CN110668492A - 一种卤化亚锡/铅溶液的合成方法和应用 - Google Patents
一种卤化亚锡/铅溶液的合成方法和应用 Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title description 2
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- 238000000034 method Methods 0.000 claims abstract description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004528 spin coating Methods 0.000 claims abstract description 23
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- 239000000463 material Substances 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- -1 amine cation Chemical class 0.000 claims description 8
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- 239000000126 substance Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 229960002358 iodine Drugs 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
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- 230000005525 hole transport Effects 0.000 claims description 4
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- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims description 4
- 229960002799 stannous fluoride Drugs 0.000 claims description 4
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
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- UPHCENSIMPJEIS-UHFFFAOYSA-N 2-phenylethylazanium;iodide Chemical compound [I-].[NH3+]CCC1=CC=CC=C1 UPHCENSIMPJEIS-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 102000051759 human factor J Human genes 0.000 description 1
- 108700008420 human factor J Proteins 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- LQLLAFPHJYQKKC-UHFFFAOYSA-N iodidodioxygen(.) Chemical compound [O]OI LQLLAFPHJYQKKC-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
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- C01G19/04—Halides
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- C01G19/06—Stannous chloride
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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Abstract
本发明公开了一种卤化亚锡/铅溶液的合成方法和在制备光电器件中应用。将单质锡或铅与单质卤素以摩尔比不小于1:1的比例加入到极性溶剂中,搅拌后形成锡源化合物;在锡源化合物中加入有机‑无机源化合物、添加剂,加热搅拌,得到卤化亚锡/铅溶液。将所述卤化亚锡/铅溶液冷却、过滤后,通过旋涂法、喷涂法、刮涂法、印刷法或卷对卷法制备锡/铅卤化物钙钛矿活性层。本发明实现了溶液法制备碘化亚锡,只需一步合成,产率高,无需加热和提纯,减少了人力成本和能源损耗,有利于促进钙钛矿器件的商业化进程。而且本发明制备的碘化亚锡溶液含有过量锡粉,能够抑制碘化亚锡的氧化,可以长时间使用。
Description
技术领域
本发明涉及一种卤化亚锡/铅溶液的合成及其在钙钛矿器件中的应用,属于光电器件材料技术领域。
背景技术
铅卤钙钛矿(APbX3结构,X为卤族元素,A是阳离子)是一种优异的半导体材料,组成元素为地球富有元素,其薄膜可由简单易操作的方法制得,如旋涂、喷涂及刮涂等工艺。低廉的制造成本和优异的材料特性使得钙钛矿在光伏领域、发光领域、光电探测器领域极具前景。铅卤钙钛矿薄膜太阳能电池近年来受到的关注不断提升,并在十年内得到了最高超过25.2%的光电转换效率;铅卤钙钛矿薄膜发光二极管发展也极为快速,目前外量子效率已经超过20%。然而,铅卤钙钛矿材料的缺点也不可忽略,尤其是其组分铅对人体和环境的危害对这种光电材料的商业化应用产生巨大阻碍。
锡卤钙钛矿(ASnX3)是一类低毒性的钙钛矿材料,然而,现阶段这种材料的核心原料卤化亚锡(SnI2)的合成、提纯工艺复杂:1)首先将碘粒和过量的锡粒溶于稀盐酸溶液,在氮气氛围中加热搅拌溶解得到过饱和溶液;2)将过饱和溶液降温冷却析出碘化亚锡晶体;3)将晶体封于安瓿中,通过气相传输的方法,提纯得到高纯碘化亚锡。该原料售价较高,Sigma公司售价高达339元每克,并且该原料启封后中容易氧化。
发明内容
本发明所要解决的技术问题是:现有卤化亚锡的合成、提纯工艺复杂,铅卤钙钛矿材料对人体和环境产生危害等问题。
为了解决上述技术问题,本发明提供了一种卤化亚锡/铅溶液的合成方法,其特征在于,将单质锡或铅与单质卤素以摩尔比不小于1:1的比例加入到极性溶剂中,搅拌后形成锡源化合物;在锡源化合物中加入有机-无机源化合物、添加剂,加热搅拌,得到卤化亚锡/铅溶液。
优选地,所述卤素为氯、溴或碘。
优选地,所述极性溶剂包括甲酰胺、甲基甲酰胺、N,N-二甲基甲酰胺、二甲基亚砜、γ-丁内酯、甲醇、乙醇、异丙醇、丁醇和乙二醇中的任意一种或两种以上的混合物。
优选地,所述的有机-无机源化合物采用化学通式为A+X-的任意一种化合物或两种以上化合物的混合;其中,A+为胺类阳离子、Cs+或Rb+,所述胺类阳离子包括单个或多个胺根;X-为Cl-、Br-或I-。
更优选地,所述的有机-无机源化合物采用甲脒氢碘酸盐(FAI)或苯乙胺氢碘酸盐(PEAI)。
优选地,所述添加剂为氟化亚锡(SnF2)和硫氰化铵(NH4SCN)中的至少一种。
优选地,所述卤化亚锡/铅溶液中卤化亚锡/铅、有机-无机源化合物(优选为苯乙胺氢碘酸盐)及添加剂的摩尔比为1:0.8:0.2:0.075。
本发明还提供了上述卤化亚锡/铅溶液的合成方法制得的卤化亚锡/铅溶液在制备光电器件中的应用,其特征在于,将所述卤化亚锡/铅溶液冷却、过滤后,通过旋涂法、喷涂法、刮涂法、印刷法或卷对卷法制备锡/铅卤化物钙钛矿活性层。
优选地,所述锡/铅卤化物钙钛矿活性层为薄膜状或单晶状。
优选地,所述光电器件为太阳能电池器件、电致发光器件、光电探测器或单晶器件。
更优选地,所述太阳能电池器件包括具有空穴传输层材料的导电玻璃,导电玻璃上设有所述锡/铅卤化物钙钛矿活性层,锡/铅卤化物钙钛矿活性层上依次沉积电子传输层材料、空穴阻挡层及金属电极。
进一步地,所述空穴传输层材料为PEDOT:PSS材料,电子传输层材料为ICBA材料,空穴阻挡层为BCP材料,金属电极为Ag。
与现有技术相比,本发明的有益效果是:
1、本发明的卤化亚锡溶液制备极其简单,产率高,无需长时间反应,无需高温烧结,节省了大量的原料、能源、时间;
