TW201903077A - 具有高無裂縫限度之cigs奈米粒子墨水調配物 - Google Patents
具有高無裂縫限度之cigs奈米粒子墨水調配物 Download PDFInfo
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Abstract
本發明係關於調配基於CIGS奈米粒子之墨水之方法,該墨水可經處理以形成具有500 nm或更高之無裂縫限度(CFL)之薄膜,該方法包含於溶劑中合併CIGS奈米粒子及二元硫屬化物奈米粒子。
Description
本發明概言之係關於薄膜光伏打裝置。更特定而言,其係關於基於銅銦鎵二硒化物/二硫化物(CIGS)之薄膜光伏打裝置。
為了在商業上可行,光伏打(PV)電池必須以對化石燃料具競爭力之成本產生。為符合該等成本,PV電池必須包含低成本材料連同廉價裝置製造製程以及日光至電力之中等至高轉換效率。為使裝置構建方法成功,材料合成及裝置製造必須係商業上可擴展的。
目前,光伏打市場仍由基於矽晶圓之太陽能電池(第一代太陽能電池)佔主導地位。然而,由於矽係相對較差之光吸收劑,故該等太陽能電池中之活性層包含厚度在數微米至數百微米範圍內之矽晶圓。該等單晶晶圓之生產極其昂貴,此乃因製程涉及製造及切割高純度單晶矽晶錠,且亦極為浪費。
結晶矽晶圓之高成本導致該行業尋找較便宜的材料來製作太陽能電池,且出於此原因,許多開發工作已集中於生產高效率薄膜太陽能電池,其中材料成本與矽相比顯著降低。
如銅銦鎵二硒化物及硫化物Cu(In,Ga)(S,Se)2
(在本文中稱為「CIGS」)之半導體材料係強光吸收劑且具有與PV應用之最佳光譜範圍匹配良好之帶隙。此外,由於此等材料具有強吸收係數,因此太陽能電池中之活性層僅需要為幾微米厚。
銅銦二硒化物(CuInSe2
)由於其獨特結構及電性質而係用於薄膜PV應用之最有前景候選物中之一者。其1.0 eV之帶隙與太陽能光譜良好匹配。CuInSe2
太陽能電池可藉由CuInS2
膜之硒化製得,此乃因在硒化製程期間,Se替代S且該取代作用產生體積膨脹,此減少空隙空間且可重現地形成高品質緻密CuInSe2
吸收劑層。[Q. Guo、G.M. Ford、H.W. Hillhouse及R. Agrawal,Nano Lett.,
2009,9
, 3060]假設S由Se完全替代,所得之晶格體積膨脹為約14.6%,此係基於黃銅礦(正方晶系) CuInS2
(a
= 5.52 Å,c
= 11.12 Å)及CuInSe2
(a
= 5.78 Å,c
= 11.62 Å)之晶格參數來計算。此意味著CuInS2
奈米晶體膜可藉由在富硒氣氛中使該膜退火容易地轉化成主要地硒化物材料。因此,CuInS2
係用於生產CuInSe2
或CuIn(S,Se)2
吸收劑層之有前景替代前體。
吸收劑材料之理論最佳帶隙在1.2 eV至1.4 eV之範圍內。藉由將鎵併入至CuIn(S,Se) 2
薄膜中,可操控帶隙使得在硒化之後形成具有用於太陽能吸收之最佳帶隙之Cu x
In y
Ga z
S a
Seb
吸收劑層。
習用地,昂貴地氣相或蒸發技術(例如,金屬有機化學氣相沈積(MO-CVD)、射頻(RF)濺鍍及急驟蒸發)已用於在基板上沈積CIGS膜。儘管該等技術提供高品質膜,但其難以按比例擴大至較大面積沈積及較高製程生產量且此較昂貴。因此,已開發CIGS材料之溶液處理。一種此類方法涉及沈積CIGS奈米粒子,該等CIGS奈米粒子可經熱處理以形成結晶CIGS層。
使用CIGS奈米粒子之一個主要優點在於其可分散於介質中以形成可以類似於報紙類製程中之墨水的方式印刷於基板上之墨水。可使用諸如旋轉塗佈、狹縫塗佈及刮刀塗佈等低成本印刷技術沈積奈米粒子墨水或膏糊。可印刷太陽能電池可替代太陽能電池製造之標準習用真空沈積方法,此乃因印刷製程尤其當於捲到捲處理框架中實施時實現高得多之生產量。
