系之界面活性劑為佳。又,界面活性劑,相對於擴散劑組成物整體,以含有500~3000質量ppm、特別是600~2500質量ppm的範圍為佳。又,若為2000質量ppm以下,擴散處理後之擴散劑組成物層之剝離性優異,故更佳。界面活性劑可單獨使用、亦可組成使用。
擴散劑組成物中所含之金屬雜質(上述之硼酸酯(A)、多元醇(B)及烷氧矽烷化合物(C)所含之金屬成分以外)之濃度,以500ppb以下為佳。藉此,可抑制由於含金屬雜質所產生之光激電力效果之效率的降低。
本實施形態之擴散劑組成物,可將上述各成分以習知之方法,以任意的順序,混合成均勻溶液,藉此來調製。
參照圖1(A)~圖2(D),說明於N型半導體基板形成P型之雜質擴散層之方法、與具備藉此形成有雜質擴散層之半導體基板之太陽能電池之製造方法。圖1(A)~圖1(D)、及圖2(A)~圖2(D),係用以說明實施形態之含有雜質擴散層之形成方法之太陽能電池之製造方法的步驟截面圖。
首先,如圖1(A)所示,準備矽基板等之N型之半導體基板1。接著,如圖1(B)所示,使用周知之濕式蝕刻法,於半導體基板1之一側的主表面,形成具有微細凹凸構造之織構部1a。藉由該織構部1a,可防止半導體基板1表面之光的反射。
接著,如圖1(C)所示,於半導體基板1之織構部1a的主表面,選擇性地塗布上述之擴散劑組成物2。擴散劑組成物2,例如,可藉由噴墨印刷法、網版印刷法、噴霧塗布法、輥塗印刷法、凸版印刷法、凹版印刷法、平版印刷法等選擇性地塗布於半導體基板1的表面。如此形成既定圖型之雜質擴散層後,使用烘箱等周知之手段,乾燥擴散劑組成物2。
接著,如圖1(D)所示,將塗布有擴散劑組成物2之半導體基板1載置於擴散爐內進行燒成。燒成之後,於擴散爐內,使擴散劑組成物2所含之硼酸酯(A)之硼,由半導體基板1之表面擴散至半導體基板1內。又,亦可藉由慣用之雷射的照射,取代擴散爐加熱半導體基板1。如此,硼酸酯(A)之硼會擴散至半導體基板1內而形成P型雜質擴散層3。
接著,如圖2(A)所示,以周知之蝕刻法,除去擴散劑組成物2。接著,如圖2(B)所示,使用周知之化學氣相沉積法(CVD法)、例如使用電漿CVD法,於半導體基板1之織構部1a的主表面,形成氮化矽膜(SiN膜)所構成之鈍化膜4,該鈍化膜4亦具有作為抗反射膜的功能。
接著,如圖2(C)所示,例如藉由將銀(Ag)糊網版印刷,於半導體基板1之鈍化膜4側的主表面,將表面電極5圖型化。表面電極5,係形成圖型以提高太陽能電池的效率。又,例如,藉由將鋁(Al)糊網版印刷,於半導體基板1之另一主表面,形成內面電極6。
接著,如圖2(D)所示,將形成有內面電極6之半導體基板1載置於擴散爐內進行燒成後,使形成於內面電極6之鋁擴散至半導體基板1內。藉此,可減低內面電極6側之電阻。藉由以上之步驟,可製造本實施形態之太陽能電池10。
如以上之說明,本實施形態之擴散劑組成物,含有硼酸酯(A)、與多元醇(B)。藉此,可抑制硼酸酯(A)之凝集及析出,可抑制向外擴散的產生。因此,較佳可採用將擴散劑組成物選擇性地塗布於基板上,使雜質擴散成分局部擴散的擴散法。
又,以往之PBF,一般係樹脂或硼化合物之有機溶劑溶解性低,故其之溶劑組成係由水、與混合於水之高級性溶劑所構成。因此,當欲使用噴墨印刷法或網版印刷法將
PBF溶液塗布於基板時,由於PBF溶液的接觸,有由噴墨噴頭或網版網溶出金屬成分之虞。若金屬成分溶出,則不僅印刷裝置劣化,由於所溶出之金屬的污染擴散,太陽能電池之特性亦劣化。相對於此,本實施型態之擴散劑組成物,係含有烷氧矽烷化合物(C),具有實質上不含水的組成。因此,可避免由噴墨噴頭或網版網溶出金屬成分。
又,於使用可抑制雜質擴散成分之凝集或向外擴散之產生的上述擴散劑組成物形成雜質擴散層時,可更高精度地形成雜質擴散層。再者,由於藉由使用前述擴散劑組成物可以更高精度形成雜質擴散層,故可提升含有如此之雜質擴散層之太陽能電池的可靠性。
