CN111403607A - 一种螯合化钙钛矿材料、薄膜、器件及其制备方法和应用 - Google Patents
一种螯合化钙钛矿材料、薄膜、器件及其制备方法和应用 Download PDFInfo
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- CN111403607A CN111403607A CN202010217117.0A CN202010217117A CN111403607A CN 111403607 A CN111403607 A CN 111403607A CN 202010217117 A CN202010217117 A CN 202010217117A CN 111403607 A CN111403607 A CN 111403607A
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- perovskite
- chelating agent
- salt
- acid
- precursor solution
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002738 chelating agent Substances 0.000 claims abstract description 63
- 239000013522 chelant Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims description 33
- 239000010408 film Substances 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- -1 4-methoxybenzyliminothiocarbamate hydrochloride Chemical compound 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000010409 thin film Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 10
- 229940116901 diethyldithiocarbamate Drugs 0.000 claims description 9
- 239000012990 dithiocarbamate Substances 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical class OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 4
- VSWDORGPIHIGNW-UHFFFAOYSA-N Pyrrolidine dithiocarbamic acid Chemical compound SC(=S)N1CCCC1 VSWDORGPIHIGNW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical class [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 3
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 claims description 3
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 claims description 3
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical class C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 claims description 2
- KNTGXGBOYZAKTA-UHFFFAOYSA-N 4-[(4-nitrophenyl)methyl]morpholine Chemical compound C1=CC([N+](=O)[O-])=CC=C1CN1CCOCC1 KNTGXGBOYZAKTA-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- IEQPZXXXPVAXRJ-UHFFFAOYSA-M N-butylcarbamodithioate Chemical compound CCCCNC([S-])=S IEQPZXXXPVAXRJ-UHFFFAOYSA-M 0.000 claims description 2
- AXRRFZGBWNMCOW-UHFFFAOYSA-N N-dihydroxyphosphinothioylsulfanyl-N-phenylaniline Chemical compound C1(=CC=CC=C1)N(C1=CC=CC=C1)SP(O)(O)=S AXRRFZGBWNMCOW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Chemical class 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- JTPLPDIKCDKODU-UHFFFAOYSA-N acetic acid;2-(2-aminoethylamino)ethanol Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCO JTPLPDIKCDKODU-UHFFFAOYSA-N 0.000 claims description 2
- QTONSPKDOKVNBJ-UHFFFAOYSA-N acetic acid;n'-(2-aminoethyl)ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCN QTONSPKDOKVNBJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- FROZIYRKKUFAOC-UHFFFAOYSA-N amobam Chemical compound N.N.SC(=S)NCCNC(S)=S FROZIYRKKUFAOC-UHFFFAOYSA-N 0.000 claims description 2
- DCYNAHFAQKMWDW-UHFFFAOYSA-N azane;carbamodithioic acid Chemical class N.NC(S)=S DCYNAHFAQKMWDW-UHFFFAOYSA-N 0.000 claims description 2
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- CRCCWKNJNKPDAE-UHFFFAOYSA-N hydroxy-(2-methylpropoxy)-(2-methylpropylsulfanyl)-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)COP(O)(=S)SCC(C)C CRCCWKNJNKPDAE-UHFFFAOYSA-N 0.000 claims description 2
- BXYFLGJRMCIGLW-UHFFFAOYSA-N hydroxy-propan-2-yloxy-propan-2-ylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical class CC(C)OP(O)(=S)SC(C)C BXYFLGJRMCIGLW-UHFFFAOYSA-N 0.000 claims description 2