先前技術之合成方法提供對粒子形態之有限控制,且粒子溶解性通常較差,此使得墨水調配物困難。
挑戰係生產整體上較小、具有低熔融點、窄大小分佈且併入揮發性封端劑之奈米粒子,以使得該等奈米粒子可分散於介質中且封端劑可在膜烘烤製程期間容易地去除。另一挑戰係避免納入來自合成前體或有機配體之可能危及最終裝置之總體效率之雜質。
美國專利第8,784,701號及共同擁有之美國專利申請案第61/772,372號[Nanoparticle Precursor for Thin-Film Solar Cells, 2013年3月4日申請]闡述具有單分散大小分佈之膠體CIGS奈米粒子的合成,該等奈米粒子經能實現溶液可加工性且可在熱處理期間在相對較低溫度下去除之有機配體封端。
與基於奈米粒子之CIGS沈積方法相關之一個挑戰係達成高「無裂縫限度」(CFL)。基於膠體CIGS奈米粒子之墨水調配物的高有機物含量在熱處理未經處理之原沈積膜時導致高體積減小。體積之此減小可導致膜之裂縫、剝離及脫層。膜可經塗佈而無此種情況發生之臨界厚度稱為CFL。對於膠體CIGS奈米粒子,CFL通常為約100 - 150 nm,因此可需要十個或以上之塗層以形成用於PV裝置之足夠厚的膜。
已經研究增加用於光電子裝置應用之膠體奈米粒子膜之CFL的方法。一種此策略係降低墨水調配物之有機物含量,此可藉由合成具有短鏈配體之奈米粒子或將配體用更短鏈之官能團代替(例如使用配體交換製程)來達成。舉例而言,Wills等人報告在PbSe/CdSe核/殼奈米粒子之表面上將油酸酯配體與更短鏈之二硫基胺基甲酸辛基酯配體交換,以製備更緻密堆積之奈米粒子膜。[A.W. Wills、M.S. Kang、A. Khare、W.L. Gladfelter及D.J. Norris,ACS Nano
, 2010,4
, 4523] 然而,配體交換為奈米粒子合成增加了額外處理步驟,且可難以達成完全交換。在膠體合成期間利用短鏈配體鈍化奈米粒子表面之替代方法需要改變反應化學,且可導致奈米粒子聚集,使其難以溶解。
在陶瓷行業中,已知有機添加劑(例如黏合劑)可併入前體溶液中以增加其CFL。然而,此對於CIGS奈米粒子膜並不合意,此乃因有機添加劑可分解而在膜內留下碳殘餘物,該等碳殘餘物可對裝置性能有害。舉例而言,Oda等人報告,利用將明膠添加至前體溶液經由電沈積製程產生之CuGaSe2
膜的裂縫減少。然而,發現退火後碳濃度隨明膠濃度增加而增加。[Y. Oda、T. Minemoto及H. Takakura,J. Electrochem. Soc.,
2008,155
, H292] 此外,在溶液處理CIGS膜之製備中,諸如黏合劑等添加劑通常在粒子表面分解,此可阻礙晶粒生長。[T. Todorov及D.B. Mitzi,Eur. J. Inorg. Chem.,
2010,1
, 17] 陶瓷行業中所用之額外方法係增加乾燥時間以防止迅速膜收縮,然後此亦增加處理時間。
因此,業內需要增加CIGS奈米粒子膜之CFL而實質上不會增加處理時間或不會將對裝置性能及/或阻礙晶粒生長有害之組分引入膜中之方法。
闡述用以調配基於CIGS奈米粒子之墨水的方法,該墨水可經處理以形成無裂縫限度(CFL)為500 nm或更高之薄膜。在本文中,術語「CIGS」應理解為係指通式Cu w
In x
Ga 1-x
Se y
S 2-y
之任何材料(其中0.1 ≤w
≤ 2;0 ≤x
≤1及0 ≤y
≤ 2),包括其摻雜物種。該方法使得能夠在僅兩個塗佈中沈積厚度為1 μm或更高之CIGS層,同時維持高品質、無裂縫膜。可採用其他處理以形成光伏打裝置。
相關申請案之交叉參考:
本申請案主張2017年6月7日申請之美國臨時專利申請案第62/516,366號之權益,該申請案之內容以整體引用的方式併入本文中。關於由聯邦政府發起之研究或開發的聲明:不適用
