CN109065720B - A kind of perovskite solar cell with precise grain boundary doping and preparation method thereof - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 46
- 230000005525 hole transport Effects 0.000 claims abstract description 36
- 239000010936 titanium Substances 0.000 claims abstract description 32
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 230000007547 defect Effects 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 16
- -1 titanium ions Chemical class 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 72
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 30
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical group C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 20
- 239000004332 silver Substances 0.000 claims description 20
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- YMZOIRFEUWNMFP-UHFFFAOYSA-N 2,3,4,5-tetrabutylpyridine Chemical compound CCCCC1=CN=C(CCCC)C(CCCC)=C1CCCC YMZOIRFEUWNMFP-UHFFFAOYSA-N 0.000 claims description 7
- 238000003980 solgel method Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- VRGUHZVPXCABAX-UHFFFAOYSA-N methyllead Chemical compound [Pb]C VRGUHZVPXCABAX-UHFFFAOYSA-N 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000005215 recombination Methods 0.000 abstract description 11
- 230000006798 recombination Effects 0.000 abstract description 11
- 239000000969 carrier Substances 0.000 abstract description 9
- 238000011049 filling Methods 0.000 abstract description 2
- 230000003071 parasitic effect Effects 0.000 abstract description 2
- 238000002161 passivation Methods 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 62
- 238000004020 luminiscence type Methods 0.000 description 7
- 229910003074 TiCl4 Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HNCXPJFPCAYUGJ-UHFFFAOYSA-N dilithium bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].[Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HNCXPJFPCAYUGJ-UHFFFAOYSA-N 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- JAHFQMBRFYOPNR-UHFFFAOYSA-N iodomethanamine Chemical compound NCI JAHFQMBRFYOPNR-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229910052861 titanite Inorganic materials 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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Abstract
本发明涉及一种晶界精确掺杂的钙钛矿太阳能电池及其制备方法,其特征在于:导电玻璃层、致密二氧化钛膜、钛掺杂CH3NH3PbI3多晶膜、空穴传输材料层及蒸镀银电极层,钛掺杂CH3NH3PbI3多晶膜是指晶界处掺杂有钛离子,经过退火原位形成晶界缺陷钝化的CH3NH3PbI3多晶膜,钛离子的摩尔数为铅离子摩尔数的0.01%‑5%。本发明通过钛元素的掺入,有效抑制了电池内部p‑n结的载流子在晶界处复合,使得并联寄生电阻增大,从而提高了电池填充因子,光电流密度与光电转换效率。同时钛元素的掺杂比例进行了优化,进一步提高了光电转换效率。
The invention relates to a perovskite solar cell with precise grain boundary doping and a preparation method thereof, which is characterized by: a conductive glass layer, a dense titanium dioxide film, a titanium-doped CH 3 NH 3 PbI 3 polycrystalline film, and a hole transport material Titanium-doped CH 3 NH 3 PbI 3 polycrystalline film refers to a CH 3 NH 3 PbI 3 polycrystalline film that is doped with titanium ions at the grain boundary, and is annealed in situ to form a passivation of grain boundary defects. membrane, the moles of titanium ions are 0.01%-5% of the moles of lead ions. The invention effectively suppresses the recombination of the carriers of the p-n junction inside the battery at the grain boundary through the doping of titanium element, so that the parallel parasitic resistance is increased, thereby improving the battery filling factor, the photocurrent density and the photoelectric conversion efficiency. At the same time, the doping ratio of titanium element is optimized, which further improves the photoelectric conversion efficiency.
Description
技术领域technical field
本发明涉及一种晶界精确掺杂的钙钛矿太阳能电池及其制备方法。The invention relates to a perovskite solar cell with precise grain boundary doping and a preparation method thereof.
背景技术Background technique
钙钛矿太阳能电池由于其成本低,性能好,制备简单受到科研以及产业界的高度重视。钙钛矿材料从2009年用于太阳能电池,到目前效率已经超过22%,是初始时的电池效率的5倍,把染料敏化太阳能电池、有机太阳能电池等新型薄膜太阳电池甩在了身后,钙钛矿太阳能电池是近三年来发展非常迅速的低成本薄膜太阳能电池。Perovskite solar cells are highly valued by scientific research and industry due to their low cost, good performance, and simple preparation. Perovskite materials have been used in solar cells since 2009, and the current efficiency has exceeded 22%, which is 5 times the initial cell efficiency, leaving new thin-film solar cells such as dye-sensitized solar cells and organic solar cells behind. Perovskite solar cells are low-cost thin-film solar cells that have developed very rapidly in the past three years.
钙钛矿太阳能电池结构核心是具有钙钛矿晶型(ABX3)的有机金属卤化物吸光材料。在这种钙钛矿ABX3结构中,A为甲胺基(CH3NH3),B为金属铅原子,X为氯、溴、碘等卤素原子。目前在高效钙钛矿型太阳能电池中,最常见的钙钛矿材料是碘化铅甲胺(CH3NH3PbI3),它的带隙约为1.6 eV,消光系数高,几百纳米厚薄膜就可以充分吸收800 nm以下的太阳光。而且,这种材料制备简单,将含有PbI2和CH3NH3I的溶液,在常温下通过旋涂并且滴加氯苯萃取即可获得均匀薄膜。上述特性使得钙钛矿型结构CH3NH3PbI3不仅可以实现对可见光和部分近红外光的吸收,而且所产生的光生载流子不易复合,能量损失小,这是钙钛矿型太阳能电池能够实现高效率的根本原因。The core of the perovskite solar cell structure is an organometallic halide light-absorbing material with a perovskite crystal form (ABX 3 ). In this perovskite ABX 3 structure, A is a methylamine group (CH 3 NH 3 ), B is a metal lead atom, and X is a halogen atom such as chlorine, bromine, and iodine. Currently in high-efficiency perovskite solar cells, the most common perovskite material is lead iodide methylamine (CH 3 NH 3 PbI 3 ), which has a band gap of about 1.6 eV, a high extinction coefficient, and is several hundred nanometers thick. The film can fully absorb sunlight below 800 nm. Moreover, the preparation of this material is simple, and a solution containing PbI 2 and CH 3 NH 3 I can be obtained by spin coating and dropwise extraction with chlorobenzene at room temperature to obtain a uniform film. The above characteristics make the perovskite structure CH 3 NH 3 PbI 3 not only can absorb visible light and part of the near-infrared light, but also the photogenerated carriers are not easy to recombine, and the energy loss is small. This is a perovskite solar cell. The root cause of being able to achieve high efficiency.
