TWI583013B - 用於製造太陽能電池的光吸收層之墨液組成物及使用彼之製造薄膜之方法、合成核-殼結構型奈米粒子之方法、薄膜及薄膜太陽能電池 - Google Patents
用於製造太陽能電池的光吸收層之墨液組成物及使用彼之製造薄膜之方法、合成核-殼結構型奈米粒子之方法、薄膜及薄膜太陽能電池 Download PDFInfo
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- TWI583013B TWI583013B TW103126435A TW103126435A TWI583013B TW I583013 B TWI583013 B TW I583013B TW 103126435 A TW103126435 A TW 103126435A TW 103126435 A TW103126435 A TW 103126435A TW I583013 B TWI583013 B TW I583013B
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
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- H01L31/03845—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including other non-monocrystalline materials, e.g. semiconductor particles embedded in an insulating material comprising semiconductor nanoparticles embedded in a semiconductor matrix
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Description
本發明係關於一種用於製造太陽能電池的光吸收層之墨液組成物及使用彼之製造薄膜之方法。更特別地,本發明係關於一種用於製造太陽能電池的光吸收層之墨液組成物,其包含核-殼結構型奈米粒子;與雙金屬或金屬間金屬奈米粒子,或金屬硫屬化物奈米粒子,及使用彼之製造薄膜之方法。
自從發展初期,人們業已使用高成本所形成的光吸收層及作為半導體材料的矽(Si)製造太陽能電池。人們已發展出使用廉價光吸收材料例如硫硒化銅銦鎵(CIGS)或Cu(In,Ga)(S,Se)2的薄膜太陽能電池結構,以更經濟地製造具商業利益的太陽能電池。這類CIGS系太陽能電池一
般包含背電極層、n型接面部件、及p型光吸收層。含有這類CIGS層之太陽能電池具有大於19%的光電轉換效率。然而,即使CIGS系薄膜太陽能電池的潛力,In的成本及供給不足是使用CIGS系光吸收層之薄膜太陽能電池廣泛商業應用的主要障礙。因此,急需發展使用無In或低成本通用元素之太陽能電池。
因此,作為該CIGS系光吸收層替代品,近來含有非常便宜的元素銅(Cu)、鋅(Zn)、錫(Sn)、硫(S)、或硒(Se)之CZTS(Cu2ZnSn(S,Se)4)系太陽能電池已經受到重視。CZTS之直接能隙為約1.0eV至約1.5eV及吸收係數為104cm-1或更多,彼等之儲量相對高,且CZTS使用廉價之Sn與Zn。
在1996年,CZTS異質接面光伏打電池(hetero-junction PV battery)首度被報告,但CZTS系太陽能電池進步的比CIGS系太陽能電池少,且CZTS系太陽能電池之光電效率是10%或更少,比CIGS系太陽能電池之光電效率低得多。CZTS薄膜係藉由下列方法所製造:濺鍍法、複合濺鍍法、脈衝雷射沈積法、噴霧熱裂解法、電沈積/熱處理硫化法、電子束處理法、Cu/Zn/Sn/熱處理硫化法、及溶膠-凝膠法。
在製造方法方面,WO2007-134843揭示藉由真空濺鍍及在S或Se氛圍中熱處理該所得之材料同時或循序地堆疊Cu、Zn、與Sn以形成CZTS層之方法。有些論文((Phys,Stat.Sol.C.2006,3,2844./Prog.Photovolt:Res.Appl.2011;19:93-96)揭示藉由同時真空蒸鍍法將Cu、Zn、Sn、S或Se同時沈積於基底上以形成CZTS層之方
法。然而,前述相關技術之優點在於沈積是在相對良好之控制狀態進行,但缺點在於使用高價設備所以製造成本高。
