CN112521585B - 钙钛矿光电元件 - Google Patents
钙钛矿光电元件 Download PDFInfo
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- CN112521585B CN112521585B CN202011372411.5A CN202011372411A CN112521585B CN 112521585 B CN112521585 B CN 112521585B CN 202011372411 A CN202011372411 A CN 202011372411A CN 112521585 B CN112521585 B CN 112521585B
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- perovskite
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- carrier transport
- aromatic amine
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- 230000005693 optoelectronics Effects 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims description 18
- 238000004770 highest occupied molecular orbital Methods 0.000 claims description 11
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000005549 heteroarylene group Chemical group 0.000 claims description 4
- 238000004378 air conditioning Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 23
- 230000005525 hole transport Effects 0.000 abstract description 19
- 238000004381 surface treatment Methods 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 98
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000007787 solid Substances 0.000 description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 23
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 23
- 239000000178 monomer Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000001226 reprecipitation Methods 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 238000000944 Soxhlet extraction Methods 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 239000011630 iodine Chemical group 0.000 description 2
- 229910052740 iodine Chemical group 0.000 description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 2
- DLQYXUGCCKQSRJ-UHFFFAOYSA-N tris(furan-2-yl)phosphane Chemical compound C1=COC(P(C=2OC=CC=2)C=2OC=CC=2)=C1 DLQYXUGCCKQSRJ-UHFFFAOYSA-N 0.000 description 2
