TW201518201A - 光吸收層製造用之ci(g)s奈米粒子的製造方法以及利用該方法製得的ci(g)s奈米粒子 - Google Patents
光吸收層製造用之ci(g)s奈米粒子的製造方法以及利用該方法製得的ci(g)s奈米粒子 Download PDFInfo
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- TW201518201A TW201518201A TW103124269A TW103124269A TW201518201A TW 201518201 A TW201518201 A TW 201518201A TW 103124269 A TW103124269 A TW 103124269A TW 103124269 A TW103124269 A TW 103124269A TW 201518201 A TW201518201 A TW 201518201A
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Abstract
本發明揭示一種形成太陽能電池之光吸收層的CI(G)S奈米粒子之製備方法,其包括將至少一種選自由包含硫(S)、硒(Se)或其組合之化合物所組成的群組之第VI族源及銦(In)鹽溶解於溶劑中以製備第一溶液,使該第一溶液反應以形成第一前驅物粒子,將銅(Cu)鹽溶解於溶劑中以製備第二溶液,將該第二溶液與該形成有該第一前驅物之第一溶液混合以製造混合物,及在藉由使該混合物反應而合成CI(G)S奈米粒子之後純化該合成的CI(G)S奈米粒子;以及使用該方法所製得之CI(G)S奈米粒子。
Description
本發明關於一種用於製備光吸收層之CI(G)S奈米粒子的製造方法及使用彼所製得之CI(G)S奈米粒子。更特別的是,本發明關於一種形成太陽能電池之光吸收層的CI(G)S奈米粒子之製造方法,其包括將至少一種選自由包括硫(S)、硒(Se)或其組合之化合物所組成的群組之第VI族源及銦(In)鹽溶解於溶劑中以製備第一溶液;使該第一溶液反應以形成第一前驅物粒子,將銅(Cu)鹽溶解於溶劑中以製備第二溶液;將該第二溶液與該形成有該第一前驅物之第一溶液混合以製造混合物;及在藉由該混合物之反應而合成CI(G)S奈米粒子之後純化該合成的CI(G)S奈米粒子;以及使用該方法所製得之CI(G)S奈米粒子。
近來,人們更關注環境問題及天然資源枯竭,因而對於作為不造成環境污染之替代能源的太陽能電池之興趣漸
增。太陽能電池分成矽太陽能電池、薄膜型化合物太陽能電池、層狀太陽能電池等。在該等太陽能電池當中,矽半導體太陽能電池獲得最廣泛研究。
然而,由於矽太陽能電池為間接躍遷半導體(indirect transition semiconductor),其光吸收係數低於直接躍遷者之光吸收份,相較於直接躍遷者,矽太陽能電池無法有效率吸收光子。如此,矽太陽能電池需要比直接躍遷者更廣之空間電荷區。此外,為了防止空間電荷區中因延長之載子壽命而發生的電子及電洞重組,基本上需要高純度Si,如此需要由複數個步驟組成的高價、高水準及複雜加工技術,及高度真空薄膜程序。當使用高純度單晶Si時,太陽能電池展現高效率。然而,此種高純度單晶Si之製造成本高,因而為了降低製造成本,使用展現低效率之多晶Si或非晶形Si。由於此種多晶Si或非晶形Si具有低光電轉換效率,當長時間使用時,會發生諸如惡化之問題。
因此,為了改善矽太陽能電池之問題,近來研究及發展薄膜型化合物太陽能電池。
