制备方法对钙钛矿薄膜结构及形貌的影响
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摘要
采用液相连续沉积法制备了有机/无机杂化钙钛矿(CH_3NH_3PbI_3,MAPbI_3)光吸收层,并研究了不同薄膜形貌、晶体结构和光吸收能力对钙钛矿太阳能电池性能的影响。结果表明:制备工艺对吸光层形貌和器件光电性能产生很大的影响。相对于分步浸渍法,分步旋涂法(分步旋涂无机相碘化铅PbI_2和有机相甲胺碘CH_3NH_3I前驱液)和气体辅助修复法(新制初始MAPbI_3薄膜在室温下置于甲胺气氛中)能有效改善薄膜形貌和平整度,获得覆盖完全的均匀钙钛矿吸光层。同时,进一步分析了初始MAPbI_3膜的形貌对气体修复法制备全覆盖平整钙钛矿薄膜的影响,发现初始钙钛矿膜的形貌对最终修复后的膜层形貌没有影响,这可能是因为不同初始MAPbI_3膜经甲胺气体处理后均形成一种"甲胺铅化碘-甲胺"(MAPbI_3·MA)的液态中间相,再经退火处理后均获得平整、致密的钙钛矿膜层,极大地提高了MAPbI_3的结晶度和薄膜均匀性,从而提高活性层的吸光率、光电流和电池效率。
We studied the influence of surface morphology, crystal structure and optical absorption of the perovskite(CH_3NH_3PbI_3, MAPbI_3) films on the performance of the organic-inorganic hybrid perovskite solar cells which prepared by various sequential deposition technology. It is shown that deposition conditions have significant impacts on the morphologies of the MAPbI_3 adsorbent layers as well as the performance of the solar cells. Compared with the sequential MAI-soaking method, other deposition methods can effectively improve the morphology by increasing the flatness and full surface coverage. Meanwhile, the mechanism involved in the preparation of smooth, full-coverage MAPbI_3 films using the post-treatment method at room temperature(RT) was studied further. The results demonstrate that the resulting smooth MAPbI_3 thin films are virtually independent on the morphology of the raw perovskite films using various deposition methods, due to the formation and spreading of an intermediate MAPbI_3·MA liquid phase. These processes improved the morphology and crystallization of perovskite resulting in a significant enhancement in light absorption, photocurrent and the performance of solar cell devices.
We studied the influence of surface morphology, crystal structure and optical absorption of the perovskite(CH_3NH_3PbI_3, MAPbI_3) films on the performance of the organic-inorganic hybrid perovskite solar cells which prepared by various sequential deposition technology. It is shown that deposition conditions have significant impacts on the morphologies of the MAPbI_3 adsorbent layers as well as the performance of the solar cells. Compared with the sequential MAI-soaking method, other deposition methods can effectively improve the morphology by increasing the flatness and full surface coverage. Meanwhile, the mechanism involved in the preparation of smooth, full-coverage MAPbI_3 films using the post-treatment method at room temperature(RT) was studied further. The results demonstrate that the resulting smooth MAPbI_3 thin films are virtually independent on the morphology of the raw perovskite films using various deposition methods, due to the formation and spreading of an intermediate MAPbI_3·MA liquid phase. These processes improved the morphology and crystallization of perovskite resulting in a significant enhancement in light absorption, photocurrent and the performance of solar cell devices.
引文
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[2]GREEN M A,HO-BAILLIE A,SNAITH H J.The emergence of perovskite solar cells[J].Nature Photonics,2014,8(7):506-514.
[3]YANG W C,YAO Y,WU C Q.Origin of the high open circuit voltage in planar heterojunction perovskite solar cells:role of the reduced bimolecular recombination[J].Journal of Applied Physics,2015,117(9):095502.
[4]GALKOWSKI K,MITIOGLU A,MIYATA A,et al.Determination of the exciton binding energy and effective masses for methylammonium and formamidinium lead tri-halide perovskite semiconductors[J].Energy&Environmental Science,2016,9(3):962-970.
[5]PAZOS-OUTON L M,SZUMILO M,LAMBOLL R.Photon recycling in lead iodide perovskite solar cells[J].Science,2016,351(6280):1430-1433.
[6]KOJIMA A,TESHIMA K,SHIRAI Y,et al.Organometal halide perovskites as visible-light sensitizers for photovoltaic cells[J].Journal of the American Chemical Society,2009,131(17):6050-6051.
[7]NREL,Best Research-Cell Efficiencies.http://www.nrel.gov.accessed:November 2016.
[8]EPERON G E,BURLAKOV V M,DOCAMPO P,et al.Morphological control for high performance,solution-processed planar heterojunction perovskite solar cells[J].Advanced Functional Materials,2014,24(1):151-157.
[9]DUALEH A,TETREAULT N,MOEHLT,et al.Effect of annealing temperature on film morphology of organic-inorganic hybrid pervoskite solid-state solar cells[J].Advanced Functional Materials,2014,24(21):3250-3258.
[10]XIAO Z G,DONG Q F,BI C,et al.Solvent annealing of perovskite-induced crystal growth for photovoltaic-device efficiency enhancement[J].Advanced Materials,2014,26(37):6503-6509.
[11]CHEN B,YANG M J,PRIYA S,et al.Origin of J-V hysteresis in perovskite solar cells[J].Journal of Physical Chemistry Letters,2016,7(5):905-917.
[12]YUAN Y B,HUANG J S.Ion migration in organometal trihalide perovskite and its impact on photovoltaic efficiency and stability[J].Accounts of Chemical Research,2016,49(2):286-293.
[13]LI W Z,FAN J D,LI J W,et al.Controllable grain morphology of perovskite absorber film by molecular self-assembly toward efficient solar cell exceeding 17%[J].Journal of American Chemical Society,2015,137(32):10399-10405.
[14]ZUO L J,DONG S Q,MARCO N,et al.Morphology evolution of high efficiency perovskite solar cells via vapor induced intermediate phases[J].Journal of American Chemical Society,2016,138(48):15710-15716.
[15]BI D Q,YIC Y,LUO J S,et al.Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%[J].Nature Energy,2016,1:16142.
[16]ZHOU Y Y,GAME O S,PANG S P,et al.Microstructures of organometal trihalide perovskites for solar cells:their evolution from solutions and characterization[J].Journal of Physics Chemistry Letters,2015,6(23):4827-4839.
[17]ZHANG T Y,YANG M J,ZHAO Y X,et al.Controllable sequential deposition of planar CH3NH3Pb I3 perovskite films via adjustable volume expansion[J].Nano Letters,2015,15(6):3959-3963.
[18]LI L,CHEN Y H,LIU Z H,et al.The additive coordination effect on hybrids perovskite crystallization and high-performance solar cell[J].Advanced Materials,2016,28(44):9862-9868.
[19]YING C,SHI C,WU N,et al.A two-layer structured Pb I2 thin film for efficient planar perovskite solar cells[J].Nanoscale,2015,7(28):12092-12095.
[20]CHENG N,LIU P,BAI S H,et al.Enhanced performance in hole transport material free perovskite solar cells via morphology control of Pb I2 film by solvent treatment[J].Journal of Power Sources,2016,319:111-115.
[21]LV M H,DONG X,FANG X,et al.A promising alternative solvent of perovskite to induce rapid crystallization for high-efficiency photovoltaic devices[J].RSC Advances,2015,5:20521-20529.
[22]ZHAO Y X,ZHU K.Three-step sequential solution deposition of Pb I2-free CH3NH3Pb I3 perovskite[J].Journal of Materials Chemistry A,2015,3(17):9086-9091.