TWI539611B - A diffusion agent composition, a method for forming an impurity diffusion layer, and a solar cell - Google Patents
A diffusion agent composition, a method for forming an impurity diffusion layer, and a solar cell Download PDFInfo
- Publication number
- TWI539611B TWI539611B TW100114637A TW100114637A TWI539611B TW I539611 B TWI539611 B TW I539611B TW 100114637 A TW100114637 A TW 100114637A TW 100114637 A TW100114637 A TW 100114637A TW I539611 B TWI539611 B TW I539611B
- Authority
- TW
- Taiwan
- Prior art keywords
- solvent
- diffusing agent
- agent composition
- impurity
- semiconductor substrate
- Prior art date
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- 239000012535 impurity Substances 0.000 title claims description 73
- 238000009792 diffusion process Methods 0.000 title claims description 65
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- 239000000463 material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
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Description
本發明係有關一種擴散劑組成物、雜質擴散層之形成方法及太陽能電池。
一般而言,於製造太陽能電池時,在半導體基板中形成P型或N型雜質擴散層時,在半導體基板表面上塗佈含P型或N型雜質擴散成分之擴散劑,且使由經塗佈的擴散劑所成的雜質擴散成分擴散於半導體基板中,形成雜質擴散層。
在半導體基板表面上塗佈擴散劑之方法,大多數使用旋轉塗佈法,惟試行採用篩網印刷法等之其他方法。而且,伴隨於此,企求可使用於各種方法之擴散劑。例如,於專利文獻1中揭示有適用於篩網印刷法時之硼擴散用塗佈液(擴散劑組成物)。
[專利文獻1]日本特開2007-35719號公報
一般而言,於太陽能電池中大多使用的半導體基板為矽基板,該矽基板之表面上形成稱為結構(texture)之約2μm的微細凹凸。因此,在半導體基板之表面上塗佈擴散
劑組成物時,會有凸部上之擴散劑組成物流入凹部而露出凸部的可能性。另外,因為擴散劑組成物流入凹部,擴散劑組成物之層厚變得不均勻,擴散劑組成物因加熱而收縮時產生破裂,且擴散劑組成物之層自基板浮出,會有雜質擴散成分之擴散效率降低的可能性。因此,企求擴散劑組成物可均勻地塗佈於半導體基板表面上,即塗膜形成性高。
此外,在半導體基板表面上塗佈擴散劑之其他方法,試行採用噴霧塗佈法。用以使用於噴霧塗佈法時之擴散劑組成物中,除相對於擴散劑組成物而言之基板要求的塗膜形成性高外,企求不易引起噴霧噴嘴阻塞情形,即吐出安定性高。
本發明係有鑑於該情形而發明者,其目的以提供具有優異的塗膜形成性及吐出安定性,且可適合於噴霧塗佈法所採用的擴散劑組成物,使用該擴散劑組成物之雜質擴散層的形成方法,及太陽能電池。
為解決上述課題時,本發明之形態為擴散劑組成物,該擴散劑組成物,其係於半導體基板上形成雜質擴散劑層時使用的擴散劑組成物,其特徵為含有雜質擴散成分(A)、矽化合物(B)及含有沸點為100℃以下之溶劑(C1)、沸點為120~180℃之溶劑(C2)與沸點為240~300℃之溶劑(C3)的溶劑(C)。
藉由該形態,可製得具有優異的塗膜形成性及吐出安定性,且可適合於噴霧塗佈法採用的擴散劑組成物。