在薄膜型化合物半導體當中,為包括在三元化合物中之第I-III-VI族化合物的Cu(In1-xGax)(SeyS1-y)(CI(G)S)具有1eV或更之直接躍遷型能帶隙及高光吸收係數。此外,Cu(In1-xGax)(SeyS1-y)(CI(G)S)在電光性質方面非常安定。如此,Cu(In1-xGax)(SeyS1-y)(CI(G)S)為太陽能電池之光吸收層的理想材料。
基於CI(G)S之太陽能電池係藉由形成厚度為數微米
的光吸收層來製造。作為製造光吸收層之方法,有不需要前驅物之蒸發法以及在以前驅物形成薄膜之後經由熱處理而形成CI(G)S薄膜的濺鍍及電沉積法。此外,近來已介紹在非真空下塗覆前驅物材料之後進行熱處理的油墨塗覆法。在上述方法當中使用油墨塗覆法可降低加工成本及可均勻製造大面積。如此,積極進行對於油墨塗覆法之研究。作為油墨塗覆法中之前驅物,可使用各種化合物或金屬類型,諸如金屬硫族化合物、雙金屬粒子、金屬鹽、金屬氧化物等。
特別是,當使用金屬硫族化合物作為前驅物時,將Cu-Se化合物及In-Se化合物混合或合成CuInSe2粒子。當將粒子混合時,可製造部分不均勻塗層。當使用CuInSe2時,粒子生長需要長時間。
同時,由於雙金屬粒子係使用Cu-In合金合成,可解決部分不均勻性,及因快速粒子生長而減少反應時間。然而,在硒(Se)或硫(S)氣氛中,會形成具有部分欠缺Se或S之層。此外,當塗覆金屬鹽時,可製造具有高層密度之塗層,然而因包括在鹽中之陰離子之故,層會受損或會形成有機殘留物。
因此,極需要發展可形成高效率光吸收層之前驅物奈米粒子的技術,其中該塗層之塗層性質獲得改善,從而提高層密度。
因此,已完成本發明以解決上述問題及其他尚待解決的技術問題。
由於各種廣泛研究及不同實驗之故,本發明之發明人首先形成包括銦(In)及第VI族元素之第一前驅物粒子,及選擇性地進一步包括鎵(Ga),然後確認當藉由添加銅(Cu)鹽合成CI(G)S奈米粒子時,可自由地控制粒子組成及均勻地合成具有預定直徑的球狀粒子,如此完成本發明。
根據本發明一態樣,提供一種製造形成太陽能電池之光吸收層的CI(G)S奈米粒子之方法,該方法包括:(i)將至少一種選自由包括硫(S)、硒(Se)或其組合之化合物所組成的群組之第VI族源及銦(In)鹽溶解於溶劑中以製備第一溶液;(ii)使該第一溶液反應以形成第一前驅物粒子;(iii)將銅(Cu)鹽溶解於溶劑中以製備第二溶液;(iv)將該第二溶液與該形成有該第一前驅物之第一溶液混合,以製造混合物,及(v)在藉由使該混合物反應而合成CI(G)S奈米粒子之後純化該合成的CI(G)S奈米粒子。
本申請案之發明人於使用與傳統金屬硫族化合物混合的Cu-Se化合物及In-Se化合物時,均勻地混合該等化合物,從而難以控制組成。此外,由於化合物係以整塊類型
存在,難以形成具有特定直徑之球狀粒子。
因此,由於進行深入研究,本發明之發明人確認當藉由將銅(Cu)鹽代替Cu-Se(S)化合物添加至In-Se(S)化合物來製造CI(G)S奈米粒子時,Cu離子移動至In-Se(S)化合物之通道,從而使Cu離子均勻地分散在整個In-Se(S)化合物粒子中並維持In-Se(S)化合物的結構,因此組成控制容易且可輕易地製造具有預定直徑之球狀粒子。
因此,在一實施態樣中,合成之CI(G)S奈米粒子可為球狀粒子,其中銅(Cu)離子遷移至非晶形第一前驅物粒子的通道中,具有30至200nm之平均直徑,更特別是具有50至150nm之平均直徑的球狀粒子。