钙钛矿太阳能电池目前有多种结构:含多孔二氧化钛的介观电池,无多孔二氧化钛的平面电池,含多孔绝缘氧化物(三氧化二铝,氧化锆)的超结构介观电池等。Perovskite solar cells currently have various structures: mesoscopic cells with porous titania, planar cells without porous titania, and superstructured mesoscopic cells with porous insulating oxides (alumina, zirconia).
目前,研究热点集中于通过调节有机无机杂化钙钛矿的A位,B位以及X位来调节其性能,进一步优化钙钛矿的光电转换性能。目前工艺,通过溶液旋涂并且退火,难以得到单晶的平面薄膜。多晶膜由于比表面积大,表面缺陷多,导致器件内部电荷复合严重。已有对钙钛矿膜进行碘化铅掺杂来抑制晶界缺陷的报道。但是,对于其钙钛矿晶界的其它元素掺杂并抑制其缺陷和复合的报道很少。并且由于其掺杂的元素离子半径非常小,无法准确掺杂在晶界处的缺陷位置,且不能保证电池器件的重复性,因此需要探索其它元素掺杂提高电池的性能。At present, research hotspots focus on adjusting the properties of organic-inorganic hybrid perovskites by adjusting the A-site, B-site and X-site to further optimize the photoelectric conversion performance of perovskite. In the current process, it is difficult to obtain a single-crystal planar thin film by solution spin coating and annealing. Due to the large specific surface area and many surface defects of the polycrystalline film, the charge recombination inside the device is serious. There have been reports of lead iodide doping of perovskite films to suppress grain boundary defects. However, there are few reports on doping of its perovskite grain boundaries with other elements and suppressing its defects and recombination. And because the ion radius of the doped element is very small, it cannot be accurately doped at the defect position at the grain boundary, and the repeatability of the battery device cannot be guaranteed. Therefore, it is necessary to explore other element doping to improve the performance of the battery.
综上所述,现有技术存在的问题是:To sum up, the problems existing in the prior art are:
1)有机无机杂化钙钛矿材料CH3NH3PbI3需要进一步优化,提高其光电转换性能;1) The organic-inorganic hybrid perovskite material CH 3 NH 3 PbI 3 needs to be further optimized to improve its photoelectric conversion performance;
2)目前对晶界掺杂的元素对电池的开路电压和重复性造成影响,晶界缺陷造成的载流子复合问题仍未解决。2) At present, the elements doped at the grain boundary have an impact on the open circuit voltage and repeatability of the battery, and the problem of carrier recombination caused by grain boundary defects has not yet been solved.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术中存在的上述不足,而提供一种通过钙钛矿掺杂来改善多晶形成过程中缺陷的晶界精确掺杂的钙钛矿太阳能电池及其制备方法。The purpose of the present invention is to overcome the above-mentioned deficiencies in the prior art, and to provide a perovskite solar cell with precise grain boundary doping that improves the defects in the polycrystalline formation process by perovskite doping, and a preparation method thereof.
本发明解决上述问题所采用的技术方案是:一种晶界精确掺杂的钙钛矿太阳能电池,其特征在于:导电玻璃层、致密二氧化钛膜、钛掺杂CH3NH3PbI3多晶膜、空穴传输材料层及蒸镀银电极层,钛掺杂CH3NH3PbI3多晶膜是指晶界处掺杂有钛离子,经过退火原位形成晶界缺陷钝化的CH3NH3PbI3多晶膜,钛离子的摩尔数为铅离子摩尔数的0.01%-5%。The technical solution adopted by the present invention to solve the above problems is: a perovskite solar cell with precise grain boundary doping, which is characterized by: a conductive glass layer, a dense titanium dioxide film, and a titanium-doped CH 3 NH 3 PbI 3 polycrystalline film , hole transport material layer and vapor-deposited silver electrode layer, titanium-doped CH 3 NH 3 PbI 3 polycrystalline film refers to that the grain boundary is doped with titanium ions, and after annealing, the CH 3 NH is formed in situ with passivation of grain boundary defects. 3 PbI 3 polycrystalline film, the mole number of titanium ions is 0.01%-5% of the mole number of lead ions.
本发明所述钛离子的粒子半径小于CH3NH3PbI3多晶膜的晶粒半径。The particle radius of the titanium ion in the present invention is smaller than the crystal grain radius of the CH 3 NH 3 PbI 3 polycrystalline film.
本发明致密二氧化钛膜厚度为20-200纳米,钛掺杂CH3NH3PbI3多晶膜厚度为200纳米-1.5微米,空穴传输材料层厚度为50-500纳米,蒸镀银电极层厚度为50-200纳米。The thickness of the dense titanium dioxide film of the present invention is 20-200 nanometers, the thickness of the titanium - doped CH3NH3PbI3 polycrystalline film is 200 nanometers - 1.5 micrometers, the thickness of the hole transport material layer is 50-500 nanometers, and the thickness of the evaporated silver electrode layer 50-200 nm.
本发明空穴传输材料层为spiro-MeOTAD或3-己基取代聚噻吩。The hole transport material layer of the present invention is spiro-MeOTAD or 3-hexyl-substituted polythiophene.
一种晶界精确掺杂的钙钛矿太阳能电池的制备方法,其特征在于:包括如下步骤:A method for preparing a perovskite solar cell with precise grain boundary doping is characterized in that: comprising the following steps:
步骤①:将碘甲胺和碘化铅以摩尔比1:1溶解于N,N-二甲基甲酰胺中,再加入四氯化钛,搅拌均匀形成钙钛矿溶液;Step 1: dissolving methyl iodide and lead iodide in N,N-dimethylformamide at a molar ratio of 1:1, then adding titanium tetrachloride, and stirring to form a perovskite solution;
步骤②:使用溶胶凝胶法在导电玻璃上沉积致密二氧化钛膜;致密二氧化钛膜在300℃-500℃处理后再进行四氯化钛处理,烧结后备用;Step ②: depositing a dense titanium dioxide film on the conductive glass by a sol-gel method; the dense titanium dioxide film is treated at 300°C-500°C and then treated with titanium tetrachloride, and is sintered for later use;
步骤③:使用匀胶机将钙钛矿溶液通过氯苯萃取的工艺沉积在致密二氧化钛膜上,控制温度40℃-100℃烘烤30分钟,使得钙钛矿溶液在致密二氧化钛膜上结晶成为钛掺杂CH3NH3PbI3多晶膜;Step 3: Use a glue homogenizer to deposit the perovskite solution on the dense titanium dioxide film through the process of chlorobenzene extraction, and bake at a temperature of 40°C-100°C for 30 minutes, so that the perovskite solution crystallizes on the dense titanium dioxide film to become titanium dioxide. Doping CH 3 NH 3 PbI 3 polycrystalline film;
步骤④:将空穴传输材料的有机溶液均匀的旋涂在钛掺杂CH3NH3PbI3多晶膜上形成空穴传输材料层;Step ④: uniformly spin-coating the organic solution of the hole transport material on the titanium-doped CH 3 NH 3 PbI 3 polycrystalline film to form a hole transport material layer;
步骤⑤:使用蒸镀方法,在空穴传输材料层上蒸镀蒸镀银电极层。Step ⑤: Using an evaporation method, an evaporated silver electrode layer is evaporated on the hole transport material layer.
