Dedoping of Lead Halide Perovskites Incorporating Monovalent Cations

被引:117
作者
Abdi-Jalebi, Mojtaba [1 ]
Pazoki, Meysam [2 ,3 ]
Philippe, Bertrand [4 ]
Dar, M. Ibrahim [5 ]
Alsari, Mejd [1 ]
Sadhanala, Aditya [1 ]
Diyitini, Giorgio [6 ]
Imani, Roghayeh [3 ]
Lilliu, Samuele [7 ,8 ]
Kullgren, Jolla [3 ]
Rensmo, Hakan [4 ]
Gratzel, Michael [5 ]
Friend, Richard H. [1 ]
机构
[1] Univ Cambridge, Dept Phys, Cavendish Lab, JJ Thomson Ave, Cambridge CB3 0HE, England
[2] Uppsala Univ, Dept Engn Sci, Solid State Phys, Box 534, SE-75121 Uppsala, Sweden
[3] Uppsala Univ, Angstrom Lab, Dept Chem, Box 538, SE-75121 Uppsala, Sweden
[4] Uppsala Univ, Dept Phys & Astron, Mol & Condensed Matter Phys, Box 516, SE-75120 Uppsala, Sweden
[5] Ecole Polytech Fed Lausanne, Inst Chem Sci & Engn, Lab Photon & Interfaces, CH-1015 Lausanne, Switzerland
[6] Univ Cambridge, Dept Mat Sci & Met, 27 Charles Babbage Rd, Cambridge CB3 0FS, England
[7] Univ Sheffield, Dept Phys & Astron, Sheffield S3 7RH, S Yorkshire, England
[8] UAE Ctr Crystallog, Dubai, U Arab Emirates
基金
英国工程与自然科学研究理事会; 欧盟地平线“2020”; 瑞典研究理事会;
关键词
monovalent cations; dedoped perovskite thin films; enhanced optoelectronic quality; substitutional doping; interstitial doping; SOLAR-CELL; HYBRID PEROVSKITE; PERFORMANCE; CH3NH3PBI3; LENGTHS; SEGREGATION; INTERFACE; LAYERS; FILMS;
D O I
10.1021/acsnano.8b03586
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report significant improvements in the optoelectronic properties of lead halide perovskites with the addition of monovalent ions with ionic radii close to Pb2+. We investigate the chemical distribution and electronic structure of solution processed CH3NH3PbI3 perovskite structures containing Na+, Cu+, and Ag+, which are lower valence metal ions than Pb2+ but have similar ionic radii. Synchrotron X-ray diffraction reveals a pronounced shift in the main perovskite peaks for the monovalent cation-based films, suggesting incorporation of these cations into the perovskite lattice as well as a preferential crystal growth in Ag+ containing perovskite structures. Furthermore, the synchrotron X-ray photoelectron measurements show a significant change in the valence band position for Cu- and Ag-doped films, although the perovskite bandgap remains the same, indicating a shift in the Fermi level position toward the middle of the bandgap. Such a shift infers that incorporation of these monovalent cations dedope the n-type perovskite films when formed without added cations. This dedoping effect leads to cleaner bandgaps as reflected by the lower energetic disorder in the monovalent cation-doped perovskite thin films as compared to pristine films. We also find that in contrast to Ag+ and Cu+, Na+ locates mainly at the grain boundaries and surfaces. Our theoretical calculations confirm the observed shifts in X-ray diffraction peaks and Fermi level as well as absence of intrabandgap states upon energetically favorable doping of perovskite lattice by the monovalent cations. We also model a significant change in the local structure, chemical bonding of metal-halide, and the electronic structure in the doped perovskites. In summary, our work highlights the local chemistry and influence of monovalent cation dopants on crystallization and the electronic structure in the doped perovskite thin films.
引用
收藏
页码:7301 / 7311
页数:11
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