- HYVVJDQGXFXBRZ-UHFFFAOYSA-N metam Chemical compound CNC(S)=S HYVVJDQGXFXBRZ-UHFFFAOYSA-N 0.000 claims description 2
- XFOAZOPAGIZIHX-UHFFFAOYSA-N methyl(phenyl)carbamodithioic acid Chemical compound SC(=S)N(C)C1=CC=CC=C1 XFOAZOPAGIZIHX-UHFFFAOYSA-N 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims description 2
- 125000006503 p-nitrobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1[N+]([O-])=O)C([H])([H])* 0.000 claims description 2
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- LMNZTLDVJIUSHT-UHFFFAOYSA-N phosmet Chemical compound C1=CC=C2C(=O)N(CSP(=S)(OC)OC)C(=O)C2=C1 LMNZTLDVJIUSHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001205 polyphosphate Chemical class 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 claims description 2
- USIPWJRLUGPSJM-UHFFFAOYSA-K trisodium 2-(2-aminoethylamino)ethanol triacetate Chemical compound [Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCNCCO USIPWJRLUGPSJM-UHFFFAOYSA-K 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims 3
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 claims 1
- 229920000768 polyamine Polymers 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- LESFYQKBUCDEQP-UHFFFAOYSA-N tetraazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound N.N.N.N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LESFYQKBUCDEQP-UHFFFAOYSA-N 0.000 claims 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims 1
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明涉及一种螯合化钙钛矿材料、薄膜、器件及其制备方法和应用。是将螯合剂添加在钙钛矿的溶液中制得;所述的螯合剂,包括具有配位原子能和金属离子产生配位的络合剂或螯合剂,或通过络合剂或螯合剂与相应的金属离子配位反应后形成的螯合物或络合物;本发明有效的钝化钙钛矿薄膜本体缺陷及表面缺陷,减少载流子的非辐射复合,从而有效的提升钙钛矿太阳能电池的效率及长期运作稳定性。
Description
技术领域
本发明涉及利用螯合剂螯合钙钛矿材料,以达到提升钙钛矿薄膜稳定性,并提升钙钛矿电池的光电效率及光照稳定性的方法。尤其是一种螯合化钙钛矿材料、薄膜、器件及其制备方法和应用。
背景技术
