TWI605492B - 用於製造摻雜ｐ的矽層之方法及藉由彼所製造之光伏打單元、以及經塗布之基板 - Google Patents

用於製造摻雜ｐ的矽層之方法及藉由彼所製造之光伏打單元、以及經塗布之基板 Download PDF

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TWI605492B
TWI605492B TW100131266A TW100131266A TWI605492B TW I605492 B TWI605492 B TW I605492B TW 100131266 A TW100131266 A TW 100131266A TW 100131266 A TW100131266 A TW 100131266A TW I605492 B TWI605492 B TW I605492B
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史蒂芬 偉伯
麥瑟斯 帕茲
哈洛德 史都格
傑斯明 藍科爾
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贏創德固賽有限責任公司
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Description

用於製造摻雜p的矽層之方法及藉由彼所製造之光伏打單元、以及經塗布之基板
本發明有關用於製造摻雜p的矽層之方法，尤其是從液態含矽烷之調和物製造該矽層之方法。本發明另外有關塗布摻雜p的矽層之基板。本發明另外有關以硼化合物為底質之特定摻雜劑用於矽層之摻雜p的用途。
矽層之合成對於半導體產業極為重要，尤其是對於電子組件層或光電組件層(例如用於太陽能電池、光二極體及電晶體者)之製造極重要。
太陽能電池之製造需要具有不同摻雜的半導體層。藉由在適當基板上沉積一或多層矽層，可能製造一或多個p-n接面或pin或nip接面，其作為太陽能電池。該沉積係利用適合薄層之施加裝置(例如捲對捲(roll-to-roll)塗布機)進行。藉由適當熱處理來安定所形成之層，使得通常假定該層為微晶、奈米晶及非晶形結構之混合物。除非明確指明，否則因為在大部分情況下不易確切區分及定義，或者對於所獲致之結果重要性不大，故所有微晶、奈米晶及/或非晶形層通常於此處應稱為「經轉化Si層」。
原則上可能經由各種方法而製造摻雜p的矽層。然而，其中CVD技術具有必須在高度真空下進行之缺點。以氣相沉積為基礎之方法具有其他缺點：該等方法i)在熱反應型態(reaction regime)之情況下需要非常高溫，或ii)在引入呈電磁輻射形式之用於分解前驅物的能量之情況下需要高能量密度。二者情況均只有在極高之設備複雜度下以受控制且均勻方式引入分解該前驅物所需的能量時方為可行。由於製造摻雜p的矽層的其他方法亦具有不利，因此摻雜p的矽層較佳係經由從液相沉積形成。
在此等製造摻雜p的矽層的液相方法中，液態反應物或含有固態或液態反應物之溶液、摻雜劑及隨意的其他添加劑係施加於待塗布之基板，然後熱轉化或以電磁輻射轉化成摻雜p的矽層。
較佳之可使用反應物為氫矽烷，且以硼化合物作為摻雜劑。該等氫矽烷基本上由矽及氫原子組成，且具有於轉化時反應以產生沉積之矽及氣態氫的優點。該沉積之矽可仍含有對於電子性質有益之殘留氫含量。該等硼化合物基本上由硼原子及烴基或氫原子組成。
先前技術尤其包括藉由添加第III主族元素化合物或選自SiaXbYc型之雜原子環狀矽烷化合物而從液態H-矽烷製造摻雜p的矽層的液相方法。
US 5,866,471 A特別描述使用直鏈或環狀氫矽烷及經矽基取代之直鏈或環狀氫矽烷，其可於摻雜劑之存在下熱分解以產生n型或p型半導體膜。上述物質在室溫下為固態且可溶於有機溶劑中，較佳具有3至10000之聚合度，較佳具有5至30之聚合度。彼等另外較佳可在介於200與700℃之間熱分解，固化時間在10分鐘至10小時之範圍內。