同時,PCT/US/2010-035792揭示藉由將在基底上的含有CZTS/Se奈米粒子之墨液熱處理以形成薄膜。在形成CZTS前驅物粒子之方法方面,Journal,J.Am.Chem.Soc.,2009,131,11672揭示藉由熱注射法在高溫下將含有Cu、Sn與Zn前驅物之溶液及含有S或Se之溶液混合以形成CZTS奈米粒子。此外,US2011-0097496揭示使用以肼溶解Cu、Zn、Sn鹽與過量的S或Se所製備的用於形成該CZTS層之前驅物,接著藉由熱處理及硒化以形成CZTS層之方法。然而,熱注射法有穩定性的問題。此外,含有含過量S或Se之硫屬化合物的肼是一種高毒性、高反應性、高爆炸性溶劑,所以使用肼之溶液製程需承擔高風險。此外,肼很難處理,所以在製造程序上有難度。
因此,高度需要發展使用比現行的CZTS層製造方法更低價且更安全的製造方法之含有高效率光吸收層且有穩定的抗氧化性之薄膜太陽能電池的技術。
因此,本發明之目的是解決前述難題及其他尚待解決的技術難題。
由於各式各樣精深研究及各式各樣實驗之結果,本發明之發明人證實當使用核-殼結構型奈米粒子,該核-殼結構型奈米粒子包含含有含銅(Cu)的硫屬化物之核及含有含鋅(Zn)的硫屬化物之殼,與含錫(Sn)之雙金屬或金屬間金屬奈米粒子,或含錫(Sn)之硫屬化物奈米粒子製造光吸收層時,由於低價且安全的製造程序所以可提升產能,且由於用於CZTS系太陽能電池之具有高密度且有穩定的抗氧化性之光吸收層的生長所以可改良光電效率。
根據本發明一方面,本發明提供一種用於製造太陽能電池的光吸收層之墨液組成物,其包含核-殼結構型奈米粒子,該核-殼結構型奈米粒子包含含有含銅(Cu)的硫屬化物之核及含有含鋅(Zn)之硫屬化物;與含錫(Sn)之雙金屬或金屬間金屬奈米粒子,或含錫(Sn)之硫屬化物奈米粒子的殼,分散於溶劑中。
在這裡,術語「硫屬化物」意指含有第VI族元素例如硫(S)與/或硒(Se)之材料。
一般來說,當使用CZTS結晶式奈米粒子形成CZTS薄膜時,先前所形成之結晶很小且由此在後續的薄膜製造過程很難擴大晶體粒徑。結果,各個晶粒很小且因此擴大界面,因此電子損失發生在界面處,導致效率劣化。
和前述相比,當用Cu、Zn與Sn形成非CZTS結晶且透過第二相分開存在的CZTS薄膜時,在薄膜形成步驟過
程中及結晶生長同時,各種元素重排及由此可改良薄膜密度與晶體粒徑。
因此,用於薄膜之奈米粒子必須包含Cu、Zn與Sn且不得為CZTS結晶型。
因此,由於精深研究之結果,本發明之發明人證實當使用由於適當地混合二種硫屬化物與金屬及可大量生產之金屬奈米粒子或金屬硫屬化物奈米粒子而形成穩定相之核-殼結構型前驅物形成薄膜時,可適當地解決前述難題。
在一特定具體實施方式中,該可大量生產之雙金屬或金屬間金屬奈米粒子可為作為含錫(Sn)的雙金屬或金屬間金屬奈米粒子之Cu3Sn或Cu6Sn5。該金屬硫屬化物奈米粒子可為作為含錫(Sn)的硫屬化物奈米粒子之SnzS(0.5z2.0)與/或SnwSe(0.5w2.0)且,特別地,可為選自由下列所組成之群組中的至少一種:SnS、SnS2、SnSe與SnSe2。
在這裡,為了調整CZTS薄膜之組成比例,另外需要該含錫(Sn)的雙金屬或金屬間金屬奈米粒子、或含錫(Sn)的硫屬化物奈米粒子及含有其他金屬元素之硫屬化物。然而,當Cu之硫屬化物或含Zn之硫屬化物被分別合成及混合時,金屬之組成比例可能不均勻。因此,本發明之發明者發展出含Cu與Zn之核-殼結構型奈米粒子且,如此,解決了由於不均勻之組成所引起的難題。
在一種特定具體實施方式中,該含銅(Cu)之硫屬化物可為選自由下列所組成之群組中的至少一種:CuS、
CuxS(1.7x2.0)、CuSe與CuySe(1.7y2.0),特別地,可為選自由下列所組成之群組中的至少一種:Cu2S、CuS、Cu2Se與CuSe,且,更特別地,可為CuS與/或CuSe。
此外,該含鋅(Zn)之硫屬化物可為ZnS與/或ZnSe。
同時,在結構方面,當該含鋅(Zn)之硫屬化物是核及該含銅(Cu)之硫屬化物是殼時,由於Zn與Cu之不同的電離傾向,在核-殼結構型奈米粒子製造過程中,該含鋅(Zn)之硫屬化物核的某些Zn可被電離同時Cu可被容易地還原。因此,該含鋅(Zn)之硫屬化物核與含銅(Cu)之硫屬化物殼未明確地形成且可能容易形成混合型態。因此,當和該含銅(Cu)之硫屬化物是核的情形相比時,該結構沒有任何特殊的優點且鋅(Zn)離子反而可能消失。
反之,如本發明所述,當該含銅(Cu)之硫屬化物是核及該含鋅(Zn)之硫屬化物是殼時,可藉由調控該核與殼之厚度而容易地調控最終CZTS薄膜之組成比例,且,如此,可形成具有各式各樣的組成比例之CZTS薄膜。在一種特定具體實施方式中,該核之直徑可為20奈米到200奈米。
在此範圍之外,當該含有含銅(Cu)之硫屬化物的核之粒徑太大時,含有所形成之殼的核-殼結構型奈米粒子之粒徑大幅擴大,且,如此,在厚度為1微米到2微米之最終薄膜中的粒子中間的孔隙擴大。反之,當核之直徑太小時,粒子可能容易凝縮。此外,該殼之厚度變成太薄,且,如此,該殼不能適當地形成以提供具有適當組成比例