由於在該等範圍外之具有小於30nm的平均直徑的CI(G)S奈米粒子需要的粒子生長時間長故較不宜。由於具有大於200nm之平均直徑的CI(G)S奈米粒子的塗層不緻密且在熱處理之後經常形成龜裂或空隙而造成低品質層,故此等粒子亦不宜。
此處,第一前驅物粒子為非晶形。具有遷移之銅(Cu)離子的CI(G)S奈米粒子為非晶形,或因遷移至非晶形第一前驅物粒子之Cu離子緣故,一些具有遷移之銅(Cu)離子的CI(G)S奈米粒子可為晶體形式。
下文將詳細描述本發明CI(G)S奈米粒子之製造方法。如上述,本發明先形成第一前驅物粒子及於步驟(i)中可製備第一溶液,其基於步驟(i)之第一溶液中1莫耳銦包括0.5至2莫耳之第VI族源。
當第一溶液中包括之第VI族源的量少於0.5莫耳(其低於上述範圍)時,第VI族元素不足,因而會部分形成缺乏第VI族元素的層。然而,當包括之第VI族源的量大於0.5莫耳時,保留一些不與金屬鹽反應之第VI族源,因此沉澱S或Se。沉澱之S或Se與Cu離子反應,因而形成Cu-Se(S)化合物。因此,引發組成之不均勻性,從而降低太陽能電池之效率。
步驟(ii)之形成第一前驅物粒子的反應可藉由使第一溶液在130至170℃維持1至4小時(視所希望之粒度而定)來進行。
在高於上述溫度範圍之溫度下的反應不宜,原因係構成第一前驅物粒子(In-Se(S)粒子)之Se或S的沉澱進展得更多,因而In-Se(S)粒子中的Se或S的比降低。
此處,第一前驅物粒子可藉由多元醇反應合成。在一實施態樣中,第一溶液及第二溶液之溶劑可為多元醇溶劑。
該多元醇溶劑可為例如選自由以下所組成之群組中的至少一者:乙二醇、二乙二醇、二乙二醇乙基醚、二乙二醇丁基醚、三乙二醇、四乙二醇、聚(乙二醇)(分子量:200至100,000)、聚(乙二醇)二丙烯酸酯、聚(乙二醇)二苯甲酸酯、二丙二醇、三丙二醇及甘油,特別是可為乙二醇、二乙二醇、三乙二醇或四乙二醇。
如上述製造之第一前驅物粒子可為In-Se、In-S或In-Se-S化合物。在一實施態樣中,鎵(Ga)鹽可另外添加於第
一溶液中,且在此情況下,第一前驅物粒子可為In-Ga-Se、In-Ga-S或In-Ga-Se-S化合物。
同時,如上述,由於本發明之CI(G)S奈米粒子係藉由在製造不包括銅(Cu)鹽之第一前驅物粒子之後分別地混合包括銅(Cu)鹽之第二溶液而製造,亦可輕易地控制銦(In)對第VI族元素的組成比及銅(Cu)之組成。具體地說,作為CI(G)S光吸收層中所使用之金屬的較佳組成比,銅(Cu)及銦(In)或銦(In)及鎵(Ga)係以0.2~1:1之莫耳比包括在該CI(G)S光吸收層中。在一實施態樣中,於本發明之步驟(iv)的混合物中,可包括基於1莫耳銦(In)或銦(In)及鎵(Ga)計為0.2至1莫耳之銅(Cu)。
當步驟(iv)之混合物中基於1莫耳之In+Ga包括1莫耳或更多銅(Cu)(低於上述組成)時,除了CI(G)S奈米粒子外,諸如Cu2Se(S)之相保留在層內部且作為太陽能電池的兩個電極之間的分流位點,因而造成薄膜太陽能電池之品質下降。
考慮到最短時間及使銅(Cu)離子均勻地滲過第一前驅物粒子之通道的所希望粒度,步驟(v)之形成CI(G)S奈米粒子的反應可藉由使第一溶液及第二溶液之混合物在150至190℃下維持2至5小時來進行。
同時,本發明之製造方法中所使用的金屬鹽及第VI族源無限制,只要該金屬鹽及第VI族源包括以下元素即可。例如,作為銅(Cu)、銦(In)及鎵(Ga)之來源的鹽可為選自由以下所組成之群組中的至少一種類型:氯化物、硝