本發明另一形態為雜質擴散層之形成方法,該雜質擴散層之形成方法,其特徵為含有在半導體基板上藉由噴霧塗佈處理印刷上述形態之擴散劑組成物,形成特定圖案之雜質擴散劑層之圖案形成步驟,及使擴散劑組成物之雜質擴散成分(A)擴散於半導體基板之擴散步驟。
藉由該形態,可更為高精度地形成雜質擴散層。
本發明另一形態為太陽能電池,該太陽電池,其特徵為具備藉由上述形態之雜質擴散層的形成方法形成雜質擴散層之半導體基板。
藉由該形態,可製得信賴性更高的太陽能電池。
藉由本發明,可提供一種具有優異的塗膜形成性及吐出安定性,且可適合噴霧塗佈法採用的擴散劑組成物,使用該擴散劑組成物之雜質擴散層的形成方法,及太陽能電池。
於下述中,以適合的實施形態更詳細地說明本發明。實施形態不為限定發明之例示,實施形態所記載的全部特徵或其組合,不一定必須限於發明之本質者。
本實施形態之擴散劑組成物,係在半導體基板上形成雜質擴散劑層時使用的擴散劑組成物,較佳者為藉由噴霧塗佈形成雜質擴散劑層時使用的擴散劑組成物。因此,本
實施形態之擴散劑組成物,含有雜質擴散成分(A)、矽化合物(B),及含有沸點為100℃以下之溶劑(C1)、沸點為120~180℃之溶劑(C2)與沸點為240~300℃之溶劑(C3)之溶劑(C)。於下述中,詳細說明有關本實施形態之擴散劑組成物的各成分。
雜質擴散成分(A),一般而言作為摻雜劑於製造太陽能電池時使用的化合物。雜質擴散成分(A)為含有III族(第13族)元素之化合物的P型雜質擴散成分,或含有V族(第15族)元素之化合物的N型雜質擴散成分,於形成太陽能電池之電極的步驟中,可於半導體基板內形成P型或N型雜質擴散層(雜質擴散範圍)。含有III族元素之化合物的P型雜質擴散成分,於形成太陽能電池之電極的步驟中,在N型半導體基板內可形成P型雜質擴散層,在P型半導體基板內可形成P+(高濃度P型)之雜質擴散層。雜質擴散成分(A)中所含的III族元素之化合物,例如B2O3、Al2O3等,雜質擴散成分(A)中含有1種以上此等之化合物。而且,含有V族元素之化合物的N型雜質擴散成分,於形成太陽能電池之電極的步驟中,可在P型半導體基板內形成N型雜質擴散層,可在N型半導體基板內形成N+型(高濃度N型)雜質擴散層。雜質擴散成分(A)中所含的V族元素之化合物,例如P2O5、Bi2O3、Sb(OCH2CH3)3、SbCl3、As(OC4H9)3等。
雜質擴散成分(A)之濃度,係視半導體基板上所形成的雜質擴散層之層厚等而定予以適當調整。例如,雜質擴散成分(A)相對於擴散劑組成物之全部質量而言,以含有0.1質量%以上較佳,以含有1.0質量%以上更佳。而且,雜質擴散成分(A)以相對於擴散劑組成物之全部質量而言含有10質量%以下較佳。
矽化合物(B)只要是在半導體基板上形成矽系被覆時使用的習知的化合物即可,沒有特別的限制。矽化合物(B)例如選自使SiO2微粒子及烷氧基矽烷水解所得的反應生成物(以下適當稱為烷氧基矽烷之水解生成物)所成群中之至少1種。於下述中,各說明有關SiO2微粒子及烷氧基矽烷之水解生成物。
SiO2微粒子之大小,以平均粒徑為1μm以下較佳。平均粒徑提高為1μm時,使用噴霧塗佈裝置塗佈擴散劑組成物時,恐會妨礙噴霧噴嘴之擴散劑組成物通過。SiO2微粒子之具體例,如氣相二氧化矽等。
水解生成物之出發材料的烷氧基矽烷係以下述一般式(1)所示之含Si的化合物。
R1 nSi(OR2)4-n (1)[式中,R1係氫原子、烷基或芳基,R2係烷機或芳基,n係表示0、1或2之整數。R1為複數個時,複數個R1可為相同或不相同。(OR2)為複數個時,複數個之(OR2)可相同或不同。]
R1為烷基時,以碳數1~20之直鏈狀或支鏈狀烷基較佳,以碳數1~4之直鏈狀或支鏈狀烷基更佳。R1中至少一個以烷基或芳基較佳。芳基例如苯基。
R2為烷基時,以碳數1~5之直鏈狀或支鏈狀烷基較佳,就水解速度而言以碳數1~3之烷基更佳。n以0較佳。芳基例如苯基。
上述一般式(1)之n為0時,烷氧基矽烷(i)例如以下述一般式(2)表示。
Si(OR21)a(OR22)b(OR23)c(OR24)d (2)[上述式(2)中,R21、R22、R23及R24係各獨立地表示與上述R2相同的烷基或芳基。a、b、c及d係0≦a≦4,0≦b≦4,0≦c≦4,0≦d≦4,且滿足a+b+c+d=4之條件的整數。]
上述一般式(1)之n為1時的烷氧基矽烷(ii),例如以下述一般式(3)表示。
R31Si(OR32)e(OR33)f(OR34)g (3)[上述式(3)中,R31係表示與上述R1相同的氫原子、烷基或芳基,R32、R33及R34係各獨立地表示與上述R2相同