之最終薄膜。
同時,在形成核之後,當殼形成於該核表面時,藉由該反應器之反應時間、反應溫度與濃度調控該殼的厚度。因此,藉由調控該反應條件所形成之殼的厚度可較佳地是1奈米到75奈米。
該含有含鋅(Zn)之硫屬化物的殼之厚度的決定條件是所欲CZTS薄膜的整體組成比例及對核的組成比例。在最終薄膜中的Cu:Zn:Sn組成比例較佳地是約1.5~2.5:0.9~1.5:1。因此,當將金屬奈米粒子混合以形成CZTS薄膜時,在該核-殼結構型奈米粒子中的Cu:Zn組成比例可為0.3~1.3:0.9~1.5。因此,當該核之直徑是20奈米到200奈米時,該殼之厚度可為在前述範圍內。
同時,如前文所提到,在最終薄膜中的Cu:Zn:Sn組成比例較佳地是約1.5~2.5:0.9~1.5:1。因此,該核-殼結構型奈米粒子;及含錫(Sn)之雙金屬或金屬間金屬奈米粒子或含錫(Sn)之硫屬化物奈米粒子可經混合以符合0.5<Cu/(Sn+Zn)<1.4。
在一特定具體實施方式中,該溶劑不被特別限制,只要該溶劑是一般的有機溶劑即可且可為選自下列之中的一種有機溶劑或至少一種選自下列之中的有機溶劑混合物:烷類、烯類、炔類、芳香烴類、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、磷酸酯類、亞碸類、及醯胺類。
特別地,該醇類可為至少一種選自下列之中的混合溶
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)、二乙二醇一乙醚(DEGMEE)、乙二醇一甲醚(EGMME)、乙二醇一乙醚(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-(乙基胺基)乙醇、2-(甲基胺基)乙醇、及2-胺基-2-甲基-1-丙醇。
該胺類可為至少一種選自下列之中的混合溶劑: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-羥基乙基哌、二丁胺、及三(2-胺基乙基)胺。
該硫醇類可為至少一種選自下列之中的混合溶劑:1,2-乙二硫醇、戊硫醇、己硫醇、及巰基乙醇。
該烷類可為至少一種選自下列之中的混合溶劑:己烷、庚烷、及辛烷。
該芳香烴類可為至少一種選自下列之中的混合溶劑:甲苯、二甲苯、硝基苯、及吡啶。
該有機鹵化物類可為至少一種選自下列之中的混合溶劑:三氯甲烷、二氯甲烷、四氯甲烷、二氯乙烷、及氯苯。
該腈類可為乙腈。
該酮類可為至少一種選自下列之中的混合溶劑:丙酮、環己酮、環戊酮、及乙醯丙酮。
該醚類可為至少一種選自下列之中的混合溶劑:乙醚、四氫呋喃、及1,4-二烷。
該亞碸類可為至少一種選自下列之中的混合溶劑:二甲亞碸(DMSO)及環丁碸。
該醯胺類可為至少一種選自下列之中的混合溶劑:二甲基甲醯胺(DMF)及N-甲基-2-吡咯啶酮(NMP)。
該酯類可為至少一種選自下列之中的混合溶劑:乳酸乙酯、γ-丁內酯、及乙醯乙酸乙酯。
該羧酸類可為至少一種選自下列之中的混合溶劑:丙酸、己酸、間-2,3-二巰基丁二酸、硫代乳酸、及硫代乙醇酸。
然而,該溶劑只被給予作為實例,且本發明具體實施方式不限於此。
在某些情况下,可另外加入添加劑以製造該墨液組成物。
該添加劑可例如為選自由下列所組成之群組中的至少一種:分散劑、界面活性劑、聚合物、黏合劑、交聯劑、乳化劑、消泡劑、乾燥劑、填料、填充劑、增稠劑、薄膜處理劑、抗氧化劑、助流劑、整平劑、及腐蝕抑制劑。特別地,該添加劑可為選自由下列所組成之群組中的至少一種: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。
本發明也提供一種製造該核-殼結構型奈米粒子的方法,該方法包含:(i)製備第一溶液,其含有至少一種選自由包含硫(S)、或硒(Se)、或硫(S)與硒(Se)之化合物的群組的第VI族源;(ii)製備含有銅(Cu)鹽之第二溶液及含有鋅(Zn)鹽之第三溶液;(iii)混合該第一溶液與第二溶液而製造混合物;(iv)透過該混合物之反應而合成含銅(Cu)的硫屬化物核粒子;及(v)藉由混合該第三溶液與包含該合成的核粒子之產物而形成殼,然後純化該殼。
在一種特定具體實施方式中,該第一溶液、第二溶液與第三溶液之溶劑各獨立地可為選自由下列所組成之群組中的至少一種:水、甲醇、乙醇、二醇類溶劑、十八碳烯胺、二甲亞碸及二甲基甲醯胺。
該二醇類溶劑不被特別限制且可為選自由下列所組成之群組中的至少一種:例如乙二醇、二乙二醇、NMP、二乙二醇一乙醚(DEGMEE)及三乙二醇。
在一種特定具體實施方式中,該包含於第一溶液的第VI族源可為選自由下列所組成之群組中的至少一種:Se、Na2Se、K2Se、Ca2Se、(CH3)2Se、SeO2、SeCl4、H2SeO3、Na2S、K2S、Ca2S、(CH3)2S、H2SO4、S、