酸鹽、亞硝酸鹽、硫酸鹽、乙酸鹽、亞硫酸鹽、乙醯丙酮化物及氫氧化物。第VI族源可為選自由以下所組成之群組中的至少一者:Na2Se、K2Se、Ca2Se、(CH3)2Se、SeO2、SeCl4、H2SeO3、Na2S、K2S、Ca2S、(CH3)2S、H2SO4、NH2SO3H、(NH2)2SO2、Na2S2O3及其水合物,可為選自由以下所組成之群組的至少一者:硫脲、硫乙醯胺、硒脲及亞硒酸作為原始材料。
此外,本發明提供根據本發明所製造之CI(G)S奈米粒子,及包括基於該等CI(G)S奈米粒子之光吸收層的薄膜。
包括該光吸收層之薄膜係藉由將據本發明之CI(G)S奈米粒子分散在溶劑中而製備的油墨塗覆在形成電極的基板上,然後進行乾燥及熱處理而製造。
此處,形成光吸收層之塗層的厚度為0.5至3μm,更特別為2至3μm。
當薄膜厚度小於0.5μm時,光吸收層之密度及量不足,因而無法獲得所需之光電效率。另一方面,當薄膜厚度超過3.0μm時,載子移動距離增加,因此重組可能性提高,此造成效率降低。在特定實施態樣中,用於製備墨汁之溶劑只要為一般有機溶劑,其並無特別限制,且可為選自以下之一種有機溶劑:烷類、烯類、炔類、芳族類、酮類、腈類、醚類、酯類、有機鹵化物類、醇類、胺類、硫醇類、羧酸類、膦類、亞磷酸酯類、磷酸酯類、亞碸類及醯胺類,或至少一種選自彼之有機溶劑的混合物。
特別是,該等醇類可為選自以下之至少一種混合溶劑:乙醇、1-丙醇、2-丙醇、1-戊醇、2-戊醇、1-己醇、2-己醇、3-己醇、庚醇、辛醇、乙二醇(EG)、二乙二醇一甲醚(DEGMEE)、乙二醇一甲醚(EGMME)、乙二醇一甲醚(EGMEE)、乙二醇二甲醚(EGDME)、乙二醇二乙醚(EGDEE)、乙二醇一丙醚(EGMPE)、乙二醇一丁醚(EGMBE)、2-甲基-1-丙醇、環戊醇、環己醇、丙二醇丙醚(PGPE)、二乙二醇二甲醚(DEGDME)、1,2-丙二醇(1,2-PD)、1,3-丙二醇(1,3-PD)、1,4-丁二醇(1,4-BD)、1,3-丁二醇(1,3-BD)、α-萜品醇、二乙二醇(DEG)、甘油、2-(乙胺基)乙醇、2-(甲胺基)乙醇及2-胺基-2-甲基-1-丙醇。
該等胺類可為至少一種選自以下之混合溶劑:三乙胺、二丁胺、二丙胺、丁胺、乙醇胺、二伸乙三胺(DETA)、三伸乙四胺(TETA)、三乙醇胺、2-胺基乙基哌、2-羥乙基哌、二丁胺及參(2-胺基乙基)胺。
該等硫醇類可為選自以下之至少一種混合溶劑:1,2-乙二硫醇、戊硫醇、己硫醇及巰乙醇。
該等烷類可為選自以下之至少一種混合溶劑:己烷、庚烷及辛烷。
該等芳族類可為選自以下之至少一種混合溶劑:甲苯、二甲苯、硝苯及吡啶。
該等有機鹵化物類可為選自以下之至少一種混合溶劑:氯仿、二氯甲烷、四氯甲烷、二氯乙烷及氯苯。
該等腈類可為乙腈。
該等酮類可為選自以下之至少一種混合溶劑:丙酮、環己酮、環戊酮及丙酮乙醯。
該等醚類可為選自以下之至少一種混合溶劑:乙醚、四氫呋喃及1,4-二烷。
該等亞碸類可為選自以下之至少一種混合溶劑:二甲亞碸(DMSO)及環丁碸。
該等醯胺類可為選自以下之至少一種混合溶劑:二甲基甲醯胺(DMF)及正甲基-2-吡咯啶酮(NMP)。
該等酯類可為選自以下之至少一種混合溶劑:乳酸乙酯、γ-丁內酯及乙醯乙酸乙酯。
該等羧酸類可為選自以下之至少一種混合溶劑:丙酸、己酸、內消旋-2,3-二巰基丁二酸、α-巰丙酸及巰乙酸。
然而,該等溶劑僅作為實例,本發明之實施態樣不局限於此。
在一些情況中,可另外將添加劑添加至油墨中。