在本文中,揭示用於製備CIGS奈米粒子墨水之方法,該墨水可沈積於基板上並退火以形成厚度為500 nm或更高而無裂縫、剝離或脫層之膜。藉由重複沈積及退火製程,可在兩個塗佈步驟中沈積1 μm或更高之膜,其中兩個層之間及對下伏基板具有良好黏著,以形成均勻膜。可採用其他處理以製作PV裝置。高CFL使能夠在僅兩個塗佈步驟中形成高品質CIGS吸收劑層,此相對於用以形成CIGS薄膜之先前技術基於奈米粒子之沈積方法降低勞動強度及處理時間。使用本方法,可達成500 nm或更高之無裂縫限度而不需要添加黏合劑至墨水調配物。黏合劑之使用可係不期望的,此乃因其可在奈米粒子表面分解,阻礙晶粒生長。期望高膜品質以最佳化PV裝置之性能特徵,例如開路電壓(VOC
)、短路電流(JSC
)、填充因子(FF)及總體功率轉換效率(PCE)。
墨水調配物包含溶解或分散於溶液中之有機物封端之CIGS奈米粒子及有機物封端之二元第13族硫屬化物奈米粒子之組合。如本文所用術語「二元第13族硫屬化物」係指形式Ma
Xb
之化合物,其中M係第13族元素,X係第16族元素,且a與b係> 0。鈍化奈米粒子表面之有機配體提供溶解性,此允許奈米粒子被處理成墨水。墨水調配物之有機組分可藉由在相對較低處理溫度下熱退火來移除,此完全在PV裝置處理方案內。此使碳殘餘物(可對裝置性能有害)能夠在燒結之前自膜移除。
可採用硒化製程以部分或完全將Cu(In,Ga)S2
及/或二元硫化物奈米粒子轉化為Cu(In,Ga)Se2
,以形成Cu(In,Ga)(S,Se)2
或Cu(In,Ga)Se2
吸收劑層。為生長較大晶粒,硒化製程亦可係合意的,該等較大晶粒由於促進晶粒邊界處之電荷載體重組而係合意的。因此,期望大約吸收劑層厚度之粒度以最大化光伏打裝置之PCE。
在一個實施例中,CIGS奈米粒子具有富銅化學計量比,其中Cu/(In+Ga) > 1。與InSe及/或InS及/或GaSe及/或GaS奈米粒子(或其合金)組合,此可用於調諧CIGS吸收劑層之帶隙。奈米粒子之固有化學組成(即,Cu:In:Ga比率)可在奈米粒子合成期間進行操縱。根據本發明之一個具體製備程序之說明
根據某些實施例,CIGS裝置係自CIGS奈米粒子及二元硫化物奈米粒子如下製備:a)
將CIGS奈米粒子溶解/分散於溶劑中,以形成墨水A
。b)
將二元銦硫屬化物奈米粒子溶解/分散於溶劑中,以形成墨水B
。c)
將二元鎵硫屬化物奈米粒子溶解/分散於溶劑中,以形成墨水C
。d)
合併墨水A
、B
及C
,以形成墨水D
。e)
將墨水D
沈積於基板上以形成膜。f)
在惰性氣氛中退火。g)
重複步驟e)及f),直至退火膜達到期望厚度。h)
視需要實施其他膜處理步驟,例如退火、燒結、硒化、KCN蝕刻。i)
沈積n
型半導體層以形成接面。j)
沈積固有ZnO以形成延伸耗盡區。k)
沈積窗口層。l)
沈積金屬網格。m)
將裝置囊封。
可溶液處理之Cu(In,Ga)(S,Se)2
奈米粒子之製備闡述於美國專利第8,784,701號、美國專利第9,466,743號及美國專利申請公開案第2015/0136213號,其內容以整體引用的方式併入本文中。二元硒化物奈米粒子之製備闡述於美國專利第9,359,202號中,其內容以整體引用的方式併入本文中。實例
富Cu之CIGS奈米粒子之製備
富Cu之Cu(In,Ga)S2
奈米粒子係根據美國專利申請公開案第2015/0136213號(其以整體引用的方式併入本文中)製備。奈米粒子用1-辛烷硫醇及油胺封端,且Cu:In:Ga之比率(如藉由感應耦合電漿分析所測定)係1.414:0.665:0.335。
InS奈米粒子之製備
將烘箱乾燥之250-ml圓底燒瓶(RBF)裝填8.109 g In(OAc)3
、1.5 g S粉末、24 ml油胺(≥98%一級胺)及30 ml Bz2
O。燒瓶裝配有分餾頭及收集器並將混合物在100℃下脫氣30分鐘,然後用N2
回填。
添加28 ml脫氣之1-辛烷硫醇並將混合物加熱至200℃並持續2小時,然後使其冷卻至160℃並使其攪拌過夜。