的烷基或芳基。e、f及g係0≦e≦3,0≦f≦3,0≦g≦3,且滿足e+f+g=3之條件的整數。]
上述一般式(1)之n為2時的烷氧基矽烷(iii),例如以下述一般式(4)表示。
R41R42Si(OR43)h(OR44)i (4)[上述式(4)中,R41及R42係表示與上述R1相同的氫原子、烷基或芳基。R41及R42中至少1個為烷基或芳基。R43及R44係各獨立地表示與上述R2相同的烷基或芳基。h及i係0≦h≦2,0≦i≦2,且滿足h+i=2之條件的整數。]
烷氧基矽烷(i)之具體例,如四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四丁氧基矽烷、四戊氧基矽烷、四苯氧基矽烷、三甲氧基單乙氧基矽烷、二甲氧基二乙氧基矽烷、三乙氧基單甲氧基矽烷、三甲氧基單丙氧基矽烷、單甲氧基三丁氧基矽烷、單甲氧基三戊氧基矽烷、單甲氧基三苯氧基矽烷、二甲氧基二丙氧基矽烷、三丙氧基單甲氧基矽烷、三甲氧基單丁氧基矽烷、二甲氧基二丁氧基矽烷、三乙氧基單丙氧基矽烷、二乙氧基二丙氧基矽烷、三丁氧基單丙氧基矽烷、二甲氧基單乙氧基單丁氧基矽烷、二乙氧基單甲氧基單丁氧基矽烷、二乙氧基單丙氧基單丁氧基矽烷、二丙氧基單甲氧基單乙氧基矽烷、二丙氧基單甲氧基單丁氧基矽烷、二丙氧基單乙氧基單丁氧基矽烷、二丁氧基單甲氧基單乙氧基矽烷、二丁氧基單乙氧基單丙氧基矽烷、單甲氧基單乙氧基單丙氧基單丁氧基矽烷等之四烷氧基矽烷,其中,以四甲氧基矽烷、四乙氧基矽烷較
佳。
烷氧基矽烷(ii)之具體例,如甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三丙氧基矽烷、甲基三戊氧基矽烷、乙基三甲氧基矽烷、乙基三丙氧基矽烷、乙基三戊氧基矽烷、乙基三苯氧基矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽烷、丙基三戊氧基矽烷、丙基三苯氧基矽烷、丁基三甲氧基矽烷、丁基三乙氧基矽烷、丁基三丙氧基矽烷、丁基三戊氧基矽烷、丁基三苯氧基矽烷、甲基單甲氧基二乙氧基矽烷、乙基單甲氧基二乙氧基矽烷、丙基單甲氧基二乙氧基矽烷、丁基單甲氧基二乙氧基矽烷、甲基單甲氧基二丙氧基矽烷、甲基單甲氧基二戊氧基矽烷、甲基單甲氧基二苯氧基矽烷、乙基單甲氧基二丙氧基矽烷、乙基單甲氧基二戊氧基矽烷、乙基單甲氧基二苯氧基矽烷、丙基單甲氧基二丙氧基矽烷、丙基單甲氧基二戊氧基矽烷、丙基單甲氧基二苯氧基矽烷、丁基單甲氧基二丙氧基矽烷、丁基單甲氧基二戊氧基矽烷、丁基單甲氧基二苯氧基矽烷、甲基甲氧基乙氧基丙氧基矽烷、丙基甲氧基乙氧基丙氧基矽烷、丁基甲氧基乙氧基丙氧基矽烷、甲基單甲氧基單乙氧基單丁氧基矽烷、乙基單甲氧基單乙氧基單丁氧基矽烷、丙基單甲氧基單乙氧基單丁氧基矽烷、丁基單甲氧基單乙氧基單丁氧基矽烷等。其中,甲基三烷氧基矽烷(特別是甲基三甲氧基矽烷、甲基三乙氧基矽烷)較佳。
烷氧基矽烷(iii)之具體例,如甲基二甲氧基矽烷、甲基甲氧基乙氧基矽烷、甲基二乙氧基矽烷、甲基甲氧基丙
氧基矽烷、甲基甲氧基戊氧基矽烷、甲基甲氧基苯氧基矽烷、乙基二丙氧基矽烷、乙基甲氧基丙氧基矽烷、乙基二戊氧基矽烷、乙基二苯氧基矽烷、丙基二甲氧基矽烷、丙基甲氧基乙氧基矽烷、丙基乙氧基丙氧基矽烷、丙基二乙氧基矽烷、丙基二戊氧基矽烷、丙基二苯氧基矽烷、丁基二甲氧基矽烷、丁基甲氧基乙氧基矽烷、丁基二乙氧基矽烷、丁基乙氧基丙氧基矽烷、丁基二丙氧基矽烷、丁基甲基二戊氧基矽烷、丁基甲基二苯氧基矽烷、二甲基二甲氧基矽烷、二甲基甲氧基乙氧基矽烷、二甲基二乙氧基矽烷、二甲基二戊氧基矽烷、二甲基二苯氧基矽烷、二甲氧基乙氧基丙氧基矽烷、二甲基二丙氧基矽烷、二乙基二甲氧基矽烷、二乙基甲氧基丙氧基矽烷、二乙基二乙氧基矽烷、二乙基乙氧基丙氧基矽烷、二丙基二甲氧基矽烷、二丙基二乙氧基矽烷、二丙基二戊氧基矽烷、二丙基二苯氧基矽烷、二丁基二甲氧基矽烷、二丁基二乙氧基矽烷、二丁基二丙氧基矽烷、二丁基甲氧基戊氧基矽烷、二丁基甲氧基苯氧基矽烷、甲基乙基二甲氧基矽烷、甲基乙基二乙氧基矽烷、甲基乙基二丙氧基矽烷、甲基乙基二戊氧基矽烷、甲基乙基二苯氧基矽烷、甲基丙氧基二甲氧矽烷、甲基丙基二乙氧基矽烷、甲基丁基二甲氧基矽烷、甲基丁基二乙氧基矽烷、甲基丁基二丙氧基矽烷、甲基乙基乙氧基丙氧基矽烷、乙基丙基二甲氧基矽烷、乙基丙基甲氧基乙氧基矽烷、二丙基二甲氧基矽烷、二丙基甲氧基乙氧基矽烷、丙基丁基二甲氧基矽烷、丙基丁基二乙氧基矽烷、二
丁基甲氧基乙氧基矽烷、二丁基甲氧基丙氧基矽烷、二丁基乙氧基丙氧基矽烷等,其中,以甲基二甲氧基矽烷、甲基二乙氧基矽烷較佳。