該添加劑可為例如選自由以下所組成之群組的至少一者:分散劑、界面活性劑、聚合物、黏合劑、交聯劑、乳化劑、抗成形劑(anti-forming agent)、乾燥劑、填料、增積劑、增稠劑、膜調節劑、抗氧化劑、流化劑、調平劑及腐蝕抑制劑。特別是,該添加劑可為選自由以下所組成之群組的至少一者:聚乙烯吡咯啶酮(PVP)、聚乙烯醇、Anti-terra 204、Anti-terra 205、乙基纖維素及DispersBYK110。
該塗覆可為例如選自由以下所組成之群組中的任一者:濕式塗覆、噴霧塗覆、旋塗、刮刀塗覆、接觸印刷、頂部進料反轉印刷(top feed reverse printing)、底部進料反轉印刷(bottom feed reverse printing)、噴嘴進料反轉印刷(nozzle feed reverse printing)、凹版印刷、微凹版印刷、反轉微凹版印刷、輥塗、縫模塗覆、毛細節塗覆、噴墨印刷、噴射沉積及噴霧沉積。
熱處理可在400℃至900℃之溫度下進行。
由於本發明之CI(G)S奈米粒子包括第VI族元素,熱處理可減少至5至10分鐘,且第VI族元素仍具有相同反應性。
此外,本發明提供使用該薄膜所製造之薄膜太陽能電池。
本技術中已知製造薄膜太陽能電池之方法,因此本文中省略其詳細描述。
從以下詳細描述並結合附圖,將更清楚暸解本發明之上述及其他目的、特徵及其他優點;該等附圖中:圖1為根據實施例1所形成之CI(G)S奈米粒子的掃描式電子顯微鏡(SEM)影像;圖2為根據實施例2所形成之CI(G)S奈米粒子的掃描式電子顯微鏡(SEM)影像;圖3為根據實施例2所形成之CI(G)S奈米粒子的穿
透式電子顯微鏡(TEM)影像;圖4為根據實施例2所形成之CI(G)S奈米粒子的EDX分析之結果的影像;圖5為根據實施例3所形成之CI(G)S奈米粒子的掃描式電子顯微鏡(SEM)影像;圖6為根據實施例4所形成之CI(G)S奈米粒子的掃描式電子顯微鏡(SEM)影像;圖7為根據對照實例1所形成之CI(G)S奈米粒子的掃描式電子顯微鏡(SEM)影像;圖8為根據對照實例2所形成之CI(G)S奈米粒子的掃描式電子顯微鏡(SEM)影像;圖9為顯示根據實施例5所製備之薄膜的SEM影像;圖10為顯示根據實施例5所製備之薄膜的XRD圖;圖11為顯示根據實施例6所製備之薄膜的SEM影像;圖12為顯示根據實施例6所製備之薄膜的XRD圖;圖13為顯示根據實施例7所製備之薄膜的SEM影像;圖14為顯示根據實施例7所製備之薄膜的XRD圖;圖15為顯示根據對照實例3所製備之薄膜的SEM影像;及圖16為顯示根據對照實例3所製備之薄膜的XRD圖。
茲參考以下實施例更詳細描述本發明。該等實例僅用以舉例說明本發明,且不應被視為限制本發明之範圍及精神。
將5毫莫耳之硝酸銦水溶液及10毫莫耳之亞硒酸溶解於70ml之乙二醇中及混合之後,將混合物加熱至150℃且反應2小時。在將50ml之溶解有5毫莫耳的氮氧化Cu(II)之乙二醇添加至該混合物之後,將所形成之混合物加熱至150℃且維持4小時。在該反應完成之後,藉由離心作用純化該混合物以製造具有Cu離子遷移之非晶形InSe2粒子的大約CuInSe2組成之CI(G)S奈米粒子。
將7毫莫耳之硝酸銦水溶液、3毫莫耳之硝酸鎵水溶液及20毫莫耳之亞硒酸溶解於150ml之乙二醇中及混合之後,將混合物加熱至150℃且反應1小時。在將50ml之溶解有10毫莫耳的氮氧化Cu(II)之乙二醇添加至該混合物之後,使其在150℃維持2小時,然後在170℃維持1小時。在該反應完成之後,藉由離心作用純化該混合物以製造具有Cu離子遷移之非晶形In(Ga)Se粒子的大約CuIn(Ga)Se2組成之CI(G)S奈米粒子。