- -1 (4-phenyl) (2, 4, 6-trimethylphenyl) Chemical group 0.000 description 1
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
一种包含如式(I)所示的重复单元的芳香胺聚合物与包含该芳香胺聚合物的钙钛矿光电元件。以本发明的芳香胺聚合物作为空穴传输材料时,其所制得的下载子传输层无需再经表面处理,即能以湿式涂布方法在该下载子传输层上积层钙钛矿活性层,且同时能提升钙钛矿光电元件的能量转换效率(PCE)与稳定性;
Description
技术领域
本发明是有关于一种聚合物及包含前述聚合物的钙钛矿光电元件,特别是指一种芳香胺聚合物及包含前述芳香胺聚合物的钙钛矿光电元件。
背景技术
钙钛矿光电材料近年发展迅速,因其具有良好的光学性质与电性且可用在湿式涂布制程,所以被用来制作低成本且高功能性的钙钛矿光电元件,例如太阳能电池、发光二极管或光传感器等。
常见被用来作为钙钛矿光电元件中下载子传输层的空穴传输材料包含如金属氧化物的无机材料或如PEDOT:PSS或聚[双(4-苯基)(2,4,6-三甲基苯基)胺]{poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine],PTAA}的有机高分子。其中,金属氧化物通常需高温制程且表面仍需额外做钝化处理,而PEDOT:PSS又有易吸附水气而造成导电度下降的疑虑。因此,考虑钙钛矿光电元件的商业化,PTAA较适合作为空穴传输材料。
然而,PTAA薄膜的表面能较低,所以属于疏水性材质。未经表面处理的PTAA薄膜难以被表面能较高的钙钛矿前驱液(用在制备钙钛矿光电元件中的钙钛矿活性层)所湿润,因而难以进行湿式涂布。现有的解决方式是对PTAA薄膜进行表面处理以提高其表面能,藉以提升表面亲水性。常见的做法为先将其表面涂布一层如DMF或DMSO的溶剂层,或是对其表面进行电浆或臭氧处理。然而,溶剂层的处理方式不适合规模性量产,电浆或臭氧等表面处理方式又会伤害PTAA材料产生缺陷而有形成载子陷阱的疑虑,且对元件寿命也会有不良影响。
因此,如何改良作为空穴传输材料的PTAA的化学结构来改善空穴传输材料的表面能,以实现能利用湿式涂布方法制备钙钛矿活性层,且同时能提升钙钛矿光电元件的能量转换效率(power conversion efficiency,PCE)与稳定性,对于钙钛矿光电元件的商业化特别重要。
发明内容
因此,本发明的第一目的,即在提供一种芳香胺聚合物。以本发明的芳香胺聚合物作为空穴传输材料时,其所制得的下载子传输层无需再经表面处理,即能以湿式涂布方法在该下载子传输层上积层钙钛矿活性层,且同时能提升钙钛矿光电元件的能量转换效率(PCE)与稳定性。
于是,本发明芳香胺聚合物,包含下式(I)所示的重复单元:
其中,
W为
Y为
W与Y不相同;
a与b分别为实数,且0≤a<0.8,0.2<b≤1,并a与b的总和为1;
n1至n4分别为0、1或2;
m1与m2分别为0或1;
B1至B5分别为氢、甲基、甲氧基或-O(CH2)n5OCH3,n5为1~8,且B1至B5中的至少一者为甲氧基或-O(CH2)n5OCH3;
Ar1为芳基或杂芳基;
Ar2至Ar5分别为亚芳基或亚杂芳基;
L1与L2分别为
及
R1至R5分别C1~C40烷基、-(CH2)n6N(CH3)2、-(CH2)n6N+R6(CH3-)2X-或-(CH2)n6N+H(CH3)2X-,且n6为1~8,R6为甲基或乙基,X为氯、溴或碘。
因此,本发明的第二目的,即在提供一种钙钛矿光电元件。
于是,本发明钙钛矿光电元件包含前述的芳香胺聚合物。
本发明的效果在于:由于本发明芳香胺聚合物中的Y重复单元具有B1至B5官能基且B1至B5中的至少一者为甲氧基或-O(CH2)n5OCH3,所以相较于现有PTAA(对应的苯基上仅有甲基取代),本发明芳香胺聚合物会具有较高的极性,进而能提高其表面能(亲水性)。因此,以本发明的芳香胺聚合物作为空穴传输材料时,其所制得的下载子传输层无需再经表面处理,即能以湿式涂布方法在该下载子传输层上积层钙钛矿活性层,且同时还能提升钙钛矿光电元件的能量转换效率(PCE)与稳定性。