目前,能源危机和环境问题是全球亟需解决的重要问题之一。作为最易获得的可再生能源,太阳能较之其他能源,取之不尽、用之不竭、安全环保,是新能源中最重要的一部分。而太阳能电池通过光电或光化学效应直接将光能转换为电能,对改善能源危机和资源匮乏有着重要的作用。其中钙钛矿太阳电池是一种新兴太阳能电池技术。目前有机无机杂化钙钛矿电池能量转换效率已经高达25.2%,已经超过了很多经过多年发展的其他类型太阳能电池。虽然有较高的光电效率,但因钙钛矿结构对湿度及温度的敏感性,使其晶格被破坏导致钙钛矿材料的不稳定一直是制约其进一步发展的最大原因。减少钙钛矿电池相应的电压损失,提升其光电转换效率及稳定性一直是钙钛矿电池面临的技术问题。
调控钙钛矿的组成成分,特别对卤素阴离子的调控,能有效的改善钙钛矿对湿度的敏感性。如纯碘的钙钛矿中引入相应的氯、溴离子,通过影响薄膜质量,从而对钙钛矿的稳定性起到积极作用;通过其它方法,如拟卤素硫氰根离子替换卤素碘离子亦可以大幅提升钙钛矿的湿度稳定性。而钙钛矿太阳能器件的稳定性除了与吸收材料本身的稳定性有关,传输层及界面对电池的稳定性也有很大影响。除了移除以Spiro-OMeTAD为主的不稳定传输材料之外,通过无机材料替换有机传输材料成亦能加提升器件的稳定性。如使用无机化合物CuI作为空穴传输材料,制备的器件在没有封装,暴露在空气中光照2小时,光电效率几乎不变。最终也可通过对太阳能电池封装提升器件对空气湿度及温度的敏感性。但尚需同时解决钙钛矿材料本身的稳定性,及器件结构的优化和设计。
发明内容
本发明的目的在于提供一种螯合化钙钛矿材料、薄膜、器件及其制备方法和应用,此制备方法简单,可重复性高。
为实现上述目的,本发明采用如下技术方案:
一种螯合化钙钛矿材料,是将螯合剂添加在钙钛矿的溶液中制得;所述的螯合剂,不仅包括具有配位原子(氧,氮,硫,磷,砷,硒原子为主)能和金属离子产生配位的络合剂或螯合剂(多数是有机配体),这里也包括通过络合剂或螯合剂与相应的金属离子配位反应后形成的螯合物或络合物;
所述的螯合剂包括:氨羧络合剂(氨基三乙酸金属盐);EDTA系列(乙二胺四乙酸盐、乙二胺四乙酸铵盐、乙二胺四乙酸二钠盐、乙二胺四乙酸四钠盐);DTPA系列(二乙烯三胺五乙酸、二乙烯三胺五乙酸盐、二乙烯三胺五乙酸五钠、二乙烯三胺五乙酸五钠盐);固胺系列(三乙烯二胺、丙四胺四乙酸);HEDT系列(羟乙基乙二胺三乙酸盐、羟乙基乙二胺、羟乙基乙二胺三乙酸三钠盐);双硫腙盐;柠檬酸盐及多磷酸盐;硫代氨基甲酸酯,包括二烷基二硫代氨基甲酸酯(例如福美双、福美锌、福美铁),4-硝基苄基吗啉-4-二硫代氨基甲酸酯和亚烷基双二硫代氨基甲酸酯(例如代森锰、代森锌、代森锰锌、代森联、甲基代森锌);4-(4-硝基苄基)吗啡啉;4-甲氧基苄基亚胺基硫代氨基甲酸酯盐酸盐;二硫代氨基甲酸盐,如二乙基二硫代氨基甲酸盐,二甲基二硫代氨基甲酸盐,甲基二硫代氨基甲酸盐,丁基二硫代氨基甲酸盐,含有其它苯环基团或烃基基团的R-二硫代氨基甲酸(R为有级链,为烃基、苯环基团、及烃基与苯环基团组合);二硫代氨基甲酸铵盐,如,二乙基二硫代氨基甲酸铵盐,硫代氨基甲酸铵盐,吡咯烷二硫代氨基甲酸铵(APDC)盐,吡咯啶二硫代氨基甲酸铵盐,N-甲基-N-苯基二硫代氨基甲酸铵盐,代森铵,及含有其它烃基与苯环基团的二硫代氨基甲酸铵盐;二硫代磷酸盐,包括,二乙基二硫代磷酸(铵)盐,O,O-二丁基二硫代磷酸盐,二烷基二硫代磷酸盐,二甲酚基二硫代磷酸,甲酚二硫代磷酸,二硫代磷酸酯钾盐-D6,二异丁基二硫代磷酸盐,二苯胺基二硫代磷酸,二丁基二硫代磷酸铵;二硫代磷酸酯盐,包括三环己基锡基O,O-二乙基-二硫代磷酸酯,O,O-二甲基-S-(酞酰亚胺基甲基)二硫代磷酸酯,O,O-二硫代磷酸二乙金属酯盐,二硫代磷酸O,O-二乙基S-[(2-嘧啶基硫基)甲基]酯,二硫代磷酸O-间甲苯基O-对甲苯基酯铜盐,二硫代磷酸二异丙酯盐及其它结构含有二硫代磷酸的盐或酯类化合物。以上的螯合物包括但不局限于以上具体所述的化合物(各类盐中的阳离子可以是有机铵离子,如NH3+,NH4+;也可以是一种或两种元素周期表中的金属离子,如钠、镁、铝、钙、铅、锌、铜、铁、镍、镉、铅、锰、银、铟、镓、锡、锑、铋、钴、钼、钴、锆、铌、镧系)。