EP 1 085 579 A1描述製造太陽能電池之方法，其中藉由熱、光及/或雷射處理轉化含有矽烷之液態組成物。該液態塗布組成物可含有溶劑與式SinXm(X=H、Hal，n5，m=n、2n-n、2n)之環狀矽化合物及式SiaXbYc(X=H、Hal，Y=B、P，a3，c=1至a，且b=a至2a+c+2)之經改質矽烷化合物。該液態組成物轉化成摻雜p的Si層或其他層之轉化作用可利用乾燥步驟後之轉化步驟來進行。所指定之典型乾燥溫度範圍為100至200℃。此處，亦陳述成為矽層之重要轉化作用僅自300℃起發生，非晶形層在300℃至550℃之範圍中形成，而多晶層係自550℃起形成。
EP 1 357 154 A1描述含有聚矽烷之「較高級矽烷」的組成物，其可藉由使用UV輻射照射可光聚合矽烷而製備。該可光聚合矽烷可為通式SinXm(其中n3，m4，X=H、Hal)之矽烷；明確化合物的範例是式SinX2n之環狀矽烷、式SinH2n-2之雙或多環結構、及分子中具有環狀結構的其他矽烷指定的化合物，彼等展現出對於光具有極高反應性且可有效率地光聚合。「較高級矽烷」之組成物可藉由熱分解或光分解而在基板上轉化為矽膜。在該情況下，第III或V主族元素化合物可在該聚合作用之前或之後使用。為此目的，藉由熱(通常為100至200℃)乾燥該潮濕膜，然後藉由熱及/或光轉化。非晶膜可藉由在低於550°之溫度下熱處理而獲得，在更高溫度下之結果為多晶膜。該等實例指出轉化時間為10分鐘(350℃、400℃、500℃)，而摻雜劑物質為PH3、P4、B5H9、B10H14。此處之缺點係因安定的團簇而導致長轉化時間，及其毒性。硼原子團簇之高安定性使硼之均勻分布變複雜，且此相對大量添加硼是必要的(10原子%硼)。
EP 1640342 A1描述含有聚矽烷之「較高級矽烷」的組成物，以GPC測量，其平均分子量在800至5000 g/mol之範圍中。該組成物亦可含有第3或5主族之元素。該實例中，環戊矽烷與十硼烷一起照射。該膜係在400℃下固化30分鐘，然後在800℃下固化5分鐘。此處之缺點係因安定的團簇而導致長轉化時間，及其毒性。硼原子團簇之高安定性使硼之均勻分布變複雜。
US 2008022897 A1描述使用廣泛之不同摻雜劑。其申請專利範圍只描述組成物，但無形成n型或p型Si層之方法描述。申請專利範圍第1項描述SinH2n+2(其中n=3至20)與BR3(其中各R可獨立為H、烷基等)之組成物。
JP2002100576 A1描述使用BH3硫化物錯合物作為摻雜劑。將該錯合物與氫矽烷熱解並利用氣相之適合的惰性有機介質而共沉積在基板上。該等實例指出沉積溫度為400℃，而轉化時間為至少20分鐘。
然而，所有該等已描述方法的共同因素係彼等需要非常長固化時間以活化該Si層中所使用之化學安定性非常高的摻雜劑。
因此本發明目的係提出一種避免先前技術缺點的摻雜p的矽層之製造方法。更明確地說，該方法應以液態矽烷調和物之沉積為基礎。此外，本發明提出製造摻雜p的矽層之液相方法，其中所使用之調和物安定並能有效率地濕潤基板，且其形成具有均勻摻雜分布之均勻摻雜p的矽層。亦特別有利的是能製造具有良好傳導性之摻雜p的aSi層。
上述目的係藉由本發明之一種用於製造至少一層配置在基板上之摻雜p的矽層之方法而獲致，該方法包括以下步驟以形成主要由矽組成之摻雜p的層：
a)提供基板，
b)提供含有至少一種矽化合物及作為摻雜劑之至少一種選自氫硼化劑的群組之化合物的調和物，
c)將該調和物施加於該基板，
d)照射及/或熱處理該經塗布之基板以形成主要由矽組成之摻雜p層。
應理解本發明內容中之氫硼化劑意指具有至少一個硼-氫鍵之硼化合物，但二硼烷除外。由於二硼烷之氣態係不利的，故本發明內容中之適用氫硼化劑將其排除在外。此外，與作為氫硼化劑之二硼烷的反應進行得非常緩慢。該氫硼化劑較佳為液態或固態。