以下将就本发明内容进行详细说明:
[芳香胺聚合物]
本发明芳香胺聚合物,包含下式(I)所示的重复单元。
[式(I)]
其中,
W为
Y为
W与Y不相同。
a与b分别表示为摩尔分率的实数,且0≤a<0.8,0.2<b≤1,并a与b的总和为1。补充说明的是,当0≤a<0.8及0.2<b≤1的情况下,用于制备钙钛矿活性层的钙钛矿前驱液皆能顺利地以湿式涂布方法涂布于本发明芳香胺聚合物上。
n1至n4分别为0、1或2。
m1与m2分别为0或1。
较佳地,当a不为0时,n1至n4皆不为0;当a为0时,m2不为0。
B1至B5分别为氢、甲基、甲氧基或-O(CH2)n5OCH3,n5为1~8,且B1至B5中的至少一者为甲氧基或-O(CH2)n5OCH3。
Ar1为芳基或杂芳基。较佳地,Ar1为
其中,R7为C1~C8烷基或-(CH2)n7OCH3,且n7为1~8。
Ar2至Ar5分别为亚芳基(arylene)或亚杂芳基(heteroarylene)。较佳地,Ar2至Ar5分别为亚苯基或亚联苯基。更佳地,Ar2至Ar5分别为(亚苯基)。
L1与L2分别为
R1至R5分别C1~C40烷基、-(CH2)n6N(CH3)2、-(CH2)n6N+R6(CH3-)2X-或-(CH2)n6N+H(CH3)2X-,且n6为1~8,R6为甲基或乙基,X为氯、溴或碘。
较佳地,L1与L2分别为且R1与R2分别为C1~C40烷基或-(CH2)n6N(CH3)2。更佳地,R1与R2分别为C1~C5烷基或-(CH2)n6N(CH3)2,且n6为1~5。
[钙钛矿光电元件]
本发明钙钛矿光电元件,包含前述的芳香胺聚合物。
较佳地,该钙钛矿光电元件包括一基板、一积层于该基板上的下电极、一积层于该下电极上的下载子传输层单元、一积层于该下载子传输层单元上的钙钛矿活性层、一积层于该钙钛矿活性层上的上载子传输层、一积层于该上载子传输层上的上载子修饰层,及一积层于该上载子修饰层上的上电极,该下载子传输层单元包含该芳香胺聚合物。
更佳地,该下载子传输层单元具有一下载子传输层,该下载子传输层包含该芳香胺聚合物。
又更佳地,该下载子传输层单元的厚度范围为0.1~200nm。又更佳地,该下载子传输层单元的厚度范围为0.1~50nm。
又更佳地,该下载子传输层单元的最高占有分子轨域(highest occupiedmolecular orbital,HOMO)与该钙钛矿活性层的最高占有分子轨域(HOMO)的能量差小于1.0eV。
更佳地,该下载子传输层单元具有数层下载子传输层,且至少一层下载子传输层包含该芳香胺聚合物。
又更佳地,邻近该钙钛矿活性层的下载子传输层包含该芳香胺聚合物。
附图说明
本发明的其他的特征及效果,将于参照图式的实施方式中清楚地呈现,其中:
图1是一剖面示意图,说明本发明钙钛矿光电元件的结构;
图2是一剖面示意图,说明本发明钙钛矿光电元件中的下载子传输层单元具有数层下载子传输层的结构;
图3是一相片,说明PTAA与实施例1~3的水接触角;
图4是一相片,说明PTAA、经表面处理的PTAA与实施例1~3的钙钛矿活性层覆盖性测试结果;及
图5是一曲线图,说明应用例2与比较应用例1的钙钛矿光电元件持续照光的稳定性结果。
【符号说明】
1:基板
2:下电极
3:下载子传输层单元
31:下载子传输层
32:下载子传输层
4:钙钛矿活性层
5:上载子传输层
6:上载子修饰层
7:上电极
具体实施方式
<制备例1>
制备单体A1
单体A1是依据下列方法所制得。
化合物2的制备方法:
先将2,4,6-三甲基苯胺化合物1(20.0g,147.9mmol)与400mL的甲苯混合于圆底瓶中,再加入碘苯(37.6g,184.3mmol)、Pd2(dba)3(6.8g,7.4mmol)、P(t-bu)3·BF4(8.5g,29.2mmol)与叔丁醇钠(40.0g,416.1mmol)后,于氮气与100℃环境下搅拌15小时。待冷却后,以硅藻土过滤。滤液先使用回旋浓缩机移除甲苯,再加入100mL甲醇搅拌10分钟后,过滤收集固体。最后,经真空干燥后得到棕色固体化合物2(30.4g,产率:71.6%)。
化合物3的制备方法:
先将化合物2(20.0g,69.5mmol)加入至1L的圆底瓶当中,再加入300mL的DMF与NBS(27.1g,14.6mmol)后,于室温下搅拌3小时。接着,将反应溶液缓慢倒进含有1L水的2L烧杯中(固体析出)。最后,过滤收集固体,再经真空干燥后得到土黄色固体化合物3(29.3g,产率:70.1%)。
单体A1的制备方法:
于氮气下先将化合物3(10.0g,22.4mmol)入料于250mL反应瓶中,再加入100mL的无水四氢呋喃后,于-70℃下,逐滴加入正丁基锂(29.6mL,74.1mmol)并搅拌1小时。接着,先于-70℃下加入硼酸三甲酯(15.4g,148.2mmol)并搅拌1小时,再于10℃下缓慢加入20mL 4N盐酸水溶液后,于室温下搅拌0.5小时。先去除水层并以无水硫酸镁干燥,再浓缩除去溶剂后,经再结晶(THF/庚烷(heptane)=1:6)纯化得到白色中间体(5.2g)。先将中间体与20mL氯仿入料于100mL反应瓶中,再加入频哪醇(Pinacol)(3.6g,30.5mmol)后,于室温下搅拌4小时。最后,反应溶液先以硅胶过滤,再将滤液浓缩除去溶剂后,经由再结晶(THF/MeOH=1:8)纯化得到白色固体单体A1(4.8g,产率:39.6%)。
<制备例2>
制备单体A2
单体A2是依据下列方法所制得。
化合物5的制备方法:
先将化合物4(20.0g,162.4mmol)与400mL的甲苯混合于圆底瓶中,再加入碘苯(82.8g,406.0mmol)、Pd2(dba)3(7.4g,8.1mmol)、P(t-bu)3·BF4(9.4g,32.4mmol)与叔丁醇钠(46.8g,487.2mmol)后,于氮气及100℃下搅拌15小时。待冷却后,先以硅藻土过滤,滤液再使用回旋浓缩机移除甲苯后,加入100mL甲醇搅拌10分钟。最后,先过滤收集固体,经真空干燥后得到棕色固体化合物5(26.0g,产率:59.0%)。
单体A2的制备方法:
先将化合物5(10.0g,36.3mmol)加入至1L的圆底瓶当中,再加入200mL的DMF和NBS(13.5g,76.2mmol)后,于室温下搅拌3小时。接着,先加入400mL水,再以EA萃取(100mLX3)后,以无水硫酸镁干燥。最后,浓缩除去溶剂,经真空干燥后得到红棕色油状单体A2(22.0g,产率:70.0%)。
<制备例3>
制备单体A3
单体A3是依据下列方法所制得。
化合物7的制备方法:
先将化合物6(10.0g,51.4mmol)加入至250mL的圆底瓶当中,再加入50mL DMF后,于40℃下缓慢加入NBS(27.4g,154.4mmol)。接着,于50℃下搅拌7小时。待冷却后,先将反应溶液缓慢倒进含有250mL水的1L烧杯中(固体析出),再过滤收集固体后,经真空干燥后得到白色固体化合物7(14.9g,产率:82.5%)。
单体A3的制备方法:
于氮气下先将化合物7(10.0g,28.4mmol)入料于250mL反应瓶中,再加入100mL的无水四氢呋喃后,于-70℃下逐滴加入正丁基锂(37.4mL,93.7mmol)并搅拌1小时。同温下,先加入硼酸三甲酯(19.4g,187.4mmol)并搅拌1小时,再于10℃下缓慢加入20mL 4N HCl水溶液后,于室温下搅拌0.5小时。接着,先去除水层,再以无水硫酸镁干燥并浓缩除去溶剂后,经由再结晶(THF/Heptane=1:6)纯化得到白色中间体(6.6g)。最后,先将中间体与20mL氯仿入料于100mL反应瓶中,再加入pinacol(5.1g,49.1mmol)后,于室温下搅拌4小时。最后,反应溶液先以硅胶过滤,滤液再浓缩除去溶剂后,经由再结晶(THF/MeOH=1:8)纯化得到白色固体单体A3(5.7g,产率:45.2%)。
<制备例4>
制备单体A4
单体A4是依据下列方法所制得。
单体A4的制备方法:
先于氮气下将化合物8(50.0g,154.3mmol)、N,N-二甲基-3-氯丙胺盐酸盐(73.1g,462.9mmol)、四丁基溴化铵(1.0g,3.08mmol)与500mL DMSO入料于2L反应瓶中,再加入100mL 50%NaOH溶液并于室温下搅拌7小时。接着,逾10℃下加入200mL EA和200mL水,以硅藻土过滤收集液体并将溶液pH值调至弱碱性。保留有机层并加入250mL 1N盐酸水溶液。保留水层并加入200mL10%氢氧化钠水溶液。最后,加入EA萃取(200mL*3)并以无水硫酸镁干燥。经浓缩除去溶剂后,得到白色固体单体A4(61.7g,产率:80.9%)。