所述的螯合剂可以是直接购买使用,或者是采用其它原料间接的合成所到。如,二乙基二硫代氨基甲酸盐,可通过相应的三水二乙基二硫代氨基甲酸钠盐与相应的金属盐(金属硝酸或氯化盐)反应生成所需的二乙基二硫代氨基甲酸金属螯合物;柠檬酸盐可通过柠檬酸(或柠檬酸钠)室温下与相应的金属盐反应(金属盐中的金属离子,如镁、钙、铅、锌、铜、铁、镍、镉、铅、银、铟、铝、锡、锑、铋、钴、锆、铌、钼、镧系等)。
本发明还提出了一种螯合化钙钛矿薄膜,是将含有螯合剂的钙钛矿前驱体溶液涂布在基底材料并进行退火制得;或先形成钙钛矿吸收层,之后用含有螯合剂的溶液,旋涂在钙钛矿吸收层的上、下表面制得。
所述的含有螯合剂的钙钛矿前驱体溶液,可以为螯合剂添加到钙钛矿溶液中形成的螯合前驱体溶液。也可以为相应的螯合剂作为钙钛矿前驱体溶液的一种原料,加上其它化学药品溶解之后直接形成的钙钛矿前驱体溶液,这里的螯合剂的使用量与钙钛矿前驱体溶液的摩尔比为1:1。
所述的将螯合剂适量添加在钙钛矿溶液中,这里的螯合剂添加在钙钛矿溶液中只是一种具体方法,也可以是螯合剂旋涂在钙钛矿吸收层的上、下表面或者修饰在与钙钛矿接触的传输层表面(钙钛矿吸收层与传输层的界面处),甚至可以添加在器件中与吸收材料(吸收层)接触的传输层中。方法不局限于只是添加或旋涂修饰,只要使螯合剂螯合钙钛矿材料的方法均可。
所述的螯合剂溶液是指螯合剂溶解在不破坏其组分的溶剂中,形成一定浓度的螯合剂溶液。螯合剂溶液修饰在钙钛矿吸收层上、下表面时,采用的涂布浓度小于500mg/ml。
所述的螯合剂添加在钙钛矿中,添加可以是称量螯合剂直接添加到前驱体中溶解,也可以是先把相应的螯合剂溶解在一定试剂中,然后取一定的螯合剂溶液添加到溶解好的钙钛矿溶液中最终形成后续涂布的钙钛矿前驱体溶液。所述的螯合剂添加量为螯合剂与最终形成的钙钛矿前驱体溶液的摩尔比小于80%。
本发明还提出了一种螯合化钙钛矿薄膜的应用,是将薄膜作为钙钛矿太阳能电池工序装配为器件。
所述器件的制备方法是:将螯合剂添加在钙钛矿的溶液中,然后取一定量含有螯合剂的钙钛矿前驱体溶液涂布在基底材料并进行退火,后续采用标准钙钛矿太阳能电池工序装配为器件;或先形成钙钛矿吸收层,之后用含有螯合剂的溶液,旋涂在钙钛矿吸收层的上、下表面,后续采用标准钙钛矿太阳能电池工序装配为器件。
所述的钙钛矿前驱体溶液为最终合成钙钛矿太阳能电池中对应钙钛矿吸收层的组分前驱体。例如CsPbI2Br钙钛矿光电器件,其对应的就是CsPbI2Br前驱体溶液。1.2M的CsPbI2Br无机钙钛矿前驱体溶液由312mg碘化铯,220mg溴化铅,277mg碘化铅溶解在1mL的二甲基亚砜溶剂中,室温搅拌8~16小时,无过滤,最终形成CsPbI2Br无机钙钛矿前驱体溶液。
所述基底材料,可以直接是FTO或ITO玻璃,也可以具有传输能力的材料涂敷在FTO或ITO玻璃上,形成一层传输层基底。如,TiO2基底材料为相应清洗过的FTO玻璃浸泡在0.25M的四氯化钛溶液40~80分钟,温度60~75℃。随后400~550℃马弗炉煅烧0.3~1.5h制备。
所述的含有螯合剂钙钛矿前驱体溶液,滴涂在二氧化钛电子层基底上旋涂退火成膜。
上述应用方法如下:采用标准工艺装配钙钛矿太阳能器件后,在标准太阳光辐照度的测试条件下,测试其光电转化效率。
本发明的有益效果在于:
(1)螯合剂含有特殊的路易斯酸碱原子(主要是氧,氮,硫,磷,砷,硒原子),能够有效的钝化薄膜内部的空位,减少薄膜中的缺陷态密度,提升薄膜/器件的质量及稳定性。
(2)所使用的螯合剂种类众多且来源方便,相应的复合螯合剂可通过简单的合成方式得到。例如,二乙基二硫代氨基甲酸金属化合物可通过金属硝酸或金属盐与二乙基氨基甲酸钠盐水体系合成,合成金属螯合物所需的原料简单易得。
(3)合成的二乙基二硫代氨基甲酸金属螯合物,如二乙基二硫代氨基甲酸铅Pb(DDTC)2添加到纯无机CsPbI2Br钙钛矿前驱体溶液中,使得纯无机电池效率提升至17%(电池有效面积为0.0625cm2),且组装电池后亦能在相对湿度小于15%,1480h之后维持原始效率的95%以上。