為製得上述水解生成物時使用的烷氧基矽烷,可適當選自上述烷氧基矽烷(i)~(iii)。烷氧基矽烷尤以烷氧基矽烷(i)較佳。而且,混合使用此等之烷氧基矽烷時,更佳的組合為烷氧基矽烷(i)與烷氧基矽烷(ii)之組合。使用烷氧基矽烷(i)與烷氧基矽烷(ii)時,此等之使用比例以烷氧基矽烷(i)為10~60莫耳%、烷氧基矽烷(ii)為90~40莫耳%之範圍內較佳,以烷氧基矽烷(i)為15~50莫耳%、烷氧基矽烷(ii)為85~50莫耳%之範圍內更佳。此外,烷氧基矽烷(ii)係上述一般式(3)中R31之較佳者為烷基或芳基,更佳者為烷基。
上述水解生成物,例如以使1種或2種以上選自上述烷氧基矽烷(i)~(iii),在酸觸媒、水、有機溶劑存在下進行水解的方法予以調製。
酸觸媒可使用有機酸、無機酸中任何一種。無機酸可使用硫酸、磷酸、硝酸、鹽酸等,其中,以使用磷酸、硝酸為宜。有機酸可使用甲酸、乙酸、富馬酸、馬來酸、冰醋酸、醋酸酐、丙酸、正丁酸等之羧酸,及具有含硫之酸殘基的有機酸作為有機酸。具有含硫之酸殘基的有機酸,例如有機磺酸等,此等之酯化物例如有機硫酸酯、有機亞硫酸酯等。於此等之中,特別是以有機磺酸、例如以下述一般式(5)所示之化合物較佳。
R13-X (5)[上述式(5)中,R13為可具有取代基之烴基,X為磺酸基。]
於上述一般式(5)中,R13之烴基以碳數1~20之烴基較佳。該烴基可以為飽和者,亦可為不飽和者,可為直鏈狀、支鏈狀、環狀中任何一種。R13之烴基為環狀時,例如苯基、萘基、蒽基等之芳香族烴基較佳,其中,以苯基更佳。於該芳香族烴基之芳香環中,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的烴基,可以為飽和者或不飽和者,可為直鏈狀、支鏈狀、環狀中任何一種。而且,R13之烴基可具有1個或複數個取代基,該取代基例如氟原子等之鹵素原子、磺酸基、羧基、羥基、胺基、氰基等。以上述一般式(5)所示之有機磺酸,就光阻圖型下方之形狀的改善效果而言,特別是以九氟化丁烷磺酸、甲烷磺酸、三氟化甲烷磺酸、十二烷基苯磺酸或此等之混合物等較佳。
上述酸觸媒係在水存在下使烷氧基矽烷進行水解時作用作為觸媒,使用的酸觸媒之量係在水解反應之反應系中的濃度為1~1000ppm,特別是調製於5~800ppm之範圍內較佳。水之添加量,由於可藉此改變矽氧烷聚合物之水解率,故視所得的水解率而定予以決定。
在水解反應之反應系中的有機溶劑,例如甲醇、乙醇、丙醇、異丙醇(IPA)、正丁醇之一元醇、如甲基-3-甲氧基丙酸酯、乙基-3-乙氧基丙酸酯之烷基羧酸酯、如乙
二醇、二乙二醇、丙二醇、丙三醇、三羥甲基丙烷、己三醇等之多元醇、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、丙二醇單丁醚等之多元醇的單醚類或此等之單乙酸酯類、如醋酸甲酯、醋酸乙酯、醋酸丁酯之酯類、丙酮、甲基乙酮、甲基異戊酮等之酮類、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、二乙二醇甲基乙醚之多元醇的羥基全部被烷基醚化的多元醇醚類等。此等之有機溶劑,可單獨使用,亦可2種以上組合使用。
在該反應系中藉由使烷氧基矽烷進行水解反應,製得矽氧烷聚合物。該水解反應通常在5~100小時內完成,為縮短反應時間時,以不超過80℃之溫度範圍加熱較佳。
於反應完成後,製得被合成的矽氧烷聚合物與含有反應時使用的有機溶劑之反應溶液。矽氧烷聚合物可藉由習知的方法與有機溶劑分離且乾燥而製得。
本實施形態之擴散劑組成物之矽化合物(B)的配合量,相對於擴散劑組成物之全部質量而言,以SiO2換算為2~10質量%較佳。藉由以上述範圍予以配合,可抑制在擴散劑組成物之被膜上產生破裂情形,且可得良好的雜質之擴散效果。
溶劑(C)(溶劑成分)係含有沸點為100℃以下之溶劑(C1)、沸點為120~180℃之溶劑(C2)及沸點為240~300℃之溶劑(C3)。於下述中,各說明有關各溶劑(C1)~(C3)。
溶劑(C1)係沸點為100℃以下之溶劑,在常壓下之沸點為該條件者即可,可為任何的溶劑。藉由含有溶劑(C1),可形成在擴散劑組成物中溶解有雜質擴散成分(A)之狀態,而且,擴散劑組成物之乾燥速度變快,可防止塗佈後之圖型的滲透或變寬。該溶劑(C1)之具體例,如甲醇(沸點:64.7℃)、乙醇(沸點:78.4℃)、醋酸乙酯(沸點:77.1℃)、醋酸甲酯(沸點:56.9℃)、甲基乙酮(沸點:79.5℃)、丙酮(沸點:56.5℃)等。此等之溶劑可單獨使用,亦可組合2種以上組合。溶劑(C1)特別是以乙醇更佳。