Na2S2O3、NH2SO3H與彼等之水合物,或可為選自由下列所組成之群組中的至少一種:作為有機物質的硫脲、硫代乙醯胺、與硒脲。
在一種特定具體實施方式中,該包含於第二溶液與第三溶液的鹽類可為選自由下列所組成之群組中的至少一種:氯化物、硝酸鹽、亞硝酸鹽、硫酸鹽、乙酸鹽、亞硫酸鹽、乙醯丙酮酸鹽及氫氧化物。
同時,當如步驟(iii)所述的混合該第一溶液與第二溶液時,以1mol的銅(Cu)鹽計,該混合物中的該第VI族源含量是0.5mol或更多,特別地所欲含量是在0.5mol至4mol範圍內。
在前述範圍之外,當所含有之該第VI族源含量少於0.5mol時,不可能充分供應該第VI族元素,因此未形成CuS(Se)或Cu2S(Se)穩定相,所以在後續的製程中相可能變化或經分離的金屬可能被氧化。
此外,當所含有之該第VI族源含量大於4mol時,在熱處理以製造薄膜的過程中非所欲第VI族元素的產生增加且該第VI族源被汽化,且,如此,在最終薄膜中孔隙可能過度地產生。
在這裡,藉由攪拌該混合物同時將該第二溶液慢慢逐滴加到該第一溶液,可得到具有均勻組成與粒徑的含銅(Cu)之硫屬化物核粒子。
此外,如步驟(v)所述,可將透過步驟(v)所製造之作為核粒子的含銅(Cu)之硫屬化物粒子與該含有鋅(Zn)鹽之
第三溶液混合,以在該核粒子表面形成殼。
在這裡,在該混合製程中,該殼之厚度可由該鋅(Zn)鹽濃度決定。因此,該鋅(Zn)鹽濃度可藉由最終薄膜之組成比例適當地測定。
在一種特定具體實施方式中,在該第三溶液之混合製程中,可另外添加第VI族源以解決在後續的CZTS層形成製程中該第VI族元素有部份不足的問題。在這裡,可考慮在前面的含銅(Cu)之硫屬化物核粒子形成製程中殘留的第VI族元素的份量來添加該第VI族源。
同時,可使用還原劑製造該含錫(Sn)之雙金屬或金屬間金屬奈米粒子。形成該Cu-Sn雙金屬金屬奈米粒子之方法例如包含:(i)製備含有還原劑之第一溶液;(ii)製備含有銅(Cu)鹽與錫(Sn)鹽之第二溶液;(iii)將該第二溶液逐滴加到該第一溶液以製造混合物;及(iv)透過該混合物之反應而合成一或多種的Cu-Sn雙金屬金屬奈米粒子然後純化。
在這裡,該還原劑不是有毒的肼且可為有機還原劑與/或無機還原劑。特別地,該還原劑可為選自由下列所組成之群組中的一種:LiBH4、NaBH4、KBH4、Ca(BH4)2、Mg(BH4)2、LiB(Et)3H、NaBH3(CN)、NaBH(OAc)3、抗壞血酸及三乙醇胺。該溶液之溶劑與鹽種類同於前面所述者。
當將該第二溶液逐滴加到該第一溶液以製造混合物時,該還原劑對該鹽類總重量之混合比例可為例如莫耳比1:1到1:20。
當該還原劑重量和鹽類重量相比太小時,不能使金屬鹽類充分地還原。因此,所得之雙金屬金屬奈米粒子的粒徑或份量可能太小,或很難得到具有所欲元素比例的粒子。此外,當該還原劑重量比該鹽類重量大20倍時,在純化步驟無法將還原劑及副產物有效除去。
可考慮最終產物之所欲重量來適當地決定該所含有之鹽類重量。
此外,該第一溶液與/或第二溶液可進一步包含封閉劑等以防止金屬奈米粒子氧化。
前述製造方法僅是一個實例而已。可根據所欲金屬奈米粒子對該金屬鹽類之金屬種類作出各式各樣的選擇。
此外,製造該含錫(Sn)之硫屬化物奈米粒子的方法同於製造該含銅(Cu)之硫屬化物核粒子的方法,但是利用錫(Sn)鹽而不用銅(Cu)鹽。
同時,本發明之發明者證實該如前面描述所製造的核-殼結構型奈米粒子有穩定的抗氧化性及優異的反應性。因此,由於精深研究之結果,本發明之發明者證實當使用該核-殼結構型奈米粒子;與該含錫(Sn)之雙金屬或金屬間金屬奈米粒子,或含錫(Sn)之硫屬化物奈米粒子製造光吸收層時,可製造出更優異品質的薄膜。
因此,本發明也提供一種製造使用該用於製造太陽能
電池的光吸收層之墨液組成物的薄膜之方法,該方法包含:(i)混合核-殼結構型奈米粒子;與含錫(Sn)之雙金屬或金屬間金屬奈米粒子或含錫(Sn)之硫屬化物奈米粒子及溶劑以製造墨液;(ii)將該墨液塗覆於具備電極的基底上;及(iii)乾燥然後熱處理經塗覆於該具備電極的基底上的該墨液。
步驟(ii)之形成該塗覆層的方法可例如為選自由下列所組成之群組中的至少一種:濕式塗覆、噴霧塗覆、旋轉塗覆、刮刀塗覆、接觸印刷、上進料反印、下進料反印、噴嘴進料反印、凹板印刷、微凹板印刷、反向式微凹板印刷、輥筒塗覆、狹縫式塗覆、毛細管塗覆、噴墨印刷、噴射沈積、及噴霧沈積。
該步驟(iii)之熱處理可在溫度為400℃到900℃下進行。
同時,可將硒化製程包括在內以製備具有密度高得多的太陽能電池的薄膜。該硒化製程可透過各式各樣的方法進行。