本發明並不限於上述之實施形態,亦可根據當業者之知識加入各種設計變更等之變形,加入如此之變形的實施形態亦包含於本發明之範圍內。
以下,說明本發明之實施例,但該等實施例係用以說明本發明之例示,並不因此限定本發明。
將評價試驗I所使用之擴散劑組成物之各成分及含量示於表1。又,於以下之實施例及比較例,界面活性劑,係使用聚矽氧系界面活性劑(SF8421EG:東雷道康寧股份有限公司製)。又,於實施例1~7、9及比較例1~5,
作為有機溶劑(D),係使用二丙二醇單甲醚(MFDG),其之含量,當令擴散劑組成物之總質量為100wt%時,由100wt%減去各成分之含量所剩餘部分的量,即為所有溶劑的含量。於實施例8,有機溶劑(D),係使用丙二醇單甲醚(PGME)及MFDG。PGME之含量,係如表1所示。MFDG含量,當令擴散劑組成物之總質量為100wt%時,係由100wt%減去包含PGME之各成分之含量所剩餘部分的量。
表1中之簡稱係表示以下之化合物。
TEB:硼酸三乙酯(triethyl borate)
TMB:硼酸三甲酯(trimethyl borate)
MPT:3-甲基戊烷-1,3,5-三醇
TMP:三羥甲基丙烷
EG:乙二醇
PG:丙二醇
1,3-BD:1,3-丁二醇
1,4-BD:1,4-丁二醇
MFDG:二丙二醇單甲醚
PGME:丙二醇單甲醚
PPG:聚丙二醇
又,表1中之結構C-1,係以三乙氧矽烷(Si(OC2H5)4)為出發原料之縮合生成物。又,結構C-2、C-3、C-4,分別為下述通式(8)、(9)、(10)所表示之縮合生成物。又,結構C-4之縮合生成物的分子量約為1000±500。
[通式(8)中,p:q為40:20~50:10之範圍。]
[通式(10)中,s為2~5之範圍。]
將根據上述擴散劑組成物之調製方法所調製之實施例1~9及比較例1~5之擴散劑組成物,使用塗布器(SS8261 NUU:東京應化工業股份有限公司製)塗布於樣品基板上。接著,將樣品載置於加熱板上,以150℃施以預烘烤3分鐘。藉由以上之步驟,於實施例1~7及比較例1~5製得厚度300nm、於實施例8、9製得厚度500nm的雜質擴散層。
對於各實施例及各比較例之雜質擴散層,以顯微鏡觀察確認硼酸酯(A)之凝集的有無,評價凝集抑制性(被膜
性)。當未確認到凝集時為良好(O)、確認到凝集時為不適(×)。將結果示於表1。
如表1所示,未含有上述通式(1)所表示之多元醇(B)之比較例1~5,凝集抑制性為不適。相對於此,含有上述通式(1)所表示之多元醇(B)之實施例1~9,凝集抑制性為良好。因此,當於擴散劑組成物中含有硼酸酯(A)與上述通式(1)所表示之多元醇(B)時,確認可抑制硼酸酯(A)的凝集。
參照圖3,說明評價試驗II。圖3(A)及圖3(B),係用以說明向外擴散抑制性之評價試驗中之熱擴散步驟的模式圖。
首先,準備上述試驗評價I中之實施例1~3及比較例2之擴散劑組成物。又,作為比較例6,準備習知之PBF之含硼之雜質擴散劑(PBF 3P-31A:東京應化工業股份有限公司製)。
將實施例1~3及比較例2、6之擴散劑組成物,使用塗布器(SS8261 NUU:東京應化工業股份有限公司製)塗布於N型半導體基板上。接著,將樣品基板載置於加熱板上,於實施例1~3及比較例2以200℃施以預烘烤0.5分鐘、於比較例6以150℃施以預烘烤3分鐘。藉由
以上之步驟,於實施例1~3及比較例2製得厚度800nm、於比較例6製得厚度400nm的雜質擴散層。