溶劑(C1)相對於擴散劑組成物之溶劑(C)的全部質量而言,以含有70質量%以上較佳,另外,以含有70~80質量%更佳。溶劑(C1)未達70質量%時,會有無法溶解企求量之雜質擴散成分(A)。而且,溶劑(C1)相對於擴散劑組成物之全部質量而言,以含有50~70質量%較佳。
溶劑(C2)係沸點為120~180℃、即120℃以上且
180℃以下之溶劑,在常壓下之沸點為該條件所成的溶劑即可。藉由含有溶劑(C2),可提高擴散劑組成物之塗膜形成性,可防止塗佈後所形成的擴散劑組成物層(雜質擴散劑層)產生塗佈斑點。該溶劑(C2)之具體例,如丙二醇單甲醚(PGME)(沸點:120℃)、丙二醇單乙醚(沸點:132℃)、丙二醇單丁醚(沸點:170℃)、丙二醇單丙醚(沸點:150℃)、3-甲氧基丁基乙酸酯(沸點:171℃)等。於此等之溶劑中,二元醇類以視用途而定適合的溶劑之黏度較佳。此等之溶劑可單獨使用,亦可組合2種以上組合。
溶劑(C2)相對於擴散劑組成物之溶劑成分的全部質量而言,以含有10質量%以上較佳,另外,以含有10~20質量%更佳。溶劑(C2)為10質量%以上時,可得充分的塗膜形成性的提高效果。此外,溶劑(C2)相對於擴散劑組成物之全部質量而言,以含有5~20質量%較佳。
溶劑(C3)係沸點為240~300℃,即240℃以上且300℃以下之溶劑,在常壓下之沸點為該條件所成的溶劑即可。藉由含有溶劑(C3),可抑制擴散劑組成物過度乾燥,可防止因此而導致的噴霧噴嘴阻塞的情形。結果,可提高擴散劑組成物之吐出安定性,且可藉由噴霧塗佈法形成安定的雜質擴散劑層。此外,藉由添加溶劑(C3),可提高雜質擴散性能。此係推測藉由溶劑(C3)具有的雜質擴散成分(A)中雜質化合物之還原機能者。該溶劑(C3)之具體
例,如三丙二醇單甲醚(TPGM)(沸點:242℃)、酯醇(texanol)(沸點:244℃)、丙三醇(沸點:290℃)、三乙二醇單丁醚(沸點:271℃)等。於此等之溶劑中,二元醇類以視用途而定適合的溶劑之黏度較佳。此等之溶劑可單獨使用,亦可組合2種以上組合。
溶劑(C3)相對於擴散劑組成物之溶劑成分的全部質量而言,以含有10質量%以上較佳,另外,以含有10~20質量%更佳。溶劑(C3)為10質量%以上時,可得充分的吐出安定性之提高效果。而且,溶劑(C3)相對於擴散劑組成物之全部質量而言,以含有5~20質量%較佳。
本發明形態之擴散劑組成物,亦可含有一般的界面活性劑作為其他成分(D)。例如,藉由含有界面活性劑,可提高塗佈性、平坦性、展開性,可減少塗佈後所形成的擴散劑組成物層產生塗佈斑點。該界面活性劑,可使用習知者,惟以聚矽氧烷系界面活性劑較佳。而且,界面活性劑相對於擴散劑組成物全體而言,含有500~3000質量ppm,特別是以600~2500質量ppm之範圍較佳。另外,為2000質量ppm以下時,由於擴散處理後之擴散劑組成物層的剝離性優異,故更佳。界面活性劑可單獨使用,亦可組合使用。
而且,擴散劑組成物亦可含有雜質擴散成分(A)之擴散助劑的聚丙二醇(PPG)或二丙二醇(DPG)等之添加劑作為
其他成分(D)。
本實施形態之擴散劑組成物中所含的金屬雜質(上述之雜質擴散成分(A)、矽化合物(B)及溶劑(C)中所含的金屬成分外)之濃度,以500ppb以下較佳。藉此,可抑制因含有金屬雜質所產生的光起電力效果之效率降低的情形。
本實施形態之擴散劑組成物,係使上述之各成分藉由習知的方法,以任意的順序混合形成均勻溶液予以調製。
此時,以全部固體成分濃度為6質量%以下予以調製較佳。藉由形成該濃度,可將吐出後所形成的圖型調整成適當的厚度。
參照第1(A)圖~第2(D)圖,說明有關在N型半導體基板上使用噴霧塗佈法形成P型雜質擴散層之方法,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的製造方法。第1(A)圖~第1(D)圖、及第2(A)圖第2(D)圖,係為說明含有實施形態之雜質擴散層的形成方法之太陽能電池的製造方法時之步驟截面圖。
本實施形態之雜質擴散層的形成方法,係包含使N型半導體基板中含有P型雜質擴散成分(A)之上述擴散劑組成物藉由噴霧塗佈予以印刷,形成一定圖型之雜質擴散劑層之圖型形成方法,與在半導體基板上使擴散劑組成物
之雜質擴散成分(A)擴散的擴散步驟。
首先,如第1(A)圖所示,使用矽基板等之N型半導體基板1。然後,如第1(B)圖所示,使用習知的濕式蝕刻方法,在半導體基板1之一主表面上形成具有微細的凹凸構造之結構部1a。藉由該結構部1a,防止半導體基板1表面之光的反射情形。然後,第1(C)圖所示,在半導體基板1之結構部1a側的主表面上塗佈含有P型雜質擴散成分(A)之上述擴散劑組成物2。