<实施例1>
制备芳香胺聚合物
实施例1的芳香胺聚合物是依据下列方法所制得。
实施例1的制备方法:
先将单体A1(1.0g,1.85mmol)、单体A2(0.8g,1.85mmol)、三(2-呋喃基)膦(0.09g,0.29mmol)、磷酸钾(1.1g,5.5mmol)与四丁基溴化铵(0.06g,0.18mmol)置于100mL反应瓶中,再加入甲苯50mL与水7.5mL后,使用氩气进行脱氧30分钟。接着,先加入Pd2(dba)3(0.06g,0.07mol),再加热至100℃并持续反应16小时。待反应冷却后,以硅藻土过滤。滤液先浓缩去除溶剂,经由再沉淀(THF/MeOH=1:10)析出固体后,过滤收集沉淀物。将该固体依序以甲醇和丙酮进行索氏萃取(soxhlet)。最后,将残留固体取出,经由再沉淀(THF/MeOH=1:10)析出固体。过滤收集沉淀物,经真空干燥后,得到淡黄色实施例1(0.7g)。
<实施例2>
制备芳香胺聚合物
实施例2的芳香胺聚合物是依据下列方法所制得。
实施例2的制备方法:
先将单体A2(1.0g,2.24mmol)、单体A3(0.97g,2.24mmol)、三(2-呋喃基)膦(0.1g,0.35mmol)、磷酸钾(1.4g,6.7mmol)与四丁基溴化铵(0.07g,0.22mmol)置于100mL反应瓶中,再加入甲苯50mL和水7.5mL后,使用氩气进行脱氧30分钟。接着,先加入Pd2(dba)3(0.08g,0.08mol),再加热至100℃并持续反应16小时。待反应冷却后,以硅藻土过滤。滤液浓缩去除溶剂,经由再沉淀(THF/MeOH=1:10)析出固体后,过滤收集沉淀物。将该固体依序以甲醇和丙酮进行索氏萃取(soxhlet)。最后,将残留固体取出,经由再沉淀(THF/MeOH=1:10)析出固体。过滤收集沉淀物,经真空干燥后,得到淡黄色实施例2(0.6g)。
<实施例3>
制备芳香胺聚合物
实施例3的芳香胺聚合物是依据下列方法所制得。
实施例3的制备方法:
先将化合物4(0.25g,2.03mmol)、单体A4(1.0g,2.03mmol)与50mL的甲苯混合于圆底瓶中,再加入Pd2(dba)3(0.10g,0.1mmol)、P(t-bu)3.BF4(0.11g,0.4mmol)与叔丁醇钠(0.48g,5.07mmol)后,于氮气及100℃环境下搅拌15小时。待冷却后,以硅藻土过滤。滤液使用回旋浓缩机移除甲苯,经由再沉淀(THF/MeOH=1:10)析出固体后,过滤收集沉淀物。将该固体依序以甲醇和丙酮进行索氏萃取(soxhlet)。最后,将残留固体取出,经由再沉淀(THF/MeOH=1:10)析出固体。过滤收集沉淀物,经真空干燥后,得到淡黄色实施例3(0.3g)。
<钙钛矿光电元件结构>
参阅图1,本发明的钙钛矿光电元件包括一基板1、一积层于该基板1上的下电极2、一积层于该下电极2上的下载子传输层单元3、一积层于该下载子传输层单元3上的钙钛矿活性层4、一积层于该钙钛矿活性层4上的上载子传输层5、一积层于该上载子传输层5上的上载子修饰层6,及一积层于该上载子修饰层6上的上电极7。
该下载子传输层单元3具有一层下载子传输层31,该下载子传输层31包含芳香胺聚合物。该下载子传输层单元3的最高占有分子轨域(HOMO)与该钙钛矿活性层4的最高占有分子轨域(HOMO)的能量差小于1.0eV。
特别说明的是,该下载子传输层单元3也可具有数层下载子传输层,且至少一层下载子传输层包含该芳香胺聚合物。较佳地,邻近该钙钛矿活性层4的下载子传输层包含该芳香胺聚合物。以图2的钙钛矿光电元件结构举例说明,该钙钛矿光电元件的下载子传输层单元3具有两层下载子传输层31,32,且邻近该钙钛矿活性层4的下载子传输层32包含该芳香胺聚合物。
<应用例1~3>
制备钙钛矿光电元件
应用例1~3的钙钛矿光电元件(结构参阅图1)是依据下表1所示的空穴传输材料(芳香胺聚合物)与下列方法所制得。
表1
/>
将氧化铟锡(ITO)玻璃基板(12Ω/□)依序使用清洁剂、去离子水、丙酮及异丙醇经超音波震荡清洗15分钟后,再经由UV ozone清洁机进行基板表面清洁30分钟。其中,玻璃基板即为该基板1,氧化铟锡(ITO)即为该下电极2。