(4)应用方式多样且简单,可直接将螯合剂添加在前驱体溶液中,或者旋涂在表面或界面,不需要进一步处理。其螯合剂包含的路易斯碱可以与钝化内部缺陷,且含有烷基链的螯合剂中的有机氢键亦能加强钙钛矿层与电子层的链接,减少载流子的非辐射复合及界面复合,有效减少开路电压的损失。如,相应适量的Pb(DDTC)2添加到CsPbI2Br纯无机钙钛矿中,提升其器件的开路电压至1.372V。
附图说明
图1是实施例1所制备多种二乙基氨基甲酸金属螯合物产品的粉末照片。
图2是实施例2所制备Pb(DDTC)2相应的XRD及理论计算的XRD图谱。
图3是实施例2所制备Pb(DDTC)2添加在CsPbI2Br中,形成的薄膜TOF-SIMS图谱。
图4是实施例2所制备Pb(DDTC)2添加在CsPbI2Br中,形成的钙钛矿薄膜随着时间(天数)的延长变化照片。
图5是实施例2所制备Pb(DDTC)2添加在CsPbI2Br中,装配的钙钛矿器件获得的最高效率,及器件获得最大电压下对应的电流-电压曲线图。(正扫模式)
图6是实施例2所制备Pb(DDTC)2添加在CsPbI2Br中,装配的钙钛矿器件获得的最高效率,及器件获得最大电压下对应的电流-电压曲线图。(反扫模式)
图7是实施例2所制备Pb(DDTC)2添加在CsPbI2Br中,装配的纯无机钙钛矿器件相应的稳定性测试曲线。
具体实施方式
下面,结合附图和实施例1和2,对本发明的具体实施方式做进一步详细的说明,但不应以此限制本发明的保护范围。
本文所公开的“范围”以下限和上限的形式。可以分别为一个或多个下限,和一个或多个上限。给定范围是通过选定一个下限和一个上限进行限定的。选定的下限和上限限定了特别范围的边界。所有可以这种方式进行限定的范围是包含和可组合的,即任何下限可以与任何上限组合形成一个范围。例如,针对特定参数列出了60-120和80-110的范围,理解为60-110和80-120的范围也是预料到的。此外,如果列出的最小范围值1和2,和如果列出了最大范围3,4和5,则下面的范围可全部预料到:1-2、1-4、1-5、2-3、2-4和2-5。
本发明中,除非有其他说明,数值范围“a-b”表示a到b之间的任意实数组合的缩略表示,其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数,“0-5”只是这些数值组合的缩略表示。
在本发明中,如果没有特别的说明,本文所提到的所有实施方式以及优选实施方式可以互相组合形成新的技术方案。
在本发明中,如果没有特别的说明,本文所提到的所有技术特征以及优选特征可以互相组合形成新的技术方案。
下面将结合具体实施例来具体阐述本发明的优选实施方法,但是应当理解,本领域技术人员可以在不背离权利要求书限定的范围的前提下,对这些实施例进行合理的变化、改良和相互组合,从而获得新的具体实施方法,这些通过变化、改良和相互组合获得的新的具体实施方式也都包括在本发明的保护范围之内。
实施例1
步骤一、二乙基二硫代氨基甲酸金属螯合物的制备
室温下,10mmol的硝酸铅Pb(NO3)2及20mmol的三水二乙基二硫代氨基甲酸钠Na(DDTC)·3H2O分别溶解在40ml水中。在剧烈搅拌的情况下,Na(DDTC)·3H2O水溶液逐渐滴落在Pb(NO3)2水溶液中。继续搅拌半小时,然后抽滤得到淡黄色沉淀,用去离子水及乙醇洗涤几次。抽滤所得到的沉淀产物在60℃下真空干燥过夜,最终得到所需二甲基二硫代氨基甲酸铅金属螯合物铅盐Pb(DDTC)2产物。
除二甲基二硫代氨基甲酸钠之外,其它对应的二甲基二硫代氨基甲酸金属螯合物均采用以上相同的合成方式。如,二乙基二硫代氨基甲酸铜,二乙基二硫代氨基甲酸锌,二乙基二硫代氨基甲酸钴,二乙基二硫代氨基甲酸镍,二乙基二硫代氨基甲酸铟金属螯合物可通过相应的Cu(NO3)2,ZnCl2,Co(NO3)2,Ni(NO3)2,In(NO3)3与二乙基二硫代氨基甲酸钠反应生成。
图1为所合成的部二乙基二硫代氨基甲酸铅盐Pb(DDTC)2相应的XRD图谱及粉末图片。可以看出,实际合成的粉末结晶结构与计算的相匹配。