擴散劑組成物2係藉由噴霧塗佈法塗佈於半導體基板1之表面上。換言之,藉由使用任意的噴霧塗佈裝置,自該噴霧塗佈裝置之噴霧噴嘴吐出擴散劑組成物2,將擴散劑組成物2吹附於半導體基板1之表面上,在半導體基板1之表面上印刷擴散劑組成物2。如此形成的一定圖型之雜質擴散劑層後,使使用烤箱等習知的手段塗佈的擴散劑組成物2予以乾燥。
其次,第1(D)圖所示,將塗佈有擴散劑組成物2之半導體基板1載負於電爐內予以燒成。於燒成後,使電爐內擴散劑組成物2中之P型雜質擴散成分(A)自半導體基板1之表面擴散於半導體基板1內。而且,亦可藉由慣用的雷射照射以取代電爐,使半導體基板1進行加熱。如此將P型雜質擴散成分(A)擴散於半導體基板1內,形成P型雜質擴散層3。
其次,如第2(A)圖所示,藉由周知的蝕刻法,除去擴散劑組成物2。然後,如第2(B)圖所示,使用周知的化
學氣相成長法(CVD法)、例如電漿CVD法,在半導體基板1之結構部1a側的主表面上形成矽氮化膜(SiN膜)所成的鈍化膜4。該鈍化膜4亦可作為防止反射膜之機能。
其次,如第2(C)圖所示,例如藉由使銀(Ag)糊料進行篩網印刷,在半導體基板1之鈍化膜4側之主表面上使表面電極5予以圖型化。表面電極5係在提高太陽能電池之效率下予以圖型形成。而且,例如藉由使鋁(Al)糊料進行篩網印刷,形成半導體基板1之另一主表面上形成背面電極6。
另外,如第2(D)圖所示,例如將形成有背面電極6之半導體基板1載置於電爐內予以燒成後,使形成背面電極6之鋁擴散於半導體基板1內。藉此,可減低背面電極6側之電阻。藉由上述之步驟,可製造本實施形態之太陽能電池10。
如上述說明,本實施形態之擴散劑組成物,係在半導體基板上形成雜質擴散劑層時使用的擴散劑組成物,含有雜質擴散成分(A)、矽化合物(B)與含沸點為100℃以下之溶劑(C1)、沸點為120~180℃之溶劑(C2)及沸點為240~300℃之溶劑(C3)的溶劑(C)。藉此,擴散劑組成物具有優異的塗膜形成性及吐出安定性。而且,可具有擴散劑組成物優異的擴散性能。另外,本實施形態之擴散劑組成物,由於具備該優異的塗膜形成性及吐出安定性,可適合於藉由噴霧塗佈形成雜質擴散劑層使用。然後,使用塗膜形成性、吐出安定性及擴散性優異的擴散劑組成物,形成雜質擴
散層時,可更為高精度形成雜質擴散層。另外,藉由使用該擴散劑組成物,可形成更為精度高的雜質擴散層,可提高含該雜質擴散層之太陽能電池之信賴性。
本發明不受上述實施形態所限制,以該業者之知識為基準,可加入各種設計變更等之變形,加入有該變形之形態亦包含於本發明之範圍。藉由組合上述之實施形態與下述之變形例所產生的實施形態,組合具有組合的實施形態及變形例之各效果。
上述實施形態之擴散劑組成物,可適合採用噴霧塗佈法,亦可採用旋轉塗佈法、噴墨印刷法、輥塗佈印刷法、篩網印刷法、凸版印刷法、凹版印刷法、平版印刷法等之其他印刷法。
於下述中,說明本發明之實施例,此等實施例不會超過用以說明本發明之例示,皆不為限制本發明者。
實施例I-1~I-4、比較例I-1~I-5之擴散劑組成物的成分及含有比例如表1所示。表中之各數值的單位為質量%,各成分之比例為相對於擴散劑組成物之全部質量而言之比例。而且,矽化合物(B)之含有比例為以SiO2換算之值。
表1中之簡稱係表示下述之化合物。
PPG:聚丙二醇
EtOH:乙醇
PGME:丙二醇單甲醚
HG:己二醇
MFTG:甲基丙烯三甘醇(methyl propylene triglycol)
在乙醇中添加作為雜質擴散成分(A)之B2O3,且在60℃之熱水浴中進行加熱攪拌3小時,在乙醇中溶解B2O3,作成摻雜液。將B2O3濃度調製為10%。
混合作為乙醇、矽化合物(B)之四乙氧基矽烷及濃鹽酸,作成SiO2系被膜形成用塗佈液(塗佈原液)。
使作為添加劑(D)之聚丙二醇(商品名:Sunnix.PP-
4000、三洋化成工業股份有限公司製)以乙醇予以2倍稀釋,且作成聚丙二醇濃度為50%之乙醇溶液(添加劑溶液)。
混合上述摻雜液、塗佈原液及添加劑溶液,且在混合液中添加溶劑(C),其係含作為溶劑(C1)之乙醇、作為溶劑(C2)之丙二醇單甲醚及作為溶劑(C3)之甲基丙烯三甘醇(日本乳化劑股份有限公司製、相當於TPGM),調製擴散劑組成物。擴散劑組成物之SiO2固體成分濃度為8.1質量%,B2O3固體成分濃度為1.9質量%,添加劑濃度為7.0質量%。溶劑(C)之組成比例係溶劑(C1):溶劑(C2):溶劑(C3)=8:1:1。