就第一個實例而言,從該硒化製程所得之功效可藉由將S與/或Se分散於步驟(i)之帶有核-殼結構型奈米粒子;與含錫(Sn)之雙金屬或金屬間金屬奈米粒子或含錫(Sn)之硫屬化物奈米粒子的溶劑中成粒子形式以製造墨液,及合併該步驟(iii)之熱處理而達成。
就第二個實例而言,從該硒化製程所得之功效可在S或Se存在下透過步驟(iii)之熱處理而達成。
特別地,S或Se可藉由透過加熱供應氣態H2S或H2Se或供應氣態Se或S而存在。
就第三個實例而言,在步驟(ii)後,可將S或Se堆疊於該經塗覆之基底上,接著進行步驟(iii)。特別地,該堆疊製程可藉由溶液製程或沈積法進行。
本發明也提供使用前述方法製造的薄膜。
該薄膜厚度可為0.5μm到3.0μm,較特別地是0.5μm到2.5μm。
當該薄膜厚度少於0.5μm時,該光吸收層之密度與份量不足,所以可能得不到所欲光電效率。反之,當該薄膜厚度超過3.0μm時,載子之傳輸距離增加且,因此,復合的可能性增加而造成效率減低。
本發明也提供使用該薄膜製造的薄膜太陽能電池。
製造薄膜太陽能電池之方法是該技術領域內已知的,因此在本案中省略對彼之詳細描述。
本發明之前述及其他的目的、特徵及其他優點將從下列與附圖有關的詳細描述中被更清楚地理解,其中:圖1是根據製造例1製造的CuS奈米粒子之掃瞄電子顯微鏡(SEM)影像;圖2是根據製造例1製造的CuS奈米粒子之X射線
繞射(XRD)圖;圖3是根據製造例5製造的CuS奈米粒子之掃瞄電子顯微鏡(SEM)影像;圖4是根據製造例5製造的CuS奈米粒子之X射線繞射(XRD)圖;圖5是根據製造例8製造的CuS奈米粒子之掃瞄電子顯微鏡(SEM)影像;圖6是根據製造例8製造的CuS奈米粒子之X射線繞射(XRD)圖;圖7是根據製造例12製造的CuS奈米粒子之掃瞄電子顯微鏡(SEM)影像;圖8是根據製造例12製造的CuS奈米粒子之X射線繞射(XRD)圖;圖9是根據製造例13製造的CuS奈米粒子之掃瞄電子顯微鏡(SEM)影像;圖10是根據製造例13製造的CuS奈米粒子之X射線繞射(XRD)圖;圖11是根據製造例17製造的CuS-核-ZnS-殼型奈米粒子之掃瞄電子顯微鏡(SEM)影像;圖12是根據製造例17製造的CuS-核-ZnS-殼型奈米粒子之穿透式電子顯微鏡(TEM)影像;圖13是根據製造例18製造的CuS-核-ZnS-殼型奈米粒子之掃瞄電子顯微鏡(SEM)影像;圖14是根據製造例18製造的CuS-核-ZnS-殼型奈米
粒子之穿透式電子顯微鏡(TEM)影像;圖15是根據製造例19製造的CuS-核-ZnS-殼型奈米粒子之掃瞄電子顯微鏡(SEM)影像;圖16是根據製造例19製造的CuS-核-ZnS-殼型奈米粒子之穿透式電子顯微鏡(TEM)影像;圖17是根據製造例22製造的Cu6Sn5粒子之掃瞄電子顯微鏡(SEM)影像;圖18是根據製造例22製造的Cu6Sn5粒子之XRD圖;圖19是根據實施例1形成的CZTSSe薄膜之掃瞄電子顯微鏡(SEM)影像;圖20是根據實施例1形成的CZTSSe薄膜之X射線繞射(XRD)圖;圖21是根據實施例2形成的CZTSSe薄膜之掃瞄電子顯微鏡(SEM)影像;圖22是根據實施例2形成的CZTSSe薄膜之X射線繞射(XRD)圖;及圖23是根據比較例1形成的CZTSSe薄膜之掃瞄電子顯微鏡(SEM)影像。
現在,將參見下列實施例更詳細地描述本發明。這些實施例之提供僅用於介紹本發明且不應被理解為限制了本
發明之範圍與精神。
取含有5mmol Cu(NO3)2之水溶液(100mL)逐滴加到含有5mmol Na2S之水溶液(150mL)。接著,該溶液在攪拌2小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。該所形成之粒子的掃瞄電子顯微鏡(SEM)影像與XRD圖請參見圖1與2。
在攪拌同時將含有5mmol Cu(NO3)2與10mmol硫代乙醯胺之水溶液(200mL)加熱到80℃或更多。保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。
將含有5mmol CuCl2之水溶液(60mL)加熱到80℃或更多。接著,慢慢加入含有10mmol硫代乙醯胺之水溶液(60mL),然後在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。
將含有5mmol Cu(NO3)2之二乙二醇(DEG)溶液(60mL)加熱到60℃或更多。接著,逐滴加入含有10mmol硫代乙醯胺之DEG溶液(60mL),然後在60℃攪拌1小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。