本发明所述空穴传输材料层材质为spiro-MeOTAD,空穴传输材料的有机溶液制备步骤如下:将spiro-MeOTAD溶解于氯苯中,spiro-MeOTAD的摩尔浓度为0.5-1.5M,再加入spiro-MeOTAD摩尔数80 %的四丁基吡啶和spiro-MeOTAD摩尔数30 %的双三氟甲烷磺酰亚胺锂,搅拌均匀。The hole transport material layer of the present invention is made of spiro-MeOTAD, and the preparation steps of the organic solution of the hole transport material are as follows: dissolve spiro-MeOTAD in chlorobenzene, the molar concentration of spiro-MeOTAD is 0.5-1.5M, and then add Spiro-MeOTAD molar 80% tetrabutylpyridine and spiro-MeOTAD molar 30% lithium bis-trifluoromethanesulfonimide, stir well.
本发明钙钛矿溶液中,碘甲胺和碘化铅的摩尔浓度均控制在0.8-1.2M。In the perovskite solution of the present invention, the molar concentrations of iodomethylamine and lead iodide are both controlled at 0.8-1.2M.
与现有技术相比,本发明的优点在于:使用了离子半径相对小的钛元素掺杂CH3NH3PbI3。由于钛离子比钙钛矿晶粒小得多,因此能够掺杂在钙钛矿多晶形成过程中的晶界缺陷处。钛元素的掺入,有效抑制了电池内部p-n结的载流子在晶界处复合,使得并联寄生电阻增大,从而提高了电池填充因子,光电流密度与光电转换效率。同时钛元素的掺杂比例进行了优化,进一步提高了光电转换效率。Compared with the prior art, the present invention has the advantage of using titanium element with relatively small ionic radius to dope CH 3 NH 3 PbI 3 . Since titanium ions are much smaller than perovskite grains, they can be doped at grain boundary defects during the formation of perovskite polycrystals. The incorporation of titanium element effectively inhibits the recombination of carriers in the pn junction inside the battery at the grain boundary, which increases the parallel parasitic resistance, thereby improving the battery fill factor, photocurrent density and photoelectric conversion efficiency. At the same time, the doping ratio of titanium element is optimized, which further improves the photoelectric conversion efficiency.
附图说明Description of drawings
图1是本发明实施例2的CH3NH3PbI3晶格、Ti、Pb的EDS图。FIG. 1 is an EDS diagram of the CH 3 NH 3 PbI 3 lattice, Ti, and Pb in Example 2 of the present invention.
图2是本发明对比实施例和实施例2的SEM图。FIG. 2 is a SEM image of a comparative example and Example 2 of the present invention.
图3是本发明对比实施例和实施例1-4的伏安特性曲线。FIG. 3 is the volt-ampere characteristic curves of the comparative example and Examples 1-4 of the present invention.
图4是本发明对比实施例和实施例1-4的CH3NH3PbI3多晶膜/玻璃的稳态PL光致发光谱。 4 is the steady-state PL photoluminescence spectra of the CH3NH3PbI3 polycrystalline films/glasses of Comparative Examples and Examples 1-4 of the present invention.
图5是本发明对比实施例和实施例1-4的CH3NH3PbI3多晶膜/导电玻璃的稳态PL光致发光谱。FIG. 5 is the steady-state PL photoluminescence spectra of the CH 3 NH 3 PbI 3 polycrystalline film/conductive glass of Comparative Example and Examples 1-4 of the present invention.
具体实施方式Detailed ways
下面结合附图并通过实施例对本发明作进一步的详细说明,以下实施例是对本发明的解释而本发明并不局限于以下实施例。The present invention will be further described in detail below in conjunction with the accompanying drawings and through the examples. The following examples are to explain the present invention and the present invention is not limited to the following examples.
制备TiCl4的N,N-二甲基甲酰胺溶液:取纯TiCl4液体1毫升加入到10毫升纯酒精(冰箱内保存)中,得到1M的TiCl4的酒精溶液。取50微升的TiCl4的酒精溶液加入到950微升的N,N-二甲基甲酰胺(DMF)中,稀释得到0.05M的TiCl4溶液;取100微升的TiCl4的酒精溶液加入到900微升的N,N-二甲基甲酰胺(DMF)中,稀释得到0.1M的TiCl4溶液;取200微升的TiCl4的酒精溶液加入到800微升的N,N-二甲基甲酰胺(DMF)中,稀释得到0.2M的TiCl4溶液;取500微升的TiCl4的酒精溶液加入到500微升的N,N-二甲基甲酰胺(DMF)中,稀释得到0.5M的TiCl4溶液。Prepare the N,N-dimethylformamide solution of TiCl 4 : Take 1 ml of pure TiCl 4 liquid and add it to 10 ml of pure alcohol (stored in the refrigerator) to obtain a 1M alcohol solution of TiCl 4 . Take 50 microliters of TiCl4 alcohol solution and add it to 950 microliters of N,N-dimethylformamide (DMF), dilute to obtain 0.05M TiCl4 solution; take 100 microliters of TiCl4 alcohol solution and add into 900 μl of N,N-dimethylformamide (DMF), diluted to obtain a 0.1M TiCl 4 solution; 200 μl of TiCl 4 in alcohol solution was added to 800 μl of N,N-dimethylformamide Dimethylformamide (DMF), diluted to obtain 0.2M TiCl4 solution; 500 μl of TiCl4 alcoholic solution was added to 500 μl of N,N-dimethylformamide (DMF), diluted to obtain 0.5 M in TiCl4 solution.