2、本发明制备碘化亚锡溶液有一定的抗氧化能力,因为溶液中存在过量的锡粉,抑制了卤化亚锡的氧化,可以长期使用;
3、不考虑溶剂成本,该方法制备的SnI2仅需9元每克,是Sigma公司售价的1/37。
附图说明
图1为现有碘化亚锡溶液的合成方法的流程图;
图2为实施例提供的碘化亚锡溶液的合成方法的流程图;
图3为实施例1和对比例1制备的SnI2的X射线衍射图谱;
图4为实施例1和对比例1制备的(PEA)0.2(FA)0.8SnI3薄膜的X射线衍射图谱;
图5为实施例1和对比例1制备的(PEA)0.2(FA)0.8SnI3薄膜的太阳能电池IV曲线;
图6为实施例1和对比例1制备的太阳能电池器件的示意图。
具体实施方式
为使本发明更明显易懂,兹以优选实施例,并配合附图作详细说明如下。
实施例1和对比例1中的锡粉购自Sigma-Aldrich,货号265632-100G;碘颗粒锡粉购自Sigma-Aldrich,货号207772-100G;PEDOT:PSS购自Heraeus,型号4083;ICBA购自1-Material,货号OS0571;BCP购自TCI,货号B2694-1G。苯乙胺氢碘酸盐和甲脒氢碘酸盐参考文献Liao,Yuqin,et al."Highly oriented low-dimensional tin halide perovskiteswith enhanced stability and photovoltaic performance."Journal of the AmericanChemical Society 139.19(2017):6693-6699.中合成。其余试剂均购自Sigma-Aldrich。
实施例1
一种碘化亚锡溶液的合成方法,其流程如图2所示,采用单质锡和单质碘为原料制备碘化亚锡溶液,工艺简单,加入其它原料制备(PEA)0.2(FA)0.8SnI3薄膜,用于薄膜太阳能电池:
称取锡粉末474.84mg(4mmol),碘颗粒507.6mg(2mmol),量取2000μL DMF与5000μLDMSO作为溶剂加入瓶中搅拌得到溶液E。将溶液E过滤后得到溶液F,取100ul溶液F旋涂在ITO基底上,旋涂参数为3000rpm保持30秒,并100℃加热退火10分钟得到薄膜,测得X射线衍射图谱如图3中(b)所示,证明生成产物为SnI2。
称取甲脒氢碘酸盐137.6mg(0.8mmol),11.9mg(0.075mmol)氟化亚锡,苯乙胺氢碘酸盐49.8mg(0.2mmol),量取1250uL的E溶液加入瓶中在70℃下加热搅拌1h,得到前驱液G。待前驱液G冷却至室温后,用0.22μm孔径聚四氟乙烯针筒过滤器过滤,得到前驱液H。取140μL PEDOT:PSS滴在ITO基底上,6000rpm保持60s,然后140℃退火20min,得到PEDOT:PSS基底。取140μL前驱液H滴加在PEDOT:PSS基底上,进行旋涂,旋涂分为两个过程,首先1000rpm保持10s,而后5000rpm保持30s,全程40s,在第18s左右滴加600μL甲苯。旋涂结束后,80℃退火30min,得到黑色(PEA)0.2(FA)0.8SnI3薄膜,其X射线衍射图谱如图4中(b)所示。称取20mgICBA,溶于1L氯苯中,搅拌均匀后得到溶液C取100μL的ICBA溶液,滴加在冷却后的(PEA)0.2(FA)0.8SnI3薄膜上,旋涂,旋涂参数为1000rpm保持30s,旋涂结束后70℃退火10min。称取4mg BCP,溶于4mL异丙醇中,搅拌均匀后用0.22μm孔径聚四氟乙烯针筒过滤器过滤。取150μL的BCP溶液,滴加在冷却后的ICBA薄膜上,旋涂,旋涂参数为6000rpm保持30s,旋涂结束后70℃退火10min。送入镀膜机内蒸镀100nm Al做为金属电极,厚度为100nm。图5中(b)为所得太阳能电池在一个标准太阳光强下的IV曲线,图6为对应的器件结构。
对比例1
如图1所示,为参考文献Y.Takahashi,H.Hasegawa,Y.Takahashi,T.Inabe,Hallmobility in tin iodide perovskite CH3NH3SnI3:Evidence for a dopedsemiconductor.J Solid State Chem 205,39-43(2013).的合成方法制备SnI2,工艺复杂,将SnI2和其它原料溶解用于制备(PEA)0.2(FA)0.8SnI3薄膜,用于薄膜太阳能电池:
称取碘化亚锡372.5mg(1mmol),1000μL DMF与250μL DMSO作为溶剂加入瓶中搅拌得到溶液A。将溶液A过滤后得到溶液B,取100ul溶液B旋涂在ITO基底上,旋涂参数为3000rpm保持30秒,并100℃加热退火10分钟得到薄膜,测得SnI2的X射线衍射图谱如图3中(a)所示。
称取碘化亚锡372.5mg(1mmol),甲脒氢碘酸盐137.6mg(0.8mmol),11.9mg(0.075mmol)氟化亚锡,苯乙胺氢碘酸盐49.8mg(0.2mmol),量取1000μL DMF与250μL DMSO作为溶剂加入瓶中。在70℃下加热搅拌1h,得到前驱液C。待前驱液C冷却至室温后,用0.22μm孔径聚四氟乙烯针筒过滤器过滤,得到前驱液D。取140μL PEDOT:PSS滴在ITO基底上,6000rpm保持60s,然后140℃退火20min,得到PEDOT:PSS基底。取140μL前驱液D滴加在PEDOT:PSS基底上,进行旋涂,旋涂分为两个过程,首先1000rpm保持10s,而后5000rpm保持30s,全程40s,在第18s左右滴加600μL甲苯。旋涂结束后,80℃退火30min,得到黑色(PEA)0.2(FA)0.8SnI3薄膜,其X射线衍射图谱如图4中(a)所示。称取20mgICBA,溶于1mL氯苯中,搅拌均匀。取100μL的ICBA溶液,滴加在冷却后的(PEA)0.2(FA)0.8SnI3薄膜上,旋涂,旋涂参数为1000rpm保持30s,旋涂结束后70℃退火10min。称取4mg BCP,溶于4mL异丙醇中,搅拌均匀后用0.22μm孔径聚四氟乙烯针筒过滤器过滤。取150μL的BCP溶液,滴加在冷却后的ICBA薄膜上,旋涂,旋涂参数为6000rpm保持30s,旋涂结束后70℃退火10min。送入镀膜机内蒸镀100nm Al做为金属电极,厚度为100nm。图5中(a)为所得太阳能电池在一个标准太阳光强下的IV曲线,图6为对应的器件结构。
Claims (10)
1.一种卤化亚锡/铅溶液的合成方法,其特征在于,将单质锡或铅与单质卤素以摩尔比不小于1:1的比例加入到极性溶剂中,搅拌后形成锡源化合物;在锡源化合物中加入有机-无机源化合物、添加剂,加热搅拌,得到卤化亚锡/铅溶液。
2.如权利要求1所述的碘化亚锡溶液的合成方法,其特征在于,所述卤素为氯、溴或碘。
3.如权利要求1所述的碘化亚锡溶液的合成方法,其特征在于,所述极性溶剂包括甲酰胺、甲基甲酰胺、N,N-二甲基甲酰胺、二甲基亚砜、γ-丁内酯、甲醇、乙醇、异丙醇、丁醇和乙二醇中的任意一种或两种以上的混合物。
4.如权利要求1所述的碘化亚锡溶液的合成方法,其特征在于,所述有机-无机源化合物采用化学通式为A+X-的任意一种化合物或两种以上化合物的混合;其中,A+为胺类阳离子、Cs+或Rb+,所述胺类阳离子包括单个或多个胺根;X-为Cl-、Br-或I-。
5.如权利要求1所述的碘化亚锡溶液的合成方法,其特征在于,所述添加剂为氟化亚锡和硫氰化铵中的至少一种。
6.一种权利要求1-5任意一项所述的卤化亚锡/铅溶液的合成方法制得的卤化亚锡/铅溶液在制备光电器件中的应用,其特征在于,将所述卤化亚锡/铅溶液冷却、过滤后,通过旋涂法、喷涂法、刮涂法、印刷法或卷对卷法制备锡/铅卤化物钙钛矿活性层。
7.如权利要求6所述的应用,其特征在于,所述锡/铅卤化物钙钛矿活性层为薄膜状或单晶状。
8.如权利要求6所述的应用,其特征在于,所述光电器件为太阳能电池器件、电致发光器件、光电探测器或单晶器件。
9.如权利要求8所述的应用,其特征在于,所述太阳能电池器件包括具有空穴传输层材料的导电玻璃,导电玻璃上设有所述锡/铅卤化物钙钛矿活性层,锡/铅卤化物钙钛矿活性层上依次沉积电子传输层材料、空穴阻挡层及金属电极。
10.如权利要求9所述的应用,其特征在于,所述空穴传输层材料为PEDOT:PSS材料,电子传输层材料为ICBA材料,空穴阻挡层为BCP材料,金属电极为Ag。
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