在160℃下退火約18小時後,將燒瓶打開以與大氣連通且然後添加20 ml甲苯/100 ml甲醇。將混合物在2700 G旋轉5分鐘並丟棄上清液。將所得固體分散於50 ml甲苯中並將混合物在2700 G旋轉5分鐘。將上清液放置一邊且丟棄剩餘殘餘物。
添加30 ml甲醇並將混合物在2700 G旋轉5分鐘。丟棄上清液並將所得固體分散於25 ml甲苯中。將混合物在2700 G旋轉3分鐘並將上清液轉移至玻璃小瓶。將所得殘餘物丟棄。
將InS奈米粒子溶於甲苯中並在空氣下儲存。
GaS奈米粒子之製備
將烘箱乾燥之250-ml RBF裝填10.786 g Ga(acac)3
、1.5 g S粉末、24 ml油胺(≥98% 一級胺)及30 ml Bz2
O。燒瓶裝配有分餾頭及收集器並將混合物在100℃下脫氣30分鐘,然後用N2
回填。
添加28 ml脫氣之1-辛烷硫醇並將混合物加熱至200℃並持續2小時,然後使其冷卻至160℃並使其攪拌過夜。
在160℃下退火約18小時後,將燒瓶打開以與大氣連通且然後添加20 ml甲苯/300 ml甲醇。將混合物在2700 G旋轉5分鐘並丟棄上清液。將50 ml丙-2-醇添加於油性紅色產物並將混合物劇烈震盪,然後在2700 G旋轉5分鐘。丟棄上清液並將所得固體分散於35 ml甲苯中。將混合物在2700 G旋轉5分鐘並將上清液放置一邊。丟棄剩餘殘餘物。
添加30 ml丙-2-醇/70 ml甲醇並將混合物在2700 G旋轉5分鐘。丟棄上清液並將所得油性產物用20 ml丙-2-醇沖洗。藉由離心分離沈澱並丟棄上清液。並將所得固體分散於20 ml甲苯中並將混合物在2700 G旋轉3分鐘。將上清液轉移至玻璃小瓶並丟棄任何剩餘殘餘物。
將GaS奈米粒子溶於甲苯中並在空氣下儲存。
CIGS/InS/GaS墨水之製備
將溶於甲苯中之富Cu之CIGS奈米粒子(5 mL, 1150 mg)、溶於甲苯中之InS奈米粒子(1 mL, 200 mg)及溶於甲苯中之GaS奈米粒子(389 µL, 70 mg)合併以形成墨水。根據美國專利申請公開案第2015/0136213號中所闡述之方法將墨水沈積並形成CIGS裝置。在黏著層之頂部自兩個層沈積厚度為1637 nm之無裂縫膜。黏著層之使用闡述於申請人之共同待決美國專利申請案第15/412,827號,其以整體引用的方式併入本文中。圖1顯示根據以上程序沈積於鉬塗佈之玻璃基板上之CIGS層的掃描電子顯微照片(SEM)影像。
圖1顯示根據本發明之實施例沈積於鉬塗佈之玻璃基板上之CIGS層的掃描電子顯微照片(SEM)影像。
Claims (20)
- 一種具有500 nm或更高之無裂縫限度(CFL)之墨水調配物,其包含: CIGS奈米粒子; 二元硫屬化物奈米粒子;及 溶劑。
- 如請求項1之墨水調配物,其中該CIGS奈米粒子具有下式: Cu w In x Ga 1-x Se y S 2-y ,其中0.1 ≤w ≤ 2;0 ≤x ≤1;及0 ≤y ≤ 2。
- 如請求項1之墨水調配物,其中該二元13硫屬化物奈米粒子具有下式: Ma Xb 其中M係第13族元素,X係第16族元素,且a與b係> 0.5。
- 如請求項1之墨水調配物,其中該二元硫屬化物奈米粒子係InS。
- 如請求項1之墨水調配物,其中該二元硫屬化物奈米粒子係InSe。
- 如請求項1之墨水調配物,其中該二元硫屬化物奈米粒子係GaS。
- 如請求項1之墨水調配物,其中該二元硫屬化物奈米粒子係GaSe。
- 如請求項1之墨水調配物,其中該CIGS奈米粒子具有富銅化學計量比。
- 如請求項1之墨水調配物,其中該CIGS奈米粒子之原子比Cu/(In+Ga)係大於1。
- 如請求項1之墨水調配物,其中該溶劑係甲苯。
- 如請求項1之墨水調配物,其中該CIGS奈米粒子經1-辛烷硫醇及油胺封端。
- 如請求項1之墨水調配物,其中該墨水調配物不含任何添加之黏合劑。