将表1所列的空穴传输材料(芳香胺聚合物)与溶剂甲苯混和,形成固含量为1.5wt%的溶液。将该溶液涂布于玻璃基板上,并于100~120℃烘烤10~30分钟后,形成厚度约20nm的下载子传输层31。
将钙钛矿原料成份HC(NH2)2I、CsI、PbI2、PbBr2依照莫尔比例0.83:0.17:0.85:0.15与溶剂DMF/DMSO(9:1v/v)混和,形成固含量为49wt%的钙钛矿前驱液。先将该钙钛矿前驱液涂布于该下载子传输层31上,再利用真空减压法去除溶剂,并于100~110℃下烘烤30~60分钟后,形成厚度约400nm的钙钛矿活性层4。
将PCBM与溶剂氯苯混合,形成固含量2.5wt%的溶液。将该溶液涂布于钙钛矿活性层4上,并于80~100℃烘烤10分钟后,形成厚度约50nm的上载子传输层5。
将PEI与溶剂二丁醇混合,形成固含量0.05wt%的溶液。将该溶液涂布于上载子传输层5上,并于90~100℃烘烤6分钟后,形成厚度约2nm的上载子修饰层6。
先将前述所得的样品送入真空腔体内,再于1.0×10-6torr下蒸镀银金属,形成厚度约100nm的上电极7后,得到钙钛矿光电元件。
<比较应用例1>
制备钙钛矿光电元件
比较应用例1的钙钛矿光电元件(结构参阅图1)是依据上表1所示的空穴传输材料(芳香胺聚合物)与下列方法所制得。
比较应用例1的钙钛矿光电元件的制备方法与应用例1类似,其差别在于,比较应用例1于积层钙钛矿活性层4前,需先将已积层好的下载子传输层3经由UV ozone清洁机进行表面处理5分钟,才进行钙钛矿活性层4的积层。
<芳香胺聚合物的水接触角测试>
将氧化铟锡(ITO)玻璃基板(12Ω/□)依序使用清洁剂、去离子水、丙酮及异丙醇经超音波震荡清洗15分钟后,再经由UV ozone清洁机进行基板表面清洁30分钟。
将空穴传输材料(实施例1~3的芳香胺聚合物或PTAA)与溶剂甲苯混和,形成固含量为1.5wt%的溶液。将该溶液涂布于玻璃基板上,并于100~120℃烘烤10~30分钟后,形成厚度约20nm的下载子传输层。此外,其中一测试样品,需先将以PTAA所形成的下载子传输层经由UV ozone清洁机进行表面处理5分钟。
水接触角的测试方法是通过相机撷取水滴与下载子传输层界面的图像并配合软体计算其水接触角值。图3为水接触角的测试结果。水接触角的数值列于下表2。水接触角越大,表面能越低(亲水性越低)。
表2
<钙钛矿活性层覆盖性测试>
将氧化铟锡(ITO)玻璃基板(12Ω/□)依序使用清洁剂、去离子水、丙酮及异丙醇经超音波震荡清洗15分钟后,再经由UV ozone清洁机进行基板表面清洁30分钟。
将空穴传输材料(实施例1~3的芳香胺聚合物或PTAA)与溶剂甲苯混和,形成固含量为1.5wt%的溶液。将该溶液涂布于玻璃基板上,并于100~120℃烘烤10-30分钟后,形成厚度约20nm的下载子传输层。
将钙钛矿原料成份HC(NH2)2I、CsI、PbI2、PbBr2依照摩尔比例0.83:0.17:0.85:0.15与溶剂DMF/DMSO(9:1v/v)混和,形成固含量为49wt%的钙钛矿前驱液。先将该钙钛矿前驱液涂布于该下载子传输层上,再利用真空减压法将去除溶剂,并于100~110℃下烘烤30~60分钟后,形成厚度约400nm的钙钛矿活性层。
需说明的是,其中一测试样品,需先将以PTAA所形成的下载子传输层经由UVozone清洁机进行表面处理5分钟,才进行钙钛矿活性层的积层。
图4为钙钛矿活性层利用湿式涂布于下载子传输层上的照片。
综合表2与图4的结果可以发现,采用现有未经表面处理的PTAA作为空穴传输材料的下载子传输层,因其水接触角高达80.9°(即表面能过低)而不利于下载子传输层湿式涂布钙钛矿活性层,导致钙钛矿活性层湿膜收缩严重。前述还必须将PTAA所形成的下载子传输层表面先通过表面处理(如UV ozone),才能得到覆盖性较好的钙钛矿活性层。而相较于PTAA,采用本发明的芳香胺聚合物(实施例1~3)可不需经由UV ozone进行表面处理,即可得到覆盖性良好的钙钛矿活性层。前述结果归因于本发明的芳香胺聚合物能有效提升材料的表面能。
<钙钛矿光电元件的能量转换效率(PCE)分析>