將7毫莫耳之硝酸銦水溶液、3毫莫耳之硝酸鎵水溶液及20毫莫耳之亞硒酸溶解於150ml之乙二醇中及混合之後,將混合物加熱至150℃且反應2小時。在將20ml之溶解有10毫莫耳的氮氧化Cu(II)之乙二醇添加至該混合物之後,使所形成之混合物在150℃維持2小時。在該反應完成之後,藉由離心作用純化該混合物以製造具有Cu離子遷移之非晶形In(Ga)Se粒子的大約CuIn(Ga)Se1.5組成之CI(G)S奈米粒子。
將5毫莫耳之硝酸銦水溶液及10毫莫耳之亞硒酸溶解於100ml之乙二醇中及混合之後,將混合物加熱至150℃且反應4小時。在將50ml之溶解有5毫莫耳的氮氧化Cu(II)之乙二醇添加至該混合物之後,使所形成之混合物在170℃維持4小時。在該反應完成之後,藉由離心作用純化該混合物以製造具有Cu離子遷移之非晶形InSe2粒子的大約CuInSe2組成之CI(G)S奈米粒子。
在120ml乙二醇中混合5毫莫耳之Cu(NO3)2、5毫莫耳之In(NO3)3及10毫莫耳之亞硒酸。將該混合物插入熱壓器且在210℃下藉由攪拌反應15小時。藉由離心作
用純化所製備之粒子以具有製造大約CuInSe2組成的CI(G)S奈米粒子。
在100ml之乙二醇中混合7.5毫莫耳之Cu(NO3)2、10.5毫莫耳之In(NO3)3、4.5毫莫耳之Ga(NO3)3及15毫莫耳之亞硒酸。該混合物在170℃下藉由攪拌反應6小時。藉由離心作用純化所製備之粒子以具有製造大約Cu0.5In0.7Ga0.3Se組成的CI(G)S奈米粒子。
分析實施例1至4及對照實例1及2中所形成之奈米粒子的掃描式電子顯微鏡影像係示於圖1、2及5至8。
參考圖1、2、5及6,於實施例1中所製造之CI(G)S奈米粒子的平均直徑為100nm,於實施例2中所製造之CI(G)S奈米粒子的平均為70至130nm,於實施例3中所製造之CI(G)S奈米粒子的平均直徑為60nm,及於實施例4中所製造的CI(G)S奈米粒子的平均直徑為30至80nm。因此,該等實驗之所有奈米粒子係在30至200nm之直徑範圍內且為球狀類型。
另一方面,參考圖7及8,對照實例1及2中所製造之CI(G)S奈米粒子的平均直徑具有大偏差。此外,CI(G)S奈米粒子不為球狀類型。
此外,為了詳細觀察本發明之奈米粒子,分析實施例
2中所形成的奈米粒子之穿透式電子顯微鏡(TEM)及能量色散X射線(EDX)影像係示於圖3及圖4。
參考圖3及圖4,確認一些本發明之奈米粒子係由遷移至非晶形粒子中大約50nm之內部空間的Cu離子所形成的大約10nm之小結晶粒子的新結晶作用而形成,整體富含In及Ga且均勻包含Cu、In、Ga及Se所有者。
將根據實施例1之CI(G)S奈米粒子以20%之濃度分散在醇系溶劑中以製備油墨。將Mo沉積至玻璃基板上之後,以該油墨塗覆該玻璃基板,形成塗層以製造CI(G)S薄膜。將經塗覆之玻璃基板乾燥至200℃,然後在Se氣氛下於530℃熱處理10分鐘,形成CI(G)S薄膜。所獲得之薄膜的剖面形狀及XRD相分別示於圖9及10。
將根據實施例2之CI(G)S奈米粒子以25%之濃度分散在醇系溶劑中以製備油墨。將Mo沉積至玻璃基板上之後,以該油墨塗覆該玻璃基板,形成塗層以製造CI(G)S薄膜。將經塗覆之玻璃基板乾燥至220℃,然後在Se氣氛下於550℃熱處理5分鐘,形成CI(G)S薄膜。所獲得之薄膜的剖面形狀及XRD相分別示於圖11及12。
將根據實施例3之CI(G)S奈米粒子以25%之濃度分散在醇系溶劑中以製備油墨。將Mo沉積至玻璃基板上之後,以該油墨塗覆該玻璃基板,形成塗層以製造CI(G)S薄膜。將經塗覆之玻璃基板乾燥至260℃,然後在Se氣氛下於640℃熱處理5分鐘,形成CI(G)S薄膜。所獲得之薄膜的剖面形狀及XRD相分別示於圖13及14。