根據本發明方法，較佳使用之選自氫硼化劑之群組的化合物係選自a)與錯合劑形成之BH3錯合物，該錯合劑係選自由THF；NR3(其中R=H、烷基、芳基)及SR'2(其中R'=H、烷基、芳基)組成之群組；或b)BxCxnH2xn-x型之化合物，其中x=1-4且n=3-10，其可由a)中所界定之BH3錯合物與環狀二烯反應而製得。
特佳選自a)及b)群組者為化合物BH3*THF、BH3*SMe2、BH3*NMe3或9-硼雜二環壬烷(9-BBN)、7-硼雜二環庚烷及/或11-硼雜二環十一烷。尤佳之氫硼化劑為BH3*THF、BH3*NMe3及9-硼雜二環壬烷(9-BBN)。
應暸解本發明內容中「含有至少一種矽化合物與至少一種選自至少一種選自氫硼化劑的群組之化合物」的調和物意指由至少一種矽化合物與至少一種選自該氫硼化劑群組之化合物所組成之組成物，或可從至少一種矽化合物與至少一種選自該氫硼化劑群組之化合物製造的組成物，尤其是至少一種矽化合物與至少一種選自該氫硼化劑群組之化合物的反應產物。
前文在a)及b)下提及之摻雜劑類別迄今已用於有機合成化學，尤其用於烯類之氫硼化，以在隨後之羥化中獲得對應之反馬可尼可夫(anti-Markovnikov)產物。因此，尤其令人意外的是，該類化合物可用於摻雜光電子組件之Si層。彼等為市售並可安定貯存。在大部分情況下，其為非毒性且不會形成使該Si層中之摻雜劑原子的均勻分布變複雜之團簇。
本發明方法具有數個優點。例如，可在步驟d)中獲致較短時間形成摻雜p之層。此可能因為摻雜元素比從先前技術中所使用之化合物更容易釋放所致。當摻雜元素釋放時形成之自由基亦安定且容易蒸發。另一優點係可使用非毒性市售物質。令人意外的是，另外，使用該新穎類別之摻雜劑可得到具有非常良好傳導性之摻雜p的矽層。
根據本發明方法中較佳使用之矽化合物為矽-氫化合物，較佳係具有通式SinH2n+2或SinH2n(其中n=3至20)；鹵化矽；矽有機基(silicon organyl)；寡聚矽化合物SinR2n+2或SinR2n(其中n=8至100，且R=H、鹵素、有機基，其中各R可獨立選擇)；或此等矽化合物之任何混合物。此外，上述化合物，尤其是通式SinH2n+2或SinH2n(其中n=3至20)之矽-氫化合物，在用於步驟b)之前係部分或完全寡聚，此可能形成330 g/mol至10000 g/mol，較佳為400 g/mol至3000 g/mol，更佳為500 g/mol至1000 g/mol之莫耳質量。該寡聚物可部分或完全藉由照射或熱處理進行。
特佳情況係使用矽-氫化合物，即矽烷及寡聚矽烷或聚矽烷，此係因為彼等可藉由SiH4之化學合成或催化融合而獲得，且以該等化合物之莫耳質量計具有高矽含量。特別適用於本發明方法之矽烷為具有通式SinH2n+2(其中n=3至10，較佳係n=4至8)或SinH2n(其中n=4至8，較佳係n=5及6)之矽烷。
可藉由例如寡聚一或多種通式SinH2n+2或SinH2n(其中n=3至20)矽化合物來製備寡聚矽化合物SinR2n+2或SinR2n(其中n=8至100且R=H)。可藉由例如寡聚一或多種鹵化矽來製備寡聚矽化合物SinR2n+2或SinR2n(各例中n=8至100且R=鹵素)。最後，可藉由例如寡聚一或多種矽有機基來製備寡聚矽化合物SinR2n+2或SinR2n(各例中n=8至100且R=有機基)。所有例中，可獨立選擇每一上述之R。
本發明方法之一變體中，含矽調和物可藉由寡聚及/或聚合含有至少一種具有通式SinH2n+2(其中n=3至10，較佳為n=4至8)或SinH2n(其中n=4至8，較佳為n=5及6)之較高級矽烷的混合物來製備。就利用UV照射或熱處理來寡聚而言，使用n3之上述通式之較高級矽烷。以此方式，可於一步驟中從液態低黏度混合物製備所需較高黏度之含寡聚矽烷/聚矽烷的液態混合物。
在一根據本發明之方法的另一變體中，可藉由利用能量方法(例如UV照射、熱處理(共寡聚))來寡聚及/或聚合含有至少一種矽化合物與至少一種選自至少一種選自氫硼化劑的群組之摻雜劑的混合物而製備含矽調和物。選自氫硼化劑之群組的化合物因而可在矽化合物進行任何寡聚物及/或聚合之前或之後或者期間添加。