與實施例I-1相同地,調製擴散劑組成物。SiO2固體成分濃度為7.0質量%,B2O3固體成分濃度為2.2質量%,溶劑(C)之組成比例係溶劑(C1):溶劑(C2):溶劑(C3)=7:2:1。
與實施例I-1相同地,調製擴散劑組成物。SiO2固體成分濃度為7.0質量%,B2O3固體成分濃度為2.2質量%,溶劑(C)之組成比例係溶劑(C1):溶劑(C2):溶劑
(C3)=7:1:2。
與實施例I-1相同地,調製擴散劑組成物。SiO2固體成分濃度為7.0質量%,B2O3固體成分濃度為2.2質量%,使用酯醇取代甲基丙烯三甘醇作為溶劑(C3)。
與實施例I-1相同地,調製擴散劑組成物。溶劑(C)之組成係僅作為溶劑(C1)之乙醇。
與實施例I-1相同地,調製擴散劑組成物。溶劑(C)之組成係作為溶劑(C1)之乙醇,及作為溶劑(C3)之甲基丙烯三甘醇,其組成比例係溶劑(C1):溶劑(C3)=8:2。
與實施例I-1相同地,調製擴散劑組成物。溶劑(C)之組成係作為溶劑(C1)之乙醇,及作為溶劑(C2)之丙二醇單甲醚,其組成比例係溶劑(C1):溶劑(C2)=8:2。
與實施例I-1相同地,調製擴散劑組成物。SiO2固體成分濃度為7.0質量%,B2O3固體成分濃度為2.2質量
%。溶劑(C)之組成係作為溶劑(C1)之乙醇,及作為溶劑(C2)之丙二醇單甲醚,其組成比例係溶劑(C1):溶劑(C2)=8:2。
與實施例I-1相同地,調製擴散劑組成物。SiO2固體成分濃度為7.0質量%,B2O3固體成分濃度為2.2質量%。而且,溶劑(C)之組成,作為溶劑(C1)之乙醇,相對於溶劑(C2)之比較溶劑的己二醇(沸點:198℃)、及作為溶劑(C3)之甲基丙烯三甘醇,其組成比例係溶劑(C1):比較溶劑:溶劑(C3)=8:1:1。
使各實施例及比較例之擴散劑組成物使用一般的噴嘴塗佈裝置,塗佈於N型半導體基板上。塗佈條件如下所述。換言之,噴嘴係使用2流體噴嘴(SUJ1A:Spraying System公司製),吐出量:0.1g/min,氣體流量:20L/min,掃描速度:400mm/s予以塗佈。而且,溫度:23℃,濕度:40%。其次,觀察噴霧塗佈裝置之噴嘴阻塞情形,評估擴散劑組成物之吐出安定性。於噴嘴前端沒有擴散劑組成物產生結晶物,產生的結晶物極為少量,可長時間(例如1小時以上)之塗膜形成時為「○」,噴嘴前端有結晶物產生,不易在長時間(例如1小時以上)之塗膜形成時為「△」,藉由產生結晶物,無法形成塗膜時為
「×」。評估結果如表1所示。而且,前述「不易長時間
形成塗膜」之判斷基準,該業者可藉由實驗等予以適當設定。
另外,形成擴散劑組成物之塗膜後,將半導體基板載置於熱板上,在150℃下進行烘烤處理5分鐘。然後,使用SEM(掃描型電子顯微鏡)攝影半導體基板及塗膜之截面,觀察SEM照片中在半導體基板表面上所形成的塗膜之形狀,評估擴散劑組成物之塗膜形成性。使半導體基板表面全部範圍以擴散劑組成物之塗膜被覆時為「○」,部分的半導體基板表面露出時為「×」。評估結果如表1所示。而且,比較例I-1中因噴嘴阻塞而無法形成塗膜,無法觀察塗膜形狀。
如表1所示,不含溶劑(C2)、溶劑(C3)之比較例I-1,吐出安定性顯著降低,因此無法形成塗膜(即塗膜形成性亦低)。而且,不含溶劑(C2)之比較例1-2,I-5,塗膜形成性低。此外,不含溶劑(C3)之比較例I-3,I-4,吐出安定性低。對此而言,可確認含有溶劑(C1)、溶劑(C2)及溶劑(C3)之實施例,皆具有良好的吐出安定性與塗膜形成性。
相對於含有溶劑(C1)、溶劑(C3),不含溶劑(C2)之比較例I-2,I-5而言,含有溶劑(C1)、溶劑(C2)及溶劑(C3)之實施例可提高塗膜形成性,預測溶劑(C2)可提高塗膜形成性。此係相對於不含溶劑(C2)、溶劑(C3)之比較例I-1,
與含有溶劑(C3)、不含溶劑(C2)之比較例I-2,I-5而言,含有溶劑(C2)、不含溶劑(C3)之比較例I-3,I-4亦可提高塗膜形成性。
此外,相對於含有溶劑(C1)、溶劑(C2)、不含溶劑(C3)之比較例I-3,I-4而言,含有溶劑(C1)、溶劑(C2)及溶劑(C3)之實施例,由於可提高吐出安定性,溶劑(C3)可提高吐出安定性。此係相對於不含溶劑(C2)、溶劑(C3)之比較例I-1,與含有溶劑(C2)、不含溶劑(C3)之比較例I-3,I-4而言,含有溶劑(C3)、不含溶劑(C2)之比較例I-2,I-5亦可提高吐出安定性。