將含有5mmol Cu(NO3)2之DEG溶液(300mL)加熱到120℃。接著,逐滴加入含有10mmol硫代乙醯胺之DEG溶液(100mL),然後在120℃攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。該所形成之粒子的掃瞄電子顯微鏡(SEM)影像與XRD圖請參見圖3與4。
將含有5mmol Cu(NO3)2與10mmol硫代乙醯胺之乙二醇(EG)溶液(80mL)加熱到100℃。接著,保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。
將DEG溶液(200mL)加熱到120℃或更多,然後,逐滴加到含有10mmol硫代乙醯胺之DEG溶液(50mL)。接著,逐滴加入含有5mmol Cu(NO3)2之DEG溶液(50mL)。保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。
將含有5mmol Cu(NO3)2之EG溶液(250mL)加熱到170℃或更多,然後,逐滴加入含有10mmol硫代乙醯胺之EG溶液(50mL)。接著,保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。該所形成之粒子的掃瞄電子顯微鏡(SEM)影像與XRD圖請參見圖5與6。
將含有5mmol Cu(NO3)2之DEG溶液(250mL)加熱到170℃或更多。接著,逐滴加入含有10mmol硫代乙醯胺之DEG溶液(50mL)。接著,保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。
將二甲基甲醯胺(DMF)溶液(200mL)加熱到120℃或更多,然後,逐滴加入含有10mmol硫代乙醯胺之DMF溶液(50mL)。接著,逐滴加入含有5mmol Cu(NO3)2之DMF溶液(50mL),然後,保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。
將含有5mmol Cu(NO3)2之水溶液(250mL)加熱到170℃或更多,然後,逐滴加入含有10mmol硫代乙醯胺之EG溶液(50mL)。接著,保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。
將含有PVP(3g)之DEG溶液(200mL)加熱到120℃或更多,然後,逐滴加入含有10mmol硫代乙醯胺之DEG溶液(50mL)。接著,逐滴加入含有5mmol Cu(NO3)2之DEG溶液(50mL),然後,保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到
CuS奈米粒子。該所形成之粒子的掃瞄電子顯微鏡(SEM)影像與XRD圖請參見圖7與8。
將含有十二烷胺(1g)之DEG溶液(200mL)加熱到120℃或更多,然後,逐滴加入含有10mmol硫代乙醯胺之DEG溶液(50mL)。接著,逐滴加入含有5mmol Cu(NO3)2之DEG溶液(50mL),然後,保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。該所形成之粒子的掃瞄電子顯微鏡(SEM)影像與X射線繞射(XRD)圖請參見圖9與10。
取含有50mmol檸檬酸之水溶液(100mL)逐滴加到含有5mmol硫代硫酸鈉之水溶液(100mL),然後,加熱到80℃或更多。接著,逐滴加入含有5mmol Cu(NO3)2之水溶液(50mL),然後,保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。
取含有50mmol檸檬酸之EG溶液(100mL)逐滴加到含有5mmol硫代硫酸鈉之EG溶液(100mL),然後,加熱到80℃或更多。接著,逐滴加入含有5mmol Cu(NO3)2之EG溶液(50mL)。接著,保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。
將含有5mmol硫脲之EG溶液(100mL)加熱到80℃或更多,然後,逐滴加入含有5mmol Cu(NO3)2之EG溶液(100mL)。接著,保持該溫度,該溶液在攪拌3小時同時反應。透過離心將所形成之粒子純化,得到CuS奈米粒子。
在室溫下取含有10mmol硫代乙醯胺與8mmol ZnCl2之DEG溶液(100mL)逐滴加到5mmol的根據實施例5合成之CuS奈米粒子。將所得之溶液加熱到80℃或更多,保持該溫度,攪拌3小時。接著,透過離心將所形成之粒子純化。結果,ZnS殼形成於該CuS奈米粒子表面。該所形成之粒子的掃瞄電子顯微鏡(SEM)影像與穿透式電子顯微鏡(TEM)影像請參見圖11與12。