对比实施例。Comparative Example.
本实施例制备纯净的CH3NH3PbI3钙钛矿太阳能电池。In this example, pure CH 3 NH 3 PbI 3 perovskite solar cells were prepared.
首先, 称取0.461克PbI2 与0.159克CH3NH3I共同溶解于1毫升N,N-二甲基甲酰胺(DMF)中,搅拌混合均匀形成钙钛矿溶液。First, 0.461 g of PbI 2 and 0.159 g of CH 3 NH 3 I were weighed and dissolved in 1 ml of N,N-dimethylformamide (DMF), and stirred and mixed to form a perovskite solution.
使用溶胶凝胶法在导电玻璃层上沉积一层致密二氧化钛膜(100纳米);致密二氧化钛膜经450℃处理后再进行四氯化钛处理,烧结后备用。A dense titanium dioxide film (100 nanometers) is deposited on the conductive glass layer by a sol-gel method; the dense titanium dioxide film is treated at 450° C. and then treated with titanium tetrachloride, and is sintered for later use.
使用匀胶机将钙钛矿溶液通过氯苯萃取的工艺沉积在致密二氧化钛膜上。通过精确控制温度在40~100℃烘烤30分钟,使得钙钛矿溶液结晶成为CH3NH3PbI3多晶膜。The perovskite solution was deposited on the dense titania film by a process of chlorobenzene extraction using a spinner. The perovskite solution was crystallized into a CH 3 NH 3 PbI 3 polycrystalline film by precisely controlling the temperature at 40-100 °C for 30 minutes.
将空穴传输材料spiro-MeOTAD的氯苯溶液(浓度为0.6M,加入spiro-MeOTAD摩尔数80 % 的四丁基吡啶(tBP)和spiro-MeOTAD摩尔数30 %的双三氟甲烷磺酰亚胺锂(Li-TFSI))均匀的旋涂在CH3NH3PbI3多晶膜,形成空穴传输材料层。The hole transport material spiro-MeOTAD in chlorobenzene solution (concentration of 0.6M, adding 80% moles of spiro-MeOTAD tetrabutylpyridine (tBP) and 30% moles of spiro-MeOTAD bistrifluoromethanesulfonylidene) Lithium amine (Li-TFSI)) was uniformly spin-coated on the CH 3 NH 3 PbI 3 polycrystalline film to form a hole transport material layer.
使用蒸镀方法,在空穴传输材料层上蒸镀蒸镀银电极层。The silver electrode layer was vapor-deposited on the hole-transporting material layer using the vapor-deposition method.
本实施例中的CH3NH3PbI3多晶膜厚度为600纳米,空穴传输材料层厚度为300纳米,蒸镀银电极层厚度为90纳米。In this embodiment, the thickness of the CH 3 NH 3 PbI 3 polycrystalline film is 600 nanometers, the thickness of the hole transport material layer is 300 nanometers, and the thickness of the vapor-deposited silver electrode layer is 90 nanometers.
在室温环境,使用氙灯模拟太阳光,光强为95.6mW/cm2(太阳光模拟器型号:Newport 91192A) 条件下,测得钙钛矿太阳能电池(有效光照面积为0.07cm2)的光电转换效率为14.0%(短路电流密度22.2mAcm-2,开路电压1.09V,填充因子0.61)。The photoelectric conversion of perovskite solar cells (effective illumination area 0.07cm 2 ) was measured at room temperature using a xenon lamp to simulate sunlight with a light intensity of 95.6mW/cm 2 (sunlight simulator model: Newport 91192A). The efficiency is 14.0% (short circuit current density 22.2mAcm -2 , open circuit voltage 1.09V, fill factor 0.61).
实施例1。Example 1.
制备钛掺杂CH3NH3PbI3的N,N-二甲基甲酰胺溶液,Ti的摩尔浓度为碘化铅摩尔浓度的0.05%,用于制备钙钛矿太阳能电池。The N,N-dimethylformamide solution of Ti-doped CH 3 NH 3 PbI 3 was prepared, and the molar concentration of Ti was 0.05% of that of lead iodide, which was used to prepare perovskite solar cells.
首先, 称取0.461克PbI2 与0.159克CH3NH3I共同溶解于1毫升N,N-二甲基甲酰胺(DMF)中,搅拌混合均匀后滴加0.05M的TiCl4溶液10微升,搅拌均匀后成为钙钛矿溶液备用。First, weigh 0.461 g of PbI 2 and 0.159 g of CH 3 NH 3 I and dissolve them in 1 ml of N,N-dimethylformamide (DMF), stir and mix evenly, and then dropwise add 10 μl of 0.05M TiCl 4 solution , and after stirring evenly, it becomes a perovskite solution for later use.
使用溶胶凝胶法在导电玻璃层上沉积一层致密二氧化钛膜(100纳米);致密二氧化钛膜经450℃处理后再进行四氯化钛处理,烧结后备用。A dense titanium dioxide film (100 nanometers) is deposited on the conductive glass layer by a sol-gel method; the dense titanium dioxide film is treated at 450° C. and then treated with titanium tetrachloride, and is sintered for later use.
使用匀胶机将钙钛矿溶液通过氯苯萃取的工艺沉积在致密二氧化钛膜上。通过精确控制温度在40~100℃烘烤30分钟,使得钙钛矿溶液结晶成为钛掺杂CH3NH3PbI3多晶膜。The perovskite solution was deposited on the dense titania film by a process of chlorobenzene extraction using a spinner. The perovskite solution was crystallized into a titanium-doped CH 3 NH 3 PbI 3 polycrystalline film by precisely controlling the temperature to bake at 40-100 °C for 30 minutes.
将空穴传输材料spiro-MeOTAD的氯苯溶液(浓度为0.6M,加入spiro-MeOTAD摩尔数80 % 的四丁基吡啶(tBP)和spiro-MeOTAD摩尔数30 %的双三氟甲烷磺酰亚胺锂(Li-TFSI))均匀的旋涂在CH3NH3PbI3多晶膜,形成空穴传输材料层。The hole transport material spiro-MeOTAD in chlorobenzene solution (concentration of 0.6M, adding 80% moles of spiro-MeOTAD tetrabutylpyridine (tBP) and 30% moles of spiro-MeOTAD bistrifluoromethanesulfonylidene) Lithium amine (Li-TFSI)) was uniformly spin-coated on the CH 3 NH 3 PbI 3 polycrystalline film to form a hole transport material layer.