- 一種具有500 nm或更高之無裂縫限度(CFL)的墨水調配物,其基本上由以下組成: 溶於甲苯中之CIGS奈米粒子,其中該等CIGS奈米粒子之原子比Cu/(In+Ga)係大於1; 溶於甲苯中之InS奈米粒子;及 溶於甲苯中之GaS奈米粒子。
- 一種用於製備基於CIGS之光伏打裝置之方法,其包含:a) 將CIGS奈米粒子溶解/分散於溶劑中,以形成墨水A ;b) 將二元銦硫屬化物奈米粒子溶解/分散於溶劑中,以形成墨水B ;c) 將二元鎵硫屬化物奈米粒子溶解/分散於溶劑中,以形成墨水C ;d) 合併墨水A 、B 及C ,以形成墨水D ;e) 將該墨水D 沈積於基板上,以形成膜;f) 將該膜在惰性氣氛中退火;g) 重複步驟e)及f),直至該退火膜達到期望厚度為止。
- 如請求項14之方法,其中該等CIGS奈米粒子具有下式: Cu w In x Ga 1-x Se y S 2-y ,其中0.1 ≤w ≤ 2;0 ≤x ≤1;及0 ≤y ≤ 2。
- 如請求項14之方法,其中該溶劑係甲苯。
- 如請求項14之方法,其中該等二元銦硫屬化物奈米粒子選自由InS及InSe組成之群。
- 如請求項14之方法,其中該等二元鎵硫屬化物奈米粒子選自由GaS及GaSe組成之群。
- 如請求項14之方法,其中步驟e)及f)僅重複一次且該退火膜達到至少1 μm之厚度。
- 如請求項14之方法,其中該基板係鉬塗佈之玻璃基板。
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US9956752B2 (en) * | 2012-10-04 | 2018-05-01 | Guardian Glass, LLC | Methods of making laminated LED array and/or products including the same |
JP6093044B2 (ja) | 2013-03-04 | 2017-03-08 | ナノコ テクノロジーズ リミテッド | 薄膜ソーラーセル用の銅−インジウム−ガリウム−カルコゲナイド・ナノ粒子前駆体 |
US9893220B2 (en) * | 2013-10-15 | 2018-02-13 | Nanoco Technologies Ltd. | CIGS nanoparticle ink formulation having a high crack-free limit |
JP6411499B2 (ja) | 2013-11-15 | 2018-10-24 | ナノコ テクノロジーズ リミテッド | 銅リッチな銅インジウム(ガリウム)ジセレニド/ジスルフィドの調製 |
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2018
- 2018-06-06 WO PCT/GB2018/051546 patent/WO2018224829A1/en active Application Filing
- 2018-06-06 US US16/001,698 patent/US20180355201A1/en not_active Abandoned
- 2018-06-07 TW TW107119635A patent/TWI675890B/zh not_active IP Right Cessation
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TWI675890B (zh) | 2019-11-01 |
WO2018224829A1 (en) | 2018-12-13 |
US20180355201A1 (en) | 2018-12-13 |
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