將根據實施例12合成之含有5mmol CuS奈米粒子之DEG溶液(100mL)加熱到80℃或更多,然後,逐滴加入含有16mmol硫代乙醯胺之DEG溶液(50mL)及含有8mmol ZnCl2之DEG溶液(50mL)。接著,保持該溫度,將該所得之混合物攪拌3小時。透過離心將所形成之粒子純化。結果,ZnS殼形成於該CuS奈米粒子表面。該所形成之粒子的掃瞄電子顯微鏡(SEM)影像與穿透式電子顯微鏡(TEM)影像請參見圖13與14。
取含有16mmol硫脲與8mmol Zn(OAc)2之DEG溶液(150mL)逐滴加到5mmol的根據實施例12合成之CuS奈米粒子。將所得之溶液加熱到150℃或更多,保持該溫度,攪拌3小時。接著,透過離心將所形成之粒子純化。結果,ZnS殼形成於該CuS奈米粒子表面。
取含有16mmol硫代乙醯胺之DEG溶液(100mL)加到5mmol的根據實施例13合成之CuS奈米粒子,然後加熱到100℃或更多。接著,逐滴加入含有8mmol
ZnCl2之DEG溶液(50mL)。接著,保持該溫度,將所得之溶液攪拌3小時。透過離心將所形成之粒子純化。結果,ZnS殼形成於該CuS奈米粒子表面。該所形成之粒子的掃瞄電子顯微鏡(SEM)影像與穿透式電子顯微鏡(TEM)影像請參見圖15與16。
取含有16mmol硫脲之DEG溶液(100mL)加到5mmol的根據實施例13合成之CuS奈米粒子,然後加熱到100℃或更多。接著,逐滴加入含有8mmol Zn(OAc)2之DEG溶液(50mL)。接著,保持該溫度,將所得之混合物攪拌3小時。透過離心將所形成之粒子純化。結果,ZnS殼形成於該CuS奈米粒子表面。
在氮氣氛圍中,將150mmol NaBH4之水溶液(200ml)強烈攪拌同時慢慢逐滴加入含有10mmol SnCl2與12mmol CuCl2之水溶液(100mL)。使所得之溶液反應8小時或更多。透過離心將所形成之粒子純化。結果,得到具有Cu6Sn5組成之奈米粒子。該所形成之粒子的掃瞄電子顯微鏡(SEM)影像與穿透式電子顯微鏡(TEM)影像請參見圖17與18。
將根據製造例17製造的CuS-核-ZnS-殼型奈米粒子與根據製造例22製造的Cu6Sn5粒子混合。將所得之混合物分散於醇系溶劑中以製造墨液。接著,將該墨液塗覆於經塗覆鉬(Mo)的玻璃基板上。乾燥該塗覆層,然後在575℃快速熱退火(RTA)過程中該塗覆層被該經沈積Se之玻璃基板加熱藉以提供Se氛圍。結果,製造出CZTSSe系薄膜。該所得之薄膜的掃瞄電子顯微鏡(SEM)影像與X射線繞射(XRD)圖請參見圖19與20。
將根據製造例19製造的CuS-核-ZnS-殼型奈米粒子與根據製造例22製造的Cu6Sn5粒子混合。將所得之混合物分散於由醇系溶劑組成之溶劑中以製造墨液。接著,將該墨液塗覆於經塗覆鉬(Mo)的玻璃基板上。乾燥該塗覆層,然後在575℃快速熱退火(RTA)過程中該塗覆層被該經沈積Se之玻璃基板加熱藉以提供Se氛圍。結果,製造出CZTSSe系薄膜。該所得之薄膜的掃瞄電子顯微鏡(SEM)影像與X射線繞射(XRD)圖請參見圖21與22。
分別合成CuS奈米粒子與ZnS奈米粒子。將該經合成之CuS與ZnS奈米粒子與根據製造例22製造之Cu6Sn5粒子混合,然後將所得之混合物分散於醇系混合溶劑中以製造墨液。將該墨液塗覆於經塗覆鉬(Mo)的玻璃基板上。乾燥該塗覆層,然後在575℃快速熱退火(RTA)過程中該塗覆層被該經沈積Se之玻璃基板加熱藉以提供Se氛圍。結果,製造出CZTSSe系薄膜。該所得之薄膜的掃瞄電子顯微鏡(SEM)影像請參見圖23。
參見圖19、21與23,當和藉由分別製造CuS奈米粒子與ZnS奈米粒子然後混合之墨液組成物所製造的薄膜相比時,使用根據本發明之墨液組成物所製造的CZTSSe系薄膜顯出較均勻的組成及較高的層密度。這樣的結果是由於Cu與Zn之氧化被防止且具有所欲粒徑的粒子形成,且,因此,在數百奈米面積中可容易地和含有Sn之奈米粒子進行均勻的混合且可以進行均勻的組成。
該領域之習知技藝者會瞭解在不脫離後附的申請專利範圍所揭示的本發明之範圍及精神的前提下,各式各樣的修改、加添及替換是有可能的。
如前文所述,根據本發明,藉由製造使用核-殼結構型奈米粒子,其包含含有含銅(Cu)的硫屬化物之核及含有含鋅(Zn)的硫屬化物之殼,與含錫(Sn)之雙金屬或金屬間金屬奈米粒子,或含錫(Sn)之硫屬化物奈米粒子的光吸收層,可使加工費減低且穩定的製程是有可能的,且,如此,可使產能增加。
此外,該核-殼結構型奈米粒子有穩定的抗氧化性及高反應性。所以,用於具有優異品質薄膜之CZTS系太陽能電池的光吸收層可生長。因此,根據本發明之太陽能電池的光電效率增加。
Claims (22)