將根據實施例4之CI(G)S奈米粒子以22%之濃度分散在醇系溶劑中以製備油墨。將Mo沉積至玻璃基板上之後,以該油墨塗覆該玻璃基板,形成塗層以製造CI(G)S薄膜。將經塗覆之玻璃基板乾燥至200℃,然後在Se氣氛下於575℃熱處理5分鐘,形成CI(G)S薄膜。
以與實施例1相同方式合成Cu0.2InSe及Cu2In粒子。此處,該Cu0.2InSe中之Cu:In的組成改為0.2:1。將該等Cu0.2InSe及Cu2In粒子混合,然後以25%之濃度分散在醇系溶劑中以製備油墨。將該油墨塗覆至藉由將Mo
沉積至玻璃基板上所獲得之基板上,形成塗層以製造CI(G)S薄膜。將該塗層乾燥至200℃,然後在Se氣氛下於575℃熱處理5分鐘,形成CI(G)S薄膜。
將對照實例2中合成之CI(G)S奈米粒子以16.5%之濃度分散在醇系溶劑中以製備油墨。將該油墨塗覆至藉由將Mo沉積至玻璃基板上所獲得之基板上,形成塗層以製造CI(G)S薄膜。將該塗層乾燥至260℃,然後在Se氣氛下於640℃熱處理5分鐘,形成CI(G)S薄膜。所獲得之CI(G)S薄膜的剖面形狀及XRD相分別示於圖15及16。
在使用CBD法從實施例6所獲得之CI(G)S薄膜上製造CdS緩衝層之後,將ZnO及AlZnO依序沉積至該Cds緩衝層上。然後,在該沉積之層上採用電子束形成Al電極,產生VOC為0.34V、JSC為4.05mAcm2、填充係數為25.73%、及效率為0.36%之電池。
在使用CBD法從實施例7所獲得之CI(G)S薄膜上製
造CdS緩衝層之後,將ZnO及AlZnO依序沉積至該Cds緩衝層上。然後,在該沉積之層上採用電子束形成Al電極,產生VOC為0.04V、JSC為4.94mAcm2、填充係數為24.91%、及效率為0.05%之電池。
在使用CBD法從實施例9所獲得之CI(G)S薄膜上製造CdS緩衝層之後,將ZnO及AlZnO依序沉積至該Cds緩衝層上。然後,在該沉積之層上採用電子束形成Al電極,產生VOC為0.24V、JSC為23.15mAcm2、填充係數為34.37%、及效率為1.92%之電池。
測量實施例10至12中所製造之基於CI(G)S的薄膜太陽能電池之光電效率。結果係彙總於下表1。
在表1中,JSC(其為決定每一太陽能電池之效率的變量)代表電流密度,VOC表示在零輸入電流下測量之斷路電壓,光電效率意指根據入射在太陽能電池板上之光的照射之電池輸出率,及填充因數(FF)代表最大功率點之電流密度與電壓值相乘所獲得的值除以VOC乘以JSC所獲得之值所獲得的值。
如表1所示,確認當根據本發明所製造的具有遷移之銅(Cu)離子的CI(G)S奈米粒子用於光吸收層形成時,電流密度及電壓高。
圖1至8之CI(G)S奈米粒子在熱處理期間不具有諸如氧化的問題或不形成CI(G)S相。此外,由於本發明之CI(G)S奈米粒子包括所有金屬及第VI族元素,可製備均勻組成物。另外,由於CI(G)S奈米粒子之結晶粒子與CI(G)S結晶粒子不相同,展現快速粒子生長。因此,本發明之CI(G)S奈米粒子具有高電流密度及電壓。
同時,用於對照實例3中之CI(G)S粒子具有上述問題。參考圖15及圖16,薄膜之層密度低且薄膜品質不高。因此,該薄膜不適於製造薄膜太陽能電池,及另外,當使用此種薄膜製造太陽能電池時,光電效率極低。
熟習本領域之人士將認可在不違背如附錄申請專利範圍所揭示之本發明範圍與精神的情況下,各種修改、添加及取代係屬可能。