步骤二、二乙基二硫代氨基甲酸铅盐Pb(DDTC)2掺杂钙钛矿薄膜的制备
首先称量7.5mgPb(DDTC)2,272mg碘化铯,187mg溴化铅,235.5mg碘化铅粉末溶解在1mL的二甲基亚砜溶剂中,随后室温下搅拌8-12小时,形成钙钛矿CsPbI2Br前驱体溶液,无过滤。随后取30~50μL旋涂在二氧化钛覆盖的FTO玻璃上,随后43℃加热2分钟,160℃加热10分钟,形成钙钛矿吸收层薄膜。所述的薄膜制备在氮气手套箱中完成。
二氧化钛覆盖的FTO玻璃基底为相应的FTO玻璃浸泡0.25M的四氯化钛溶液40~80分钟,温度60~75℃。随后400~550℃马弗炉煅烧。
图2为添加不同浓度Pb(DDTC)2下CsPbI2Br薄膜对应的SEM图谱。a-e图为f-k图谱对应的放大图谱。a-e图谱对应的标尺为300nm,f-k图谱对应的标尺为1μm。图片右上角对应的是添加Pb(DDTC)2相应浓度(mg/ml)。从图中可以看出随着浓度的增大,颗粒尺寸减小。
图3对CsPbI2Br添加Pb(DDTC)2形成的钙钛矿薄膜进行飞行时间二次离子质谱技术表征图谱,可以看出,代表Pb(DDTC)2组分的硫及氢离子分布在整个钙钛矿薄膜中,其中大部分分散在薄膜的表面及钙钛矿与电子层的界面处,自发形成离子分布梯度。
图4显示有无添加Pb(DDTC)2下合成的CsPbI2Br薄膜随着时间(天数)的延长其薄膜表面变化照片(放置在相对湿度12%±5%的干燥箱中),图中单个薄膜的尺寸为4cm2。可以明显的发现有Pb(DDTC)2辅助的CsPbI2Br薄膜稳定性大大提升。
步骤三、性能表征测试
相应的FTO玻璃浸泡0.25M的四氯化钛溶液40~80分钟,温度60~75℃。随后400~550℃马弗炉煅烧,形成二氧化钛覆盖的FTO玻璃基底。取30~50μL含7.5mg的Pb(DDTC)2前驱体溶液,旋涂在二氧化钛覆盖的FTO玻璃上,随后43℃加热2分钟,160℃加热10分钟,形成钙钛矿吸收层薄膜(薄膜厚度约为300nm)。薄膜冷却之后旋涂聚-3已基噻吩(P3HT)空穴层(15mg/ml的氯苯溶液),蒸镀银电极(80nm厚),装配成钙钛矿太阳能电池,通过太阳光模拟器,在100mW cm-2标准光的照射下,测试光电转化效率。电池的有效面积为0.0625cm2。
图5是采用标准工艺装配Pb(DDTC)2掺杂钙钛矿太阳能电池后,光电转化效率达到17.03%(由电压到电流的反扫模式,短路电流15.78mA/cm2,开路电压1.341V,填充因子80.52%);而正扫模式下(电流到电压模式),电池效率为16.60%(短路电流15.75mA/cm2,开路电压1.320V,填充因子79.83%)。图6是对应采用标准工艺装配Pb(DDTC)2掺杂钙钛矿太阳能电池后,反扫模式下得到的最大电压下的电流电压曲线图(光电转换效率16.31%,短路电流15.12mA/cm2,开路电压1.372V,填充因子78.63%)。
图7是采用标准工艺装配Pb(DDTC)2掺杂钙钛矿太阳能电池后,放置在相对湿度12%±5%的干燥箱中测试其湿度稳定性。从图谱可以看出Pb(DDTC)2掺杂中能明显提升无机钙钛矿的长期稳定性。
本发明通过添加相应的螯合剂能够有效钝化其钙钛矿薄膜本体及电池内部的界面缺陷,减少载流子的复合,提升其湿度及光照及湿度稳定性。通过金属螯合物二乙基二硫代氨基甲酸铅Pb(DDTC)2螯合钙钛矿电池的光活性层,有效提升其无机钙钛矿器件的光电转化效率至17%,器件的最高开路电压可达1.372V。本发明方法使得钙钛矿电池进一步实现组件化、工业化有了更新的进展。
Claims (7)
1.一种螯合化钙钛矿材料,其特征在于,是将螯合剂添加在钙钛矿的溶液中制得;所述的螯合剂,包括具有配位原子能和金属离子产生配位的络合剂或螯合剂,或通过络合剂或螯合剂与相应的金属离子配位反应后形成的螯合物或络合物;
所述的螯合剂是:氨羧络合剂:氨基三乙酸金属盐;
或EDTA系列:包括乙二胺四乙酸盐、乙二胺四乙酸铵盐、乙二胺四乙酸二钠盐、乙二胺四乙酸四钠盐;
或DTPA系列:包括二乙烯三胺五乙酸、二乙烯三胺五乙酸盐、二乙烯三胺五乙酸五钠、二乙烯三胺五乙酸五钠盐;