使用蒸镀方法,在空穴传输材料层上蒸镀蒸镀银电极层。The silver electrode layer was vapor-deposited on the hole-transporting material layer using the vapor-deposition method.
本实施例中的CH3NH3PbI3多晶膜厚度为600纳米,空穴传输材料层厚度为300纳米,蒸镀银电极层厚度为90纳米。In this embodiment, the thickness of the CH 3 NH 3 PbI 3 polycrystalline film is 600 nanometers, the thickness of the hole transport material layer is 300 nanometers, and the thickness of the vapor-deposited silver electrode layer is 90 nanometers.
本实施例中的钛掺杂CH3NH3PbI3多晶膜厚度为600纳米,空穴传输材料层厚度为300纳米,蒸镀银电极层厚度为90纳米。In this embodiment, the thickness of the titanium-doped CH 3 NH 3 PbI 3 polycrystalline film is 600 nanometers, the thickness of the hole transport material layer is 300 nanometers, and the thickness of the vapor-deposited silver electrode layer is 90 nanometers.
在室温环境,使用氙灯模拟太阳光,光强为95.6mW/cm2(太阳光模拟器型号:Newport 91192A) 条件下,测得修饰过的钙钛矿太阳能电池(有效光照面积为0.07cm2)的光电转换效率为14.8%(短路电流密度19.0mAcm-2,开路电压1.10V,填充因子0.70),比未经改性的太阳能电池效率提高了约6.0%。可以看出,微量Ti掺杂使得短路电流有所降低,但是填充因子极大地提高了。与未掺杂样品相比,参见图4,掺杂0.05%的钛元素有效提高了CH3NH3PbI3多晶膜的光致发光发光强度,说明掺杂样品抑制了晶体中电荷的复合。参见图5,导电玻璃上钛掺杂0.05%的钙钛矿层发光强度减弱则说明掺杂0.05%的钛元素增强了钙钛矿层的载流子传输能力。这是由于引入Ti掺杂对CH3NH3PbI3多晶的形成有影响,造成电流降低。但是微量Ti掺杂在CH3NH3PbI3晶界缺陷处,有效抑制了载流子的复合,同时增加载流子的传输能力,进而极大地提高电池的填充因子。At room temperature, using a xenon lamp to simulate sunlight with a light intensity of 95.6mW/cm 2 (sunlight simulator model: Newport 91192A), the modified perovskite solar cell was measured (effective light area is 0.07cm 2 ) The photoelectric conversion efficiency is 14.8% (short-circuit current density 19.0mAcm -2 , open-circuit voltage 1.10V, fill factor 0.70), which is about 6.0% higher than that of unmodified solar cells. It can be seen that the small amount of Ti doping reduces the short-circuit current, but the fill factor is greatly improved. Compared with the undoped sample, see Fig. 4, 0.05% titanium doping effectively increases the photoluminescence intensity of the CH 3 NH 3 PbI 3 polycrystalline film, indicating that the doped sample inhibits the recombination of charges in the crystal. Referring to Fig. 5, the weakening of the luminescence intensity of the perovskite layer doped with 0.05% titanium on the conductive glass indicates that the 0.05% doped titanium element enhances the carrier transport capability of the perovskite layer. This is because the introduction of Ti doping has an effect on the formation of CH 3 NH 3 PbI 3 polycrystals, resulting in a decrease in current. However, a small amount of Ti is doped at the CH 3 NH 3 PbI 3 grain boundary defect, which effectively inhibits the recombination of carriers and increases the transport capacity of carriers, thereby greatly improving the filling factor of the battery.
实施例2。Example 2.
制备钛掺杂CH3NH3PbI3的N,N-二甲基甲酰胺溶液,Ti的摩尔浓度为碘化铅摩尔浓度的0.1%,用于制备钙钛矿太阳能电池。The N,N-dimethylformamide solution of titanium-doped CH 3 NH 3 PbI 3 was prepared, and the molar concentration of Ti was 0.1% of the molar concentration of lead iodide for the preparation of perovskite solar cells.
首先, 称取0.461克PbI2 与0.159克CH3NH3I共同溶解于1毫升N,N-二甲基甲酰胺(DMF)中,搅拌混合均匀后滴加0.1M的TiCl4溶液10微升,搅拌均匀后成为钙钛矿溶液备用。First, weigh 0.461 g of PbI 2 and 0.159 g of CH 3 NH 3 I and dissolve them in 1 ml of N,N-dimethylformamide (DMF), stir and mix evenly, and then add 10 μl of 0.1 M TiCl 4 solution dropwise , and after stirring evenly, it becomes a perovskite solution for later use.
使用溶胶凝胶法在导电玻璃层上沉积一层致密二氧化钛膜(100纳米);致密二氧化钛膜经450℃处理后再进行四氯化钛处理,烧结后备用。A dense titanium dioxide film (100 nanometers) is deposited on the conductive glass layer by a sol-gel method; the dense titanium dioxide film is treated at 450° C. and then treated with titanium tetrachloride, and is sintered for later use.
使用匀胶机将钙钛矿溶液通过氯苯萃取的工艺沉积在致密二氧化钛膜上。通过精确控制温度在40~100℃烘烤30分钟,使得钙钛矿溶液结晶成为钛掺杂CH3NH3PbI3多晶膜。The perovskite solution was deposited on the dense titania film by a process of chlorobenzene extraction using a spinner. The perovskite solution was crystallized into a titanium-doped CH 3 NH 3 PbI 3 polycrystalline film by precisely controlling the temperature to bake at 40-100 °C for 30 minutes.
将空穴传输材料spiro-MeOTAD的氯苯溶液(浓度为0.6M,加入spiro-MeOTAD摩尔数80 % 的四丁基吡啶(tBP)和spiro-MeOTAD摩尔数30 %的双三氟甲烷磺酰亚胺锂(Li-TFSI))均匀的旋涂在CH3NH3PbI3多晶膜,形成空穴传输材料层。The hole transport material spiro-MeOTAD in chlorobenzene solution (concentration of 0.6M, adding 80% moles of spiro-MeOTAD tetrabutylpyridine (tBP) and 30% moles of spiro-MeOTAD bistrifluoromethanesulfonylidene) Lithium amine (Li-TFSI)) was uniformly spin-coated on the CH 3 NH 3 PbI 3 polycrystalline film to form a hole transport material layer.