本發明方法中所使用之含矽調和物通常為液態調和物。該液態調和物係由上述矽化合物組成，隨意地呈與溶劑形成的混合物之形式。較佳之可使用溶劑係選自由具有1至12個碳原子之直鏈、支鏈或環狀飽和、不飽和或芳族烴(隨意地部分或完全鹵化)、醇、醚、羧酸、酯、腈、胺、醯胺、亞碸及水所組成之群組。特佳者為正戊烷、正己烷、正庚烷、正辛烷、正癸烷、十二烷、環己烷、環辛烷、環癸烷、二環戊烷、苯、甲苯、間二甲苯、對二甲苯、1,3,5-三甲苯、二氫化茚、茚、四氫萘、十氫萘、二乙醚、二丙醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇甲基乙基醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙基醚、四氫呋喃、對二噁烷、乙腈、二甲基甲醯胺、二甲亞碸、二氯甲烷及氯仿。
具有特別良好使用性之溶劑為烴類，正戊烷、正己烷、正庚烷、正辛烷、正癸烷、十二烷、環己烷、環辛烷、環癸烷、苯、甲苯、間二甲苯、對二甲苯、1,3,5-三甲苯、二氫化茚及茚。
若合宜，可額外添加其他溶劑、其他摻雜劑及/或其他輔助劑。在該情況下，該等其他劑或物質可實際上在寡聚及/或聚合之前或只在其後各別獨立地添加於該混合物。在該情況下，寡聚及/或聚合作用亦可藉由照射或熱處理而部分或全部進行，此可確立330 g/mol至10 000 g/mol，較佳為400 g/mol至3000 g/mol，更佳為500 g/mol至1000 g/mol之莫耳質量。在根據整體調和物計之溶劑的比例可為5至99重量%，較佳為25至85重量%，更佳為50至85重量%。
可以習知方式對基板塗布該含矽調和物。較佳情況係藉由以下方法沉積該調和物：選自印刷或塗布法(尤其是快乾/凹版印刷、噴墨印刷、套版印刷、數位套版印刷及網版印刷)、噴霧法、旋塗法(「旋轉塗布」)、浸塗法(「浸漬塗布」)之方法，及選自彎液面塗布、狹縫塗布、狹縫模具式塗布及淋幕式塗布之方法。
該經塗布基板之熱處理可以習知方式進行，尤其是實質上排除O2及H2O。例如，塗布該調和物之基板可加熱至200至1000℃，較佳為250至700℃，更佳為300至650℃之溫度。根據本發明，此形成主要由矽組成之至少部分經轉化的層。在新製造之層的情況下，亦可能使用UV燈(例如波長為254 nm或波長為180 nm)藉由交聯來進行上游之固化。在本發明方法之較佳具體實例中，在無照射情況下對該經塗布之基板進行熱處理。原則上，熱處理可使用烘箱、加熱輥、熱板、紅外線或微波輻射等進行。然而，在捲對捲方法中特佳係使用熱板或加熱輥進行熱處理，原因在於其造成之複雜度低。
溫度從200℃至1000℃。該等層亦可在氫與氮或氫與氬之形成氣體混合物(例如體積比為5/95至10/90之H2/N2或體積比為5/95至10/90之H2/Ar)之下，於250℃至700℃，較佳為300℃至650℃的溫度下加熱來進行後加熱。
在經塗布基板的熱處理中，該主要由矽組成之至少部分寡聚膜通常在短於10分鐘內轉化，較佳在短於5分鐘內轉化。該轉化可在200 mbar至高達50 bar之壓力下發生。該轉化較佳係在500 mbar至10 bar之壓力下發生，最佳係在800 mbar至1300 mbar之範圍中發生。就摻雜p的aSi層而言，溫度可在250℃至700℃之範圍中，較佳係在300℃至650℃之範圍中。轉化可在一或多個連續熱步驟中發生。
由於較長轉化時間，形成的層流失更多氫，氫飽和瑕疵位點，稱之為懸鍵。該等瑕疵位點可構成摻雜劑電荷載子之阱，因此導致較不良之摻雜效率。如先前技術中所述，較長轉化時間的另一缺點是造成較長塗布線，導致較高製程成本。
如上述，本發明方法適於在基板上製造「至少一層」之矽層。為了獲得在基板上之數層對應矽層，方法步驟(b)至(d)可進行多於一次。在完成該等方法步驟數次的情況下，個別層可各獨立經特殊配置，以使得每一層之性質可針對期望之目的而做個別調整。