如上述,本發明之CI(G)S奈米粒子的製造方法可首先形成包括銦(In)及第VI族元素之第一前驅物粒子,及選擇性地進一步包括鎵(Ga),然後將銅(Cu)鹽添加至該第一前驅物粒子而自由地控制粒子組成及均勻地合成具有預定直徑之球狀粒子。
因此,當使用CI(G)S奈米粒子製造光吸收層時,可解決CI(G)S薄膜的部分組成不均勻性。此外,因均勻球狀粒子之故,塗層之密度提高。此外,使用包括第VI族元素之奈米粒子,可縮減薄膜製造程序中之熱處理時間,及可解決第VI族元素的短缺現象。
Claims (17)
- 一種形成太陽能電池之光吸收層的CI(G)S奈米粒子之製備方法,該方法包括:將至少一種選自由包含硫(S)、硒(Se)或其組合之化合物所組成的群組之第VI族源及銦(In)鹽溶解於溶劑中以製備第一溶液;使該第一溶液反應以形成第一前驅物粒子;將銅(Cu)鹽溶解於溶劑中以製備第二溶液;將該第二溶液與該形成有該第一前驅物之第一溶液混合以製造混合物,及在藉由使該混合物反應而合成CI(G)S奈米粒子之後純化該合成的CI(G)S奈米粒子。
- 如申請專利範圍第1項之方法,其中該第一溶液及第二溶液各者的溶劑為多元醇溶劑。
- 如申請專利範圍第2項之方法,其中該多元醇溶劑為選自由以下所組成之群組中的至少一者:乙二醇、二乙二醇、二乙二醇乙基醚、二乙二醇丁基醚、三乙二醇、四乙二醇、聚(乙二醇)(分子量:200至100,000)、聚(乙二醇)二丙烯酸酯、聚(乙二醇)二苯甲酸酯、二丙二醇、三丙二醇及甘油。
- 如申請專利範圍第1項之方法,其中該第一溶液另外包含鎵(Ga)鹽。
- 如申請專利範圍第1或4項之方法,其中該鹽為選自由以下所組成之群組中的至少一者:氯化物、硝酸鹽、 亞硝酸鹽、硫酸鹽、乙酸鹽、亞硫酸鹽、乙醯丙酮化物及氫氧化物。
- 如申請專利範圍第1項之方法,其中該第VI族源為選自由以下所組成之群組中的至少一者:Na2Se、K2Se、Ca2Se、(CH3)2Se、SeO2、SeCl4、H2SeO3、Na2S、K2S、Ca2S、(CH3)2S、H2SO4、NH2SO3H、(NH2)2SO2、Na2S2O3及其水合物。
- 如申請專利範圍第1項之方法,其中該第VI族源為選自由以下所組成之群組的至少一者:硫脲、硫乙醯胺、硒脲及亞硒酸。
- 如申請專利範圍第1項之方法,其中該溶解之第一溶液基於1莫耳之銦計包含0.5至2莫耳之第VI族源。
- 如申請專利範圍第1項之方法,其中該混合之混合物基於1莫耳之銦(In)計包含0.2至1莫耳之銅(Cu)。
- 如申請專利範圍第1項之方法,其中該合成之CI(G)S奈米粒子為具有30至200nm之平均直徑的球狀粒子。
- 如申請專利範圍第10項之方法,其中該CI(G)S奈米粒子具有50nm至150nm之平均直徑。
- 如申請專利範圍第1項之方法,其中該合成之CI(G)S奈米粒子包含遷移至非晶形第一前驅物粒子的通道中之銅(Cu)離子。
- 如申請專利範圍第1項之方法,其中該等第一前驅物粒子為非晶形,且該等包含遷移銅(Cu)離子之CI(G)S 奈米粒子為非晶形或一部分該等CI(G)S奈米粒子因遷移至該非晶形第一前驅物粒子的Cu離子而為晶形。
- 一種CI(G)S奈米粒子,其係使用如申請專利範圍第1至13項中任一項之方法製得。
- 一種薄膜,其包含基於如申請專利範圍第14項之CI(G)S奈米粒子的光吸收層。
- 如申請專利範圍第15項之薄膜,其中該光吸收層形成厚度為2至3μm。
- 一種薄膜太陽能電池,其係使用如申請專利範圍第15項之薄膜所製得。
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