或固胺系列:包括三乙烯二胺、丙四胺四乙酸;
或HEDT系列:包括羟乙基乙二胺三乙酸盐、羟乙基乙二胺、羟乙基乙二胺三乙酸三钠盐;
或双硫腙盐;柠檬酸盐及多磷酸盐;
或硫代氨基甲酸酯:包括二烷基二硫代氨基甲酸酯,4-硝基苄基吗啉-4-二硫代氨基甲酸酯和亚烷基双二硫代氨基甲酸酯;
或4-(4-硝基苄基)吗啡啉;
或4-甲氧基苄基亚胺基硫代氨基甲酸酯盐酸盐;
或二硫代氨基甲酸盐,包括二乙基二硫代氨基甲酸盐,二甲基二硫代氨基甲酸盐,甲基二硫代氨基甲酸盐,丁基二硫代氨基甲酸盐,含有其它苯环基团或烃基基团的R-二硫代氨基甲酸,所述R为有级链,为烃基、苯环基团、及烃基与苯环基团组合;
或二硫代氨基甲酸铵盐,包括二乙基二硫代氨基甲酸铵盐,硫代氨基甲酸铵盐,吡咯烷二硫代氨基甲酸铵(APDC)盐,吡咯啶二硫代氨基甲酸铵盐,N-甲基-N-苯基二硫代氨基甲酸铵盐,代森铵,及含有其它烃基与苯环基团的二硫代氨基甲酸铵盐;
或二硫代磷酸盐,包括二乙基二硫代磷酸(铵)盐,O,O-二丁基二硫代磷酸盐,二烷基二硫代磷酸盐,二甲酚基二硫代磷酸,甲酚二硫代磷酸,二硫代磷酸酯钾盐-D6,二异丁基二硫代磷酸盐,二苯胺基二硫代磷酸,二丁基二硫代磷酸铵;
或二硫代磷酸酯盐,包括三环己基锡基O,O-二乙基-二硫代磷酸酯,O,O-二甲基-S-(酞酰亚胺基甲基)二硫代磷酸酯,O,O-二硫代磷酸二乙金属酯盐,二硫代磷酸O,O-二乙基S-[(2-嘧啶基硫基)甲基]酯,二硫代磷酸O-间甲苯基O-对甲苯基酯铜盐,二硫代磷酸二异丙酯盐及其它结构含有二硫代磷酸的盐或酯类化合物。
2.一种螯合化钙钛矿薄膜,其特征在于,是将含有权利要求1所述螯合剂的钙钛矿前驱体溶液涂布在基底材料并进行退火制得;或先形成钙钛矿吸收层,之后用含有螯合剂的溶液,旋涂在钙钛矿吸收层的上、下表面制得;
所述的含有螯合剂的钙钛矿前驱体溶液,为螯合剂添加到钙钛矿溶液中形成的螯合前驱体溶液;或为相应的螯合剂作为钙钛矿前驱体溶液的一种原料,加上其它化学药品溶解之后直接形成的钙钛矿前驱体溶液,所述螯合剂的使用量与钙钛矿前驱体溶液的摩尔比为1:1;
所述的螯合剂溶液是指螯合剂溶解在不破坏其组分的溶剂中,形成一定浓度的螯合剂溶液;螯合剂溶液修饰在钙钛矿吸收层上、下表面时,采用的涂布浓度小于500mg/ml;
所述的螯合剂添加量为螯合剂与最终形成的钙钛矿前驱体溶液的摩尔比小于80%。
3.一种螯合化钙钛矿薄膜的应用,其特征在于,是将薄膜作为钙钛矿太阳能电池工序装配为器件;
所述器件的制备方法是:将螯合剂添加在钙钛矿的溶液中,然后取一定量含有螯合剂的钙钛矿前驱体溶液涂布在基底材料并进行退火,后续采用标准钙钛矿太阳能电池工序装配为器件;或先形成钙钛矿吸收层,之后用含有螯合剂的溶液,旋涂在钙钛矿吸收层的上、下表面,后续采用标准钙钛矿太阳能电池工序装配为器件。
4.根据权利要求3所述的螯合化钙钛矿薄膜的应用,其特征在于,所述的钙钛矿前驱体溶液为最终合成钙钛矿太阳能电池中对应钙钛矿吸收层的组分前驱体。
5.根据权利要求3所述的螯合化钙钛矿薄膜的应用,其特征在于,所述基底材料是FTO或ITO玻璃,或具有传输能力的材料涂敷在FTO或ITO玻璃上,形成一层传输层基底。
6.根据权利要求5所述的螯合化钙钛矿薄膜的应用,其特征在于,采用TiO2基底材料为相应清洗过的FTO玻璃浸泡在0.25M的四氯化钛溶液40~80分钟,温度60~75℃;随后400~550℃马弗炉煅烧0.3~1.5h制备。
7.一种螯合化钙钛矿器件的制备方法,其特征在于,器件为CsPbI2Br钙钛矿光电器件,对应的是CsPbI2Br前驱体溶液;制备方法是采用1.2M的CsPbI2Br无机钙钛矿前驱体溶液由312mg碘化铯,220mg溴化铅,277mg碘化铅溶解在1mL的二甲基亚砜溶剂中,室温搅拌8~16小时,无过滤,最终形成CsPbI2Br无机钙钛矿前驱体溶液;然后将含有螯合剂钙钛矿前驱体溶液,滴涂在二氧化钛电子层基底上旋涂退火成膜,后续采用标准钙钛矿太阳能电池工序装配为器件。
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