- 一種用於製造太陽能電池的光吸收層之墨液組成物,其包含核-殼結構型奈米粒子,該核-殼結構型奈米粒子包含含有含銅(Cu)的硫屬化物之核,及含有含鋅(Zn)的硫屬化物;與含錫(Sn)的雙金屬或金屬間金屬奈米粒子,或含錫(Sn)的硫屬化物奈米粒子的殼,分散於溶劑中其中該核之直徑為20奈米到200奈米,且其中該殼之厚度為1奈米到75奈米。
- 如申請專利範圍第1項之墨液組成物,其中該含銅(Cu)的硫屬化物是選自由下列所組成之群組中的至少一種:CuS、CuxS,其中1.7x2.0、CuSe、與CuySe,其中1.7y2.0。
- 如申請專利範圍第1項之墨液組成物,其中該含鋅(Zn)的硫屬化物是ZnS及/或ZnSe。
- 如申請專利範圍第1項之墨液組成物,其中該含錫(Sn)的雙金屬或金屬間金屬奈米粒子是Cu3Sn或Cu6Sn5。
- 如申請專利範圍第1項之墨液組成物,其中該含錫(Sn)的硫屬化物奈米粒子是SnzS,其中0.5z2.0;及/或SnwSe,其中0.5w2.0。
- 如申請專利範圍第1項之墨液組成物,其中該核-殼結構型奈米粒子;及含錫(Sn)的雙金屬或金屬間金屬奈米粒子或含錫(Sn)的硫屬化物奈米粒子經混合以符合0.5<Cu/(Sn+Zn)<1.4。
- 如申請專利範圍第1項之墨液組成物,其中該溶劑是至少一種選自由下列所組成之群組中的有機溶劑:烷類、烯類、炔類、芳香烴類、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、磷酸酯類、亞碸類、及醯胺類。
- 如申請專利範圍第1項之墨液組成物,其中該墨液組成物進一步包含添加劑。
- 如申請專利範圍第8項之墨液組成物,其中該添加劑是選自由下列所組成之群組中的至少一種: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。
- 一種合成如申請專利範圍第1項之核-殼結構型奈米粒子的方法,該方法包含:製備第一溶液,其含有至少一種選自由包含硫(S)、或硒(Se)、或硫(S)與硒(Se)之化合物的群組的第VI族源;製備含有銅(Cu)鹽之第二溶液及含有鋅(Zn)鹽之第三溶液;混合該第一溶液與第二溶液而製造混合物;透過該混合物之反應而合成含銅(Cu)的硫屬化物核粒子;及藉由混合該第三溶液與包含該合成的核粒子之產物而形成殼,然後純化該殼。
- 如申請專利範圍第10項之方法,其中該第一溶 液、第二溶液與第三溶液之溶劑是選自由下列所組成之群組中的至少一種:水、甲醇、乙醇、二醇類溶劑、十八碳烯胺、二甲亞碸及二甲基甲醯胺。
- 如申請專利範圍第11項之方法,其中該二醇類溶劑是選自由下列所組成之群組中的至少一種:乙二醇、二乙二醇、NMP、二乙二醇一乙醚(DEGMEE)及三乙二醇。
- 如申請專利範圍第10項之方法,其中該鹽是選自由下列所組成之群組中的至少一種:氯化物類、硝酸鹽類、亞硝酸鹽類、硫酸鹽類、乙酸鹽類、亞硫酸鹽類、乙醯丙酮酸鹽及氫氧化物類。
- 如申請專利範圍第10項之方法,其中該第VI族源是選自由下列所組成之群組中的至少一種:Se、Na2Se、K2Se、Ca2Se、(CH3)2Se、SeO2、SeCl4、H2SeO3、Na2S、K2S、Ca2S、(CH3)2S、H2SO4、S、Na2S2O3、NH2SO3H與彼等之水合物。
- 如申請專利範圍第10項之方法,其中該第VI族源是選自由下列所組成之群組中的至少一種:硫脲、硫代乙醯胺與硒脲。
- 如申請專利範圍第10項之方法,其中在該混合之混合物中,以1mol的該銅(Cu)鹽計,該第VI族源的含量是0.5mol到4mol。
- 如申請專利範圍第10項之方法,其中當該第三溶液被混合時,該第VI族源被進一步加到包含該合成的 核粒子之該產物中。
- 一種製造使用如申請專利範圍第1項之用於製造太陽能電池的光吸收層之墨液組成物的薄膜之方法,該方法包含:混合核-殼結構型奈米粒子;與含錫(Sn)的雙金屬或金屬間金屬奈米粒子或含錫(Sn)的硫屬化物奈米粒子及溶劑而製造墨液組成物;將該墨液組成物塗覆於具備電極的基底上;及乾燥與熱處理經塗覆於該具備電極的基底上的該墨液組成物。
- 如申請專利範圍第18項之方法,其中藉由下列方式而進行該塗覆:濕式塗覆、噴霧塗覆、旋轉塗覆、刮刀塗覆、接觸印刷、上進料反印、下進料反印、噴嘴進料反印、凹板印刷、微凹板印刷、反向式微凹板印刷、滾筒塗覆、狹縫式塗覆、毛細管塗覆、噴墨印刷、噴射沈積(jet deposition)、與噴霧沈積(spray deposition)。
- 如申請專利範圍第18項之方法,其中該熱處理是在400℃到900℃範圍內進行。
- 一種薄膜,其係藉由如申請專利範圍第18至20項中任一項之方法所製造。
- 一種薄膜太陽能電池,其係使用如申請專利範圍第21項之薄膜所製造。
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