使用蒸镀方法,在空穴传输材料层上蒸镀蒸镀银电极层。The silver electrode layer was vapor-deposited on the hole-transporting material layer using the vapor-deposition method.
本实施例中的CH3NH3PbI3多晶膜厚度为600纳米,空穴传输材料层厚度为300纳米,蒸镀银电极层厚度为90纳米。In this embodiment, the thickness of the CH 3 NH 3 PbI 3 polycrystalline film is 600 nanometers, the thickness of the hole transport material layer is 300 nanometers, and the thickness of the vapor-deposited silver electrode layer is 90 nanometers.
本实施例中的钛掺杂CH3NH3PbI3多晶膜厚度为600纳米,空穴传输材料层厚度为300纳米,蒸镀银电极层厚度为90纳米。In this embodiment, the thickness of the titanium-doped CH 3 NH 3 PbI 3 polycrystalline film is 600 nanometers, the thickness of the hole transport material layer is 300 nanometers, and the thickness of the vapor-deposited silver electrode layer is 90 nanometers.
在室温环境,使用氙灯模拟太阳光,光强为95.6mW/cm2(太阳光模拟器型号:Newport 91192A) 条件下,测得修饰过的钙钛矿太阳能电池(有效光照面积为0.07cm2)的光电转换效率为17.4%(短路电流密度22.3mAcm-2,开路电压1.09V,填充因子0.72),比未经改性的太阳能电池效率(14.0%,短路电流密度22.2mAcm-2,开路电压1.09V,填充因子0.61)提高24.3%。可以看到,通过掺杂电池填充因子大幅提高了。与未掺杂样品相比,参见图4,掺杂0.1%的钛元素提高了CH3NH3PbI3多晶膜的发光强度,说明掺杂样品抑制了晶体中电荷的复合。参见图5,导电玻璃层上钛掺杂0.1%钙钛矿层发光强度极大减弱,则说明掺杂0.1%的钛元素有效增强了钙钛矿层的载流子传输能力。0.1% Ti掺杂的钙钛矿性能提高的原因是适量的Ti掺杂在钙钛矿晶界缺陷处,有效抑制了载流子的复合,从而极大地增加载流子的传输能力,进而极大提高电池的填充因子。本实例为最佳实例。At room temperature, using a xenon lamp to simulate sunlight with a light intensity of 95.6mW/cm 2 (sunlight simulator model: Newport 91192A), the modified perovskite solar cell was measured (effective light area is 0.07cm 2 ) The photoelectric conversion efficiency is 17.4% (short-circuit current density 22.3mAcm -2 , open circuit voltage 1.09V, fill factor 0.72), which is higher than that of the unmodified solar cell (14.0%, short-circuit current density 22.2mAcm -2 , open circuit voltage 1.09 V, fill factor 0.61) improved by 24.3%. It can be seen that the fill factor of the cell is greatly improved by doping. Compared with the undoped sample, see Figure 4, the 0.1% titanium doping improves the luminescence intensity of the CH 3 NH 3 PbI 3 polycrystalline film, indicating that the doped sample inhibits the recombination of charges in the crystal. Referring to Figure 5, the luminescence intensity of the titanium-doped 0.1% perovskite layer on the conductive glass layer is greatly weakened, indicating that the 0.1% titanium doping effectively enhances the carrier transport capability of the perovskite layer. The reason for the improved performance of 0.1% Ti-doped perovskite is that an appropriate amount of Ti is doped at the perovskite grain boundary defects, which effectively inhibits the recombination of carriers, thereby greatly increasing the transport capacity of carriers, and thus extremely. Greatly improve the fill factor of the battery. This example is the best example.
参见图1。CH3NH3PbI3晶格的EDS图为图1中a部分,Ti的EDS图为图1中b部分,Pb的EDS图为图1中c部分。b部分和a部分对比,表明Ti元素集中分布在CH3NH3PbI3晶格的晶界处;c部分和a部分对比,表明Pb元素均匀地分布在CH3NH3PbI3晶格内。说明了Ti元素在CH3NH3PbI3晶格中起到钝化缺陷的作用,从而抑制钙钛矿多晶中载流子的复合,有助于器件载流子的传输。See Figure 1. The EDS diagram of CH 3 NH 3 PbI 3 lattice is part a in FIG. 1 , the EDS diagram of Ti is part b in FIG. 1 , and the EDS diagram of Pb is part c in FIG. 1 . The comparison of part b and part a shows that Ti is concentrated at the grain boundary of CH 3 NH 3 PbI 3 lattice; the comparison of part c and a part shows that Pb element is evenly distributed in the CH 3 NH 3 PbI 3 lattice. It is illustrated that Ti element plays a role in passivating defects in the CH 3 NH 3 PbI 3 lattice, thereby inhibiting the recombination of carriers in the perovskite polycrystal and contributing to the transport of carriers in the device.
参见图2。图2中a部分为对比实施例的CH3NH3PbI3多晶膜的SEM图,b部分为本实施例的CH3NH3PbI3多晶膜的SEM图。图2中坐标尺度为1μm。图2说明Ti元素掺杂,钙钛矿晶粒比未掺杂的钙钛矿晶粒稍微变小,从而减弱了钙钛矿多晶晶界处的大缺陷的形成。See Figure 2. Part a in FIG. 2 is an SEM image of the CH 3 NH 3 PbI 3 polycrystalline film of the comparative example, and part b is an SEM image of the CH 3 NH 3 PbI 3 polycrystalline film of the present embodiment. The coordinate scale in Figure 2 is 1 μm. Figure 2 illustrates that doped with Ti, the perovskite grains are slightly smaller than the undoped perovskite grains, thereby attenuating the formation of large defects at the perovskite polygrain boundaries.
实施例3。Example 3.
制备钛掺杂CH3NH3PbI3的N,N-二甲基甲酰胺溶液,Ti的摩尔浓度为碘化铅摩尔浓度的0.2%,用于制备钙钛矿太阳能电池。The N,N-dimethylformamide solution of Ti-doped CH 3 NH 3 PbI 3 was prepared, and the molar concentration of Ti was 0.2% of the molar concentration of lead iodide for the preparation of perovskite solar cells.