接著,如圖3(A)所示,除塗布有擴散劑組成物2之半導體基板1之外,準備未塗布擴散劑組成物2之虛擬基板11。而如圖3(B)所示,於擴散爐12內將實施例1~3及比較例2、6之半導體基板1與虛擬基板11相鄰地載置。半導體基板1與虛擬基板11之間之距離r為4mm。擴散爐12,係使用光洋熱系統製VF-1000。於擴散爐12內、O2中,以600℃燒成30分鐘。之後,於N2中,於實施例1~3及比較例2以985℃加熱15分鐘、於比較例6以950℃加熱30分鐘以使硼擴散。
對於實施例1~3及比較例2、6,使用薄片電阻測定器(VR-70:國際電氣股份有限公司製)以四探針法,測定半導體基板1(塗布基板)的薄片電阻值、與虛擬基板11的薄片電阻值。各別對半導體基板1及虛擬基板11,測定25點之薄片電阻值,計算出平均值。又,計算出電阻值比(相對於半導體基板1之薄片電阻值之虛擬基板11之薄片電阻值的大小)。將結果示於表2。
如表2所示,任一之實施例皆顯示較比較例2、6高之電阻值比。比較例2、6,硼由塗布於半導體基板1之擴散劑組成物朝被膜外部飛散附著於虛擬基板11,附著之硼擴散至虛擬基板11的結果,推測虛擬基板11之薄片電阻值降低而電阻值比減小。相對於,實施例1~3,推測由於抑制了硼的朝被膜外部飛散、亦即抑制了向外擴散,故抑制了虛擬基板11之薄片電阻值的降低,可維持電阻值比為高的值。因此,可理解當擴散組成物中含有硼酸酯(A)與上述通式(1)所表示之多元醇(B)時,能抑制硼的向外擴散。
例如,以下組合的實施形態亦包含於本發明的範圍。
一種擴散劑組成物,其係於半導體基板之雜質擴散層之形成所使用的擴散劑組成物,其特徵係含有:硼酸酯(A)、
下述通式(1)所表示之多元醇(B)、與烷氧矽烷化合物(C)。
[通式(1)中,k為0~3之整數。m為1以上之整數。R2及R3,分別獨立地為氫原子、羥基、碳原子數1~5之烷基、或碳原子數1~5之羥烷基。當R2及R3為複數時,複數之R2及R3可分別為相同或相異。又,當k為2以上時,複數之R2及R3必須含有一個以上之羥基或碳原子數1~5之羥烷基。R4及R5,分別獨立地為氫原子或碳原子數1~3之烷基]。
如項目1所記載之擴散劑組成物,其中,前述硼酸酯(A),係下述通式(2)所表示;B(OR1)3 (2)
[通式(2)中,R1分別獨立地為碳原子數1~10之烷基、或碳原子數6~10之芳基。3個R1可為相同或相異]。
如項目1或2所記載之擴散劑組成物,其中,前述硼酸酯(A)之含量,係前述多元醇(B)之含量的5倍莫耳以下。
如項目1至3中任一項所記載之擴散劑組成物,其實質上不含有水。
如項目1至4中任一項所記載之擴散劑組成物,其中,前述烷氧矽烷化合物(C),係含有下述通式(3)所表示之烷氧矽烷水解所得之反應生成物。
R6 nSi(OR7)4-n (3)
[通式(3)中,R6為氫原子或有機基。R7為有機基。n為0、1、或2之整數。當R6為複數時,複數之R6可為相同或相異,當(OR7)為複數時,複數之(OR7)可為相同或相異]。
如項目1至5中任一項所記載之擴散劑組成物,其含有前述多元醇(B)以外之有機溶劑(D)。
如項目1至6中任一項所記載之擴散劑組成物,其係使用於藉選擇性塗布以形成既定圖型之雜質擴散層時。
一種雜質擴散層之形成方法,其特徵係含有:於半導體基板,將項目1至7中任一項所記載之擴散劑組成物選擇性地塗布以形成既定圖型之雜質擴散層的圖型形成步驟;與使前述擴散劑組成物所含之硼酸酯(A)中之硼,擴散於前述半導體基板的擴散步驟。
一種太陽能電池,其特徵係,具備以項目8之雜質擴散層之形成方法形成有雜質擴散層之半導體基板。
本發明可利用於擴散劑組成物、雜質擴散層之形成方法及太陽能電池。
1‧‧‧半導體基板
1a‧‧‧織構部
2‧‧‧擴散劑組成物
3‧‧‧P型雜質擴散層
4‧‧‧鈍化膜
5‧‧‧表面電極
6‧‧‧內面電極
10‧‧‧太陽能電池
11‧‧‧虛擬基板
12‧‧‧擴散層
圖1(A)~圖1(D),係用以說明實施形態之含有雜質擴散層之形成方法之太陽能電池之製造方法的步驟截面圖。