钙钛矿光伏元件的工作区域经由金属遮罩定义为0.04cm2。Keithley 2400作为电源供应器,以Lab-View程式控制,在光强度100mW/cm2的AM1.5G模拟太阳光(SAN-EI XES-40S3)的照射下量测钙钛矿光电元件的电性,并以电脑程式记录,得到电流-电压特性参数。
应用例1~2与比较应用例1的钙钛矿光电元件所使用的空穴传输材料(芳香胺聚合物),以及由前述电性分析结果所得的开路电压(open voltage;Voc)、短路电流(short-circuit current;Jsc)、填充因子(fill factor;FF)与能量转换效率(PCE)分别整理于下表3中。
表3
由表3可以发现,相较于采用经表面处理的PTAA作为空穴传输材料的钙钛矿光电元件(比较应用例1),采用本发明芳香胺聚合物作为空穴传输材料的钙钛矿光电元件(应用例1~2)具有更高的能量转换效率(PCE)。
<有机光伏电池的热稳定性测试>
将应用例2与比较应用例1的钙钛矿光电元件持续照光作模拟实际应用情况,测试结果见图5。
由图5可以发现,相较于采用经表面处理的PTAA作为空穴传输材料的钙钛矿光电元件(比较应用例1),采用本发明芳香胺聚合物作为空穴传输材料的钙钛矿光电元件(应用例2)具有更稳定的能量转换效率(PCE)。前述情况是因为本发明芳香胺聚合物所形成的下载子传输层无需像PTAA一样必须先进行表面处理才能以湿式涂布方法在该下载子传输层上积层钙钛矿活性层,所以能避免表面处理过程会伤害材料性质的风险。
综合前面实验可知,由于本发明芳香胺聚合物中的Y重复单元具有B1至B5官能基且B1至B5中的至少一者为甲氧基或-O(CH2)n5OCH3,所以相较于现有PTAA(对应的苯基上仅有甲基取代),本发明芳香胺聚合物会具有较高的极性,进而能提高其表面能(亲水性)。因此,以本发明的芳香胺聚合物作为空穴传输材料时,其所制得的下载子传输层无需再经表面处理,即能以湿式涂布方法在该下载子传输层上积层钙钛矿活性层,且同时还能提升钙钛矿光电元件的能量转换效率(PCE)与稳定性,故确实能达成本发明的目的。
惟以上所述者,仅为本发明的实施例而已,当不能以此限定本发明实施的范围,凡是依本发明申请专利范围及专利说明书内容所作的简单的等效变化与修饰,皆仍属本发明专利涵盖的范围内。
Claims (9)
1.一种钙钛矿光电元件,包含芳香胺聚合物,该芳香胺聚合物由下式(I)所示的重复单元组成:
[式(I)]
其中,
W为
Y为
W与Y不相同;
a与b分别为实数,且0≤a<0.8,0.2<b≤1,并a与b的总和为1;
n1至n4分别为0、1或2;
m1与m2分别为0或1;
B1至B5分别为氢、甲基、甲氧基或-O(CH2)n5OCH3,n5为1~8,且B1至B5中的至少一者为甲氧基或-O(CH2)n5OCH3;
Ar1为
Ar2至Ar5分别为亚芳基或亚杂芳基;
L1与L2分别为
及
R1至R2分别为C1~C40烷基或-(CH2)n6N(CH3)2,且n6为1~8。
2.如权利要求1所述的钙钛矿光电元件,其中,Ar2至Ar5分别为亚苯基或亚联苯基。
3.如权利要求2所述的钙钛矿光电元件,其中,Ar2至Ar5分别为
4.如权利要求1所述的钙钛矿光电元件,其中,该钙钛矿光电元件包括一基板、一积层于该基板上的下电极、一积层于该下电极上的下载子传输层单元、一积层于该下载子传输层单元上的钙钛矿活性层、一积层于该钙钛矿活性层上的上载子传输层、一积层于该上载子传输层上的上载子修饰层,及一积层于该上载子修饰层上的上电极,该下载子传输层单元包含该芳香胺聚合物。
5.如权利要求4所述的钙钛矿光电元件,其中,该下载子传输层单元具有一下载子传输层,该下载子传输层包含该芳香胺聚合物。
6.如权利要求5所述的钙钛矿光电元件,其中,该下载子传输层的厚度范围为0.1~200nm。
7.如权利要求5所述的钙钛矿光电元件,其中,该下载子传输层的最高占有分子轨域与该钙钛矿活性层的最高占有分子轨域的能量差小于1.0eV。
8.如权利要求4所述的钙钛矿光电元件,其中,该下载子传输层单元具有数层下载子传输层,且至少一层下载子传输层包含该芳香胺聚合物。
9.如权利要求8所述的钙钛矿光电元件,其中,邻近该钙钛矿活性层的下载子传输层包含该芳香胺聚合物。
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