首先, 称取0.461克PbI2 与0.159克CH3NH3I共同溶解于1毫升N,N-二甲基甲酰胺(DMF)中,搅拌混合均匀后滴加0.2M的TiCl4溶液10微升,搅拌均匀后成为钙钛矿溶液备用。First, weigh 0.461 g of PbI 2 and 0.159 g of CH 3 NH 3 I and dissolve them in 1 ml of N,N-dimethylformamide (DMF), stir and mix evenly, and then add 10 μl of 0.2 M TiCl 4 solution dropwise , and after stirring evenly, it becomes a perovskite solution for later use.
使用溶胶凝胶法在导电玻璃层上沉积一层致密二氧化钛膜(100纳米);致密二氧化钛膜经450℃处理后再进行四氯化钛处理,烧结后备用。A dense titanium dioxide film (100 nanometers) is deposited on the conductive glass layer by a sol-gel method; the dense titanium dioxide film is treated at 450° C. and then treated with titanium tetrachloride, and is sintered for later use.
使用匀胶机将钙钛矿溶液通过氯苯萃取的工艺沉积在致密二氧化钛膜上。通过精确控制温度在40~100℃烘烤30分钟,使得钙钛矿溶液结晶成为钛掺杂CH3NH3PbI3多晶膜。The perovskite solution was deposited on the dense titania film by a process of chlorobenzene extraction using a spinner. The perovskite solution was crystallized into a titanium-doped CH 3 NH 3 PbI 3 polycrystalline film by precisely controlling the temperature to bake at 40-100 °C for 30 minutes.
将空穴传输材料spiro-MeOTAD的氯苯溶液(浓度为0.6M,加入spiro-MeOTAD摩尔数80 % 的四丁基吡啶(tBP)和spiro-MeOTAD摩尔数30 %的双三氟甲烷磺酰亚胺锂(Li-TFSI))均匀的旋涂在CH3NH3PbI3多晶膜,形成空穴传输材料层。The hole transport material spiro-MeOTAD in chlorobenzene solution (concentration of 0.6M, adding 80% moles of spiro-MeOTAD tetrabutylpyridine (tBP) and 30% moles of spiro-MeOTAD bistrifluoromethanesulfonylidene) Lithium amine (Li-TFSI)) was uniformly spin-coated on the CH 3 NH 3 PbI 3 polycrystalline film to form a hole transport material layer.
使用蒸镀方法,在空穴传输材料层上蒸镀蒸镀银电极层。The silver electrode layer was vapor-deposited on the hole-transporting material layer using the vapor-deposition method.
本实施例中的CH3NH3PbI3多晶膜厚度为600纳米,空穴传输材料层厚度为300纳米,蒸镀银电极层厚度为90纳米。In this embodiment, the thickness of the CH 3 NH 3 PbI 3 polycrystalline film is 600 nanometers, the thickness of the hole transport material layer is 300 nanometers, and the thickness of the vapor-deposited silver electrode layer is 90 nanometers.
本实施例中的钛掺杂CH3NH3PbI3多晶膜厚度为600纳米,空穴传输材料层厚度为300纳米,蒸镀银电极层厚度为90纳米。In this embodiment, the thickness of the titanium-doped CH 3 NH 3 PbI 3 polycrystalline film is 600 nanometers, the thickness of the hole transport material layer is 300 nanometers, and the thickness of the vapor-deposited silver electrode layer is 90 nanometers.
在室温环境,使用氙灯模拟太阳光,光强为95.6mW/cm2(太阳光模拟器型号:Newport 91192A) 条件下,测得修饰过的钙钛矿太阳能电池(有效光照面积为0.07cm2)的光电转换效率为14.1%(,短路电流密度20.1mAcm-2,开路电压1.10V,填充因子0.637),与未经改性的太阳能电池效率(14.0%,短路电流密度22.2mAcm-2,开路电压1.09V,填充因子0.61)差距不大。但是可以看到,通过掺杂填充因子提高了,而短路电流密度却减小了。与未掺杂样品相比,参见图4,钛掺杂0.2%的CH3NH3PbI3多晶膜发光强度减弱。参见图5,导电玻璃层上钛掺杂0.2%的CH3NH3PbI3多晶膜发光强度减弱,但是与掺杂0.1%的样品相比,却增强了。这是由于0.2%Ti仍能在钙钛矿晶界处作用,然而,随着Ti掺杂量的提高影响了CH3NH3PbI3多晶膜的形成,造成杂质缺陷,影响了电池电流的提高。At room temperature, using a xenon lamp to simulate sunlight with a light intensity of 95.6mW/cm 2 (sunlight simulator model: Newport 91192A), the modified perovskite solar cell was measured (effective light area is 0.07cm 2 ) The photoelectric conversion efficiency is 14.1% (, short circuit current density 20.1mAcm -2 , open circuit voltage 1.10V, fill factor 0.637), which is comparable to that of the unmodified solar cell (14.0%, short circuit current density 22.2mAcm -2 , open circuit voltage 1.09V, fill factor 0.61) is not much difference. It can be seen, however, that the fill factor is increased by doping, while the short-circuit current density is decreased. Compared with the undoped sample, see Fig. 4, the luminescence intensity of the 0.2% Ti-doped CH 3 NH 3 PbI 3 polycrystalline film is weakened. Referring to Fig. 5, the luminescence intensity of the CH 3 NH 3 PbI 3 polycrystalline film doped with 0.2% Ti on the conductive glass layer is weakened, but it is enhanced compared with the sample doped with 0.1%. This is because 0.2%Ti can still act at the perovskite grain boundary. However, with the increase of Ti doping amount, it affects the formation of CH 3 NH 3 PbI 3 polycrystalline film, resulting in impurity defects and affecting the battery current. improve.
实施例4。Example 4.
制备钛掺杂CH3NH3PbI3的N,N-二甲基甲酰胺溶液,Ti的摩尔浓度为碘化铅摩尔浓度的0.5%,用于制备钙钛矿太阳能电池。The N,N-dimethylformamide solution of Ti-doped CH 3 NH 3 PbI 3 was prepared, and the molar concentration of Ti was 0.5% of the molar concentration of lead iodide for the preparation of perovskite solar cells.