圖2(A)~圖2(D),係用以說明實施形態之含有雜質擴散層之形成方法之太陽能電池之製造方法的步驟截面圖。
圖3(A)及圖3(B),係用以說明向外擴散抑制性之評
價試驗中之熱擴散步驟的模式圖。
Claims (9)
- 一種擴散劑組成物,其係於半導體基板形成雜質擴散層所使用之擴散劑組成物,其特徵係含有:硼酸酯(A)、下述通式(1)所表示之多元醇(B)、與烷氧矽烷化合物(C);
[通式(1)中,k為0~3之整數;m為1以上之整數;R2及R3分別獨立地為氫原子、羥基、碳原子數1~5之烷基、或碳原子數1~5之羥烷基;R2及R3為複數時,複數之R2及R3可分別為相同或相異;又,當k為2以上時,複數之R2及R3必須含有一個以上之羥基或碳原子數1~5之羥烷基;R4及R5,分別獨立地為氫原子或碳原子數1~3之烷基]。 - 如申請專利範圍第1項之擴散劑組成物,其中,前述硼酸酯(A)係下述通式(2)所表示;B(OR1)3 (2)[通式(2)中,R1分別獨立地為碳原子數1~10之烷基、或碳原子數6~10之芳基;3個R1可為相同或相異]。
- 如申請專利範圍第1項之擴散劑組成物,其中,前述硼酸酯(A)之含量係前述多元醇(B)之含量的5倍莫耳以下。
- 如申請專利範圍第1項之擴散劑組成物,其實質上不含有水。
- 如申請專利範圍第1項之擴散劑組成物,其中前述烷氧矽烷化合物(C),係含有下述通式(3)所表示之烷氧矽烷水解所得之反應生成物;R6 nSi(OR7)4-n (3)[通式(3)中,R6為氫原子或有機基;R7為有機基;n為0、1、或2之整數;當R6為複數時,複數之R6可為相同或相異,當(OR7)為複數時,複數之(OR7)可為相同或相異]。
- 如申請專利範圍第1項之擴散劑組成物,其含有前述多元醇(B)以外之有機溶劑(D)。
- 如申請專利範圍第1項之擴散劑組成物,其係使用於藉選擇性塗布以形成既定圖型之雜質擴散層時。
- 一種雜質擴散層之形成方法,其特徵係含有:於半導體基板,將申請專利範圍第1項之擴散劑組成物選擇性地塗布以形成既定圖型之雜質擴散層的圖型形成步驟;與使前述擴散劑組成物所含之硼酸酯(A)中之硼,擴散 於前述半導體基板的擴散步驟。
- 一種太陽能電池,其特徵係,具備以申請專利範圍第8項之雜質擴散層之形成方法形成有雜質擴散層之半導體基板。
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| JP6672034B2 (ja) * | 2016-03-24 | 2020-03-25 | 東京応化工業株式会社 | 不純物拡散剤組成物、及び半導体基板の製造方法 |
| JP7051633B2 (ja) * | 2018-07-30 | 2022-04-11 | グローバルウェーハズ・ジャパン株式会社 | シリコンウェーハの製造方法 |
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| JPS5534258A (en) * | 1978-09-01 | 1980-03-10 | Tokyo Denshi Kagaku Kabushiki | Coating solution for forming silica film |
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| JP2013077804A (ja) | 2013-04-25 |
| JP6022243B2 (ja) | 2016-11-09 |
| CN103688340A (zh) | 2014-03-26 |
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