擴散劑組成物可在半導體基板之一定範圍內均勻地擴散,可使摻雜擴散範圍之電阻減低至企求之值,即企求擴散性高者。然後,評估本實施形態之擴散劑組成物的擴散性。實施例II-1~II-4、比較例II-1之擴散劑組成物的成分及含有比例如表2所示。表中之各數值之單位為質量%,各成分之比例相對於擴散劑組成物之全部質量之比例。而且,矽化合物(B)之含有比例,以SiO2換算之值。
而且,表2中之簡稱與表1相同。
與實施例I-1相同地,調製擴散劑組成物。SiO2固體成分濃度為7.0質量%,B2O3固體成分濃度為2.2質量%,溶劑(C)之組成比例係溶劑(C1):溶劑(C2):溶劑(C3)=7:2:1。
與實施例II-1相同地,調製擴散劑組成物。溶劑(C)之組成比例係溶劑(C1):溶劑(C2):溶劑(C3)=7:1:2。
與實施例II-1相同地,調製擴散劑組成物。使用酯醇取代甲基丙烯三甘醇做為溶劑(C3),溶劑(C)之組成比例係溶劑(C1):溶劑(C2):溶劑(C3)=8:1:1。
與實施例II-1相同地,調製擴散劑組成物。使用丙三醇取代甲基丙烯三甘醇做為溶劑(C3),溶劑(C)之組成比例係溶劑(C1):溶劑(C2):溶劑(C3)=8:1:1。
與實施例II-1相同地,調製擴散劑組成物。溶劑(C)之組成係作為溶劑(C1)之乙醇,及作為溶劑(C2)之丙二醇
單甲醚,其組成比例係溶劑(C1):溶劑(C2)=8:2。
與評估試驗I相同地,在N型半導體基板之表面上噴霧塗佈各實施例及比較例之擴散劑組成物。然後,將半導體基板載置熱板上,在150℃實施烘烤處理5分鐘。然後,將半導體基板載置於電爐內,在O2氣體環境、600℃、加熱30分鐘、燒成半導體基板,然後,在N2氣體環境、1000℃加熱30分鐘,使雜質擴散成分(A)予以熱擴散。然後,將半導體基板浸漬於50%濃度之HF溶液1分鐘,藉由熱擴散以剝離半導體基板表面上形成的氧化膜。使半導體基板所形成的雜質擴散層的薄片電阻值使用薄片電阻測定器(VR-70:國際電氣股份有限公司製),藉由四探針進行測定。薄片電阻值(Ω/sq.)之測定結果如表2所示。
如表2所示,任何的實施例與比較例II-1相比時,具有低的薄片電阻值。而且,由實施例II-1與實施例II-2相比時,對溶劑(C2)而言溶劑(C3)之含量多,可更為減低薄片電阻值。
本發明係利用擴散劑組成物、雜質擴散層之形成方法
及太陽能電池。
1‧‧‧半導體基板
1a‧‧‧結構部
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‧‧‧背面電極
10‧‧‧太陽能電池
[第1圖]第1(A)圖至第1(D)圖係用以說明含有實施形態之雜質擴散層的形成方法之太陽能電池的製造方法的步驟截面圖。
[第2圖]第2(A)圖至第2(D)圖係用以說明含有實施形態之雜質擴散層的形成方法之太陽能電池的製造方法的步驟截面圖。
Claims (6)
- 一種擴散劑組成物,其係於半導體基板上形成雜質擴散劑層時使用的擴散劑組成物,其特徵為含有雜質擴散成分(A)、矽化合物(B)及含有沸點為100℃以下之溶劑(C1)、沸點為120~180℃之溶劑(C2)與沸點為240~300℃之溶劑(C3)的溶劑(C),前述溶劑(C1)相對於擴散劑組成物之溶劑成分的全部質量而言含有70質量%以上,前述溶劑(C2)相對於擴散劑組成物之溶劑成分的全部質量而言含有10質量%以上,前述溶劑(C3)相對於擴散劑組成物之溶劑成分的全部質量而言含有10質量%以上,且對前述溶劑(C2)而言前述溶劑(C3)之含量為多。
- 如申請專利範圍第1項之擴散劑組成物,其中前述雜質擴散成分(A)含有III族元素之化合物或V族元素之化合物。
- 如申請專利範圍第1項之擴散劑組成物,其係使用於藉由噴霧塗佈處理形成雜質擴散劑層時。
- 如申請專利範圍第1項之擴散劑組成物,其中前述溶劑(C2)及前述溶劑(C3)為二元醇類。
- 如申請專利範圍第1項之擴散劑組成物,其中前述矽化合物(B)係選自二氧化矽微粒子及使以下述一般式(1)所示之烷氧基矽烷水解所得的反應生成物所成群的至少一種, R1 nSi(OR2)4-n (1)[式(1)中,R1為氫原子、烷基或芳基,R2為烷基或芳基,n為整數0、1或2,R1為複數個時,複數個的R1可相同或不相同,(OR2)為複數個時,複數個的(OR2)可相同或不相同]。
- 一種雜質擴散層之形成方法,其特徵為含有在半導體基板上藉由噴霧塗佈處理印刷如申請專利範圍第1項之擴散劑組成物,形成特定圖案之雜質擴散劑層之圖案形成步驟,及使前述擴散劑組成物之雜質擴散成分(A)擴散於前述半導體基板之擴散步驟。
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