根據本發明之方法可使用多種基板。較佳係由玻璃、石英玻璃、石墨、金屬、矽所組成之基板，或由在可熱相容之載體上的矽、氧化銦錫、ZnO:F或SnO2:F層所組成之基板。
較佳之金屬為鋁、不鏽鋼、Cr鋼、鈦、鉻或鉬。此外，可能使用聚合物膜，例如PEN、PET或聚醯亞胺之膜。
然而，所使用之基板亦可為已藉由本文所述之方法製造的經塗布之基板。
本發明亦提出一種如上述包含基板及摻雜p的矽層之經塗布基板，其特徵在於該摻雜p係摻雜硼，該硼係藉由選自氫硼化劑之群組的化合物導入。
上述經塗布之基板較佳可藉由本文所述之本發明方法製造。
可用之基板包括所有上述材料及配置，尤其是具有導電性基板或具有導電性表面之基板。
本發明另外提供光伏打單元，尤其是太陽能電池或太陽能電池組合，其係使用根據本文所述之本發明方法或其變體製造或可使用該方法或其變體製造。
本發明更特別係亦包括一種選自氫硼化劑之群組的化合物用於矽層之摻雜p的用途，特別是藉由包括以下步驟之方法所製造的矽層：施加含有至少一種矽化合物之調和物並照射及/或熱處理該經塗布基板以形成主要由矽組成之摻雜p的層。
提出之層厚度係使用得自柏林Sentech之SENpro橢圓偏光計測量。所指定之電測量係在具有氧濃度低於1 ppm且水含量至多1 ppm之N2氛圍的手套工作箱中以Keithley儀器進行。
實施例1：以氫硼化劑(BH3*THF)製造摻雜p的Si層
在具有氧濃度低於1 ppm且水含量至多1 ppm之N2氛圍的手套工作箱中，將3 ml之環戊矽烷與3 ml之甲苯及0.5 ml之BH3*THF錯合物混合，並在開放式容器中使用波長為254 nm之UV燈照射150分鐘之期間。此過程中，可移動的矽烷變得更稠(調和物1)。
將4滴之由0.2 ml之調和物1與0.9 ml之環辛烷組成的調和物2施加於大小為2.5 cm×2.5 cm之載玻片，並在6000 rpm下藉助於旋塗機而均勻分布在該載玻片上。隨後，藉由熱板之助，在500℃下加熱該膜持續1分鐘期間。此舉在該基板上形成暗色且實質上無氧之摻雜p的矽層。該層厚度為134 nm。傳導性測量得2×10E+05 ohmcm之比暗電阻率。
實施例2：以9-硼雜二環壬烷製造摻雜p的Si層
在具有氧濃度低於1 ppm且水含量至多1 ppm之N2氛圍的手套工作箱中，將4 ml之環戊矽烷與4 ml之環辛烷混合，並在開放式容器中使用波長為254 nm之UV燈照射持續160分鐘之期間。此過程中，可移動的矽烷變得稠(調和物3)。
將4滴之由0.075 ml之調和物3、0.141 ml之環辛烷、0.103 ml之甲苯及0.056 ml之環戊矽烷所組成之調和物4與9 mg之9-BBN摻合且施加於大小為2.5 cm×2.5 cm之載玻片，並在3000 rpm下藉助於旋塗機而均勻分布在該載玻片上。隨後，藉由熱板之助，在500℃下加熱該膜持續1分鐘期間。此舉在該基板上形成暗色且實質上無氧之摻雜p的矽層。該層厚度為149 nm。傳導性測量得約7×10E+04 ohmcm之比暗電阻率。
實施例3(對照實例)：以十硼烷製造摻雜p的Si層
在具有氧濃度低於1 ppm且水含量至多1 ppm之N2氛圍的手套工作箱中，將1.7 g之由環戊矽烷於甲苯中形成的1：1混合物與0.05 g之十硼烷混合，並在開放式容器中使用波長為254 nm之UV燈照射90分鐘之期間。此過程中，可移動的矽烷變得更稠(調和物5)。此外，單獨照射2.5 ml之環戊矽烷55分鐘。在該過程中，該環戊矽烷寡聚而產生黏性寡聚物。將0.2 ml該黏性寡聚物與0.05 ml之調和物5及0.5 ml之甲苯混合(調和物6)。
將4滴調和物6施加於大小為2.5 cm×2.5 cm之載玻片，並在3000 rpm下藉助於旋塗機而均勻分布在該載玻片上。隨後，藉由熱板之助，在500℃下加熱該膜持續1分鐘期間。此舉在該基板上形成暗色且實質上無氧之摻雜p的矽層。該層厚度為173 nm。傳導性測量得2.6×10E+09 ohmcm之比暗電阻率。