首先, 称取0.461克PbI2 与0.159克CH3NH3I共同溶解于1毫升N,N-二甲基甲酰胺(DMF)中,搅拌混合均匀后滴加0.5M的TiCl4溶液10微升,搅拌均匀后成为钙钛矿溶液备用。First, weigh 0.461 g of PbI 2 and 0.159 g of CH 3 NH 3 I and dissolve them in 1 ml of N,N-dimethylformamide (DMF), stir and mix evenly, and then add 10 μl of 0.5 M TiCl 4 solution dropwise , and after stirring evenly, it becomes a perovskite solution for later use.
使用溶胶凝胶法在导电玻璃层上沉积一层致密二氧化钛膜(100纳米);致密二氧化钛膜经450℃处理后再进行四氯化钛处理,烧结后备用。A dense titanium dioxide film (100 nanometers) is deposited on the conductive glass layer by a sol-gel method; the dense titanium dioxide film is treated at 450° C. and then treated with titanium tetrachloride, and is sintered for later use.
使用匀胶机将钙钛矿溶液通过氯苯萃取的工艺沉积在致密二氧化钛膜上。通过精确控制温度在40~100℃烘烤30分钟,使得钙钛矿溶液结晶成为钛掺杂CH3NH3PbI3多晶膜。The perovskite solution was deposited on the dense titania film by a process of chlorobenzene extraction using a spinner. The perovskite solution was crystallized into a titanium-doped CH 3 NH 3 PbI 3 polycrystalline film by precisely controlling the temperature to bake at 40-100 °C for 30 minutes.
将空穴传输材料spiro-MeOTAD的氯苯溶液(浓度为0.6M,加入spiro-MeOTAD摩尔数80 % 的四丁基吡啶(tBP)和spiro-MeOTAD摩尔数30 %的双三氟甲烷磺酰亚胺锂(Li-TFSI))均匀的旋涂在CH3NH3PbI3多晶膜,形成空穴传输材料层。The hole transport material spiro-MeOTAD in chlorobenzene solution (concentration of 0.6M, adding 80% moles of spiro-MeOTAD tetrabutylpyridine (tBP) and 30% moles of spiro-MeOTAD bistrifluoromethanesulfonylidene) Lithium amine (Li-TFSI)) was uniformly spin-coated on the CH 3 NH 3 PbI 3 polycrystalline film to form a hole transport material layer.
使用蒸镀方法,在空穴传输材料层上蒸镀蒸镀银电极层。The silver electrode layer was vapor-deposited on the hole-transporting material layer using the vapor-deposition method.
本实施例中的CH3NH3PbI3多晶膜厚度为600纳米,空穴传输材料层厚度为300纳米,蒸镀银电极层厚度为90纳米。In this embodiment, the thickness of the CH 3 NH 3 PbI 3 polycrystalline film is 600 nanometers, the thickness of the hole transport material layer is 300 nanometers, and the thickness of the vapor-deposited silver electrode layer is 90 nanometers.
本实施例中的钛掺杂CH3NH3PbI3多晶膜厚度为600纳米,空穴传输材料层厚度为300纳米,蒸镀银电极层厚度为90纳米。In this embodiment, the thickness of the titanium-doped CH 3 NH 3 PbI 3 polycrystalline film is 600 nanometers, the thickness of the hole transport material layer is 300 nanometers, and the thickness of the vapor-deposited silver electrode layer is 90 nanometers.
在室温环境,使用氙灯模拟太阳光,光强为95.6mW/cm2(太阳光模拟器型号:Newport 91192A) 条件下,测得掺杂过的钙钛矿太阳能电池(有效光照面积为0.07cm2)的光电转换效率为11.7%(短路电流密度20.0mAcm-2,开路电压1.08V,填充因子0.540),比未经改性的太阳能电池效率(14.0%,短路电流密度22.2mAcm-2,开路电压1.09V,填充因子0.61)大幅降低。可以看到,通过掺杂短路电流密度和填充因子大幅减小。与未掺杂样品相比,参见图4,钛掺杂0.5%的CH3NH3PbI3多晶膜发光强度大幅减弱。参见图5,导电玻璃层上钛掺杂0.5%的CH3NH3PbI3多晶膜发光强度有所降低,但比钛掺杂0.1%的钙钛矿却有大幅提高。这是由于过量的Ti掺杂,严重影响了矿钛矿多晶的形成,造成更多的杂质缺陷,从而增加载流子复合的几率,导致短路电流和填充因子大幅降低。At room temperature, using a xenon lamp to simulate sunlight with a light intensity of 95.6mW/cm 2 (sunlight simulator model: Newport 91192A), the doped perovskite solar cells were measured (the effective light area was 0.07cm 2 ) . ) with a photoelectric conversion efficiency of 11.7% (short circuit current density 20.0mAcm -2 , open circuit voltage 1.08V, fill factor 0.540), which is higher than that of the unmodified solar cell (14.0%, short circuit current density 22.2mAcm -2 , open circuit voltage 1.09V, fill factor 0.61) is significantly reduced. It can be seen that the short-circuit current density and fill factor are greatly reduced by doping. Compared with the undoped sample, see Fig. 4, the luminescence intensity of the 0.5% Ti-doped CH 3 NH 3 PbI 3 polycrystalline film is greatly weakened. Referring to Fig. 5, the luminescence intensity of the CH 3 NH 3 PbI 3 polycrystalline film doped with 0.5% Ti on the conductive glass layer is reduced, but it is greatly improved compared with the perovskite doped with 0.1% Ti. This is due to excessive Ti doping, which seriously affects the formation of titanite polycrystals, resulting in more impurity defects, thereby increasing the probability of carrier recombination, resulting in a substantial decrease in short-circuit current and fill factor.
此外,需要说明的是,本说明书中所描述的具体实施例,其零、部件的形状、所取名称等可以不同,本说明书中所描述的以上内容仅仅是对本发明结构所作的举例说明。凡依据本发明专利构思所述的构造、特征及原理所做的等效变化或者简单变化,均包括于本发明专利的保护范围内。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离本发明的结构或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。In addition, it should be noted that the specific embodiments described in this specification may have different shapes and names of parts and components, and the above content described in this specification is only an illustration of the structure of the present invention. All equivalent changes or simple changes made according to the structure, features and principles described in the patent concept of the present invention are included in the protection scope of the patent of the present invention. Those skilled in the art to which the present invention pertains can make various modifications or additions to the described specific embodiments or substitute in similar manners, as long as they do not deviate from the structure of the present invention or go beyond the scope defined by the claims, All should belong to the protection scope of the present invention.
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