Claims (19)

  1. 一種用於製造至少一層配置在基板上之摻雜p的矽層(p-doped silicon layer)之方法，其包括以下步驟以形成主要由矽組成之摻雜p的層：(a)提供基板，(b)提供含有至少一種矽化合物及作為摻雜劑之至少一種選自氫硼化劑的群組之化合物的調和物，其中選自氫硼化劑之群組的化合物係選自與錯合劑形成之BH3錯合物，該錯合劑係選自由THF；NR3(其中R=H、烷基、芳基)及SR'2(其中R'=H、烷基、芳基)組成之群組；(c)將該調和物施加於該基板以形成經塗布之基板，(d)照射及/或熱處理該經塗布之基板。
  2. 如申請專利範圍第1項之方法，其中該矽化合物為矽-氫化合物；鹵化矽；矽有機基(silicon organyl)；寡聚矽化合物SinR2n+2或SinR2n(其中n=8至100，且R=H、鹵素、有機基，其中各R可獨立選擇)；或此等矽化合物之任何混合物。
  3. 如申請專利範圍第1項之方法，其中，該矽化合物係具有通式SinH2n+2或SinH2n之矽-氫化合物，其中n=3至20。
  4. 如申請專利範圍第2或3項之方法，其中該矽化合物在使用於步驟b)之前，係經部分或完全寡聚以將該寡聚矽化合物之莫耳質量調整至330g/mol至10000g/mol。
  5. 如申請專利範圍第2或3項之方法，其中該矽化合物在使用於步驟b)之前，係經部分或完全寡聚以將該寡聚矽化合物之莫耳質量調整至400g/mol至3000g/mol。
  6. 如申請專利範圍第2或3項之方法，其中該矽化合物在使用於步驟b)之前，係經部分或完全寡聚以將該寡聚矽化合物之莫耳質量調整至500g/mol至1000g/molg/mol。
  7. 如申請專利範圍第1項之方法，其中該調和物包含溶劑。
  8. 如申請專利範圍第1項之方法，其中該基板係利用選自由快乾/凹版印刷、噴墨印刷、套版印刷、數位套版印刷、網版印刷、噴霧法、旋塗法、浸漬法、彎液面塗布、狹縫塗布、狹縫模具式塗布、及淋幕式塗布所組成的群組之方法塗布。
  9. 如申請專利範圍第1項之方法，其中該熱處理係在200至1000℃。
  10. 如申請專利範圍第1項之方法，其中該熱處理係在250至700℃之溫度下進行。
  11. 如申請專利範圍第1項之方法，其中該熱處理係在300至650℃之溫度下進行。
  12. 如申請專利範圍第1項之方法，其中步驟(b)至(d)進行多於一次。
  13. 如申請專利範圍第1項之方法，其中該基板為導電性基板或具有導電性表面。
  14. 一種包含基板及摻雜p的矽層之經塗布基板，其特徵在於該摻雜p係摻雜硼，該硼係藉由選自氫硼化劑之群組的化合物導入，其中選自氫硼化劑之群組的化合物係選自與錯合劑形成之BH3錯合物，該錯合劑係選自由THF；NR3(其中R=H、烷基、芳基)及SR'2(其中R'=H、烷基、芳基)組成之群組。
  15. 如申請專利範圍第14項之經塗布基板，其係根據如申請專利範圍第1至13項中任一項之方法所製造。
  16. 如申請專利範圍第14或15項之經塗布基板，其中該基板為導電性基板或具有導電性表面。
  17. 一種光伏打單元，其包含如申請專利範圍第14至16項中任一項之經塗布基板。
  18. 如申請專利範圍第17項之光伏打單元，其中該光伏打單元係太陽能電池或數個太陽能電池之組合。
  19. 一種選自氫硼化劑之群組的化合物用於矽層之摻雜p的用途，該矽層係藉由包括以下步驟之方法所製造：施加含有至少一種矽化合物之調和物並照射及/或熱處理該經塗布基板以形成主要由矽組成之摻雜p的層，其中選自氫硼化劑之群組的該化合物係選自與錯合劑形成之BH3錯合物，該錯合劑係選自由THF；NR3(其中R=H、烷基、芳基)及SR'2(其中R'=H、烷基、芳基)組成之群組。
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