Supporting Information. Rubidium Doping for Enhanced Performance of Highly Efficient Formamidinium-Based Perovskite Light-Emitting Diodes
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1 Supporting Information Rubidium Doping for Enhanced Performance of Highly Efficient Formamidinium-Based Perovskite Light-Emitting Diodes Yifei Shi, Jun Xi,, Ting Lei, Fang Yuan, Jinfei Dai, Chenxin Ran, Hua Dong, Bo Jiao and Xun Hou and Zhaoxin Wu * Key Laboratory of Photonics Technology for Information, Key Laboratory for Physical Electronics and Devices of the Ministry of Education, School of Electronic and Information Engineering, Xi an Jiaotong University, Xi an , China Global Frontier Center for Multiscale Energy Systems, Seoul National University, Seoul , Korea Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan , China *Corresponding author. zhaoxinwu@mail.xjtu.edu.cn Keywords: doping engineering, perovskite, light-emitting diodes, rubidium, formamidinium S-1
2 Figure S1. Tolerance factor of APbBr 3 perovskite with alkali metals (Li, Na, K, Rb and Cs) and MA + or FA + (the inset shows detailed ionic radii). Generally, the tolerance factor of perovskite is in the range from 0.8 to 1.0 can form a stable photoactive perovskite phase. Rb just misses a little bit this range, which makes Rb insert the perovskite lattice be a possible. S-2
3 Figure S2. (a)the top-viewed SEM image of FAPbBr 3 film with 14% Rb incorporation, (b) energy dispersive spectroscopy (EDS)of spot 1 selected from the white flake area of (a), (c)eds spectra of spot 2 selected from the uniform perovskite area of (a). S-3
4 Figure S3. Energy dispersive spectroscopy (EDS) maps of (a-f) FAPbBr 3 film with 7% Rb incorporation and (g-k) pure FAPbBr 3 film. S-4
5 Figure S4. Photos of FAPbBr 3 films with different Rb incorporation proportion in ambient (up) and under 405nm ultraviolet lamp (down). S-5
6 Figure S5. XPS spectra of pure FAPbBr 3 film (red lines) and FAPbBr 3 film with 7% Rb incorporation(blue lines). S-6
7 Figure S6. (a)histograms of peak CEs measured from 40 devices with the devices based on FAPbBr 3 film incorporated 7% Rb. (b) The lifetime of devices based on pure FAPbBr 3 and 7% Rb doping FAPbBr 3 films, respectively. S-7
8 Figure S7. Power-dependent photoluminescence spectra of (a) FAPbBr 3 with 7%Rb sample and (b) pure FAPbBr 3 sample. S-8
9 Figure S8. PL intensity as a function of photon-generated exciton density at the low pump energy. The experimental data can be well-fitted (R 2 = 0.98 for blue line and 0.97 for red line) with the following equation for two types of trapping states. Auger recombination is negligible and trap-assisted recombination is much slower than bimolecular radiative recombination at low pump fluence, the initial photo generated carrier density n c (0) can be described as i n c (0) = n tp i (0)(1 e ( a iτ 0 I PL /k) ) + I PL /k i Where n tp (0) is the trap states density and a i is the product of the trapping cross section and the carrier velocity. The k is constant and τ 0 is PL lifetime. The first term of equation represents the two types of trap states assisted pathways, while the second term represents carriers decayed through radiative recombination. Fitting the experimental results with this b equation yields a two types of trap states density, bulk trap density n tp and surface trap density n s b tp. For pure FAPbBr 3 film, n tp is about ~ cm -3 s, n tp is about ~ cm -3 b,while in comparison, for FAPbBr 3 film incorporated with 7% Rb, n tp is about ~ cm -3 s, n tp is about ~ cm -3. S-9
10 Table S1. Summary of PLQY and XRD peak position (~14ᴼ) values of different Rb content FAPbBr 3 films. Rb content PLQY (%) XRD peak position (degrees) % % 6.85% % 15.41% % 21.42% Table S2. The summary of recent researches on FAPbBr 3 -based LEDs. Date Form Device architecture Max.EQE Max.CE a) Max.Lu b) Ref [%] [cd/a] [cd/m 2 ] 2017 Thin film ITO/PEDOT/Pe/TPBi/LiF/Al This work 2017 Thin film ITO/ZnO/Pe/Ploy-TPD/MoO 3 /Al NPs ITO/PEDOT/TFB/Pe(Cs doping)/tpbi /CsCO 3 /Al 2017 NPs ITO/PEDOT:PSS/Pe+PMMA/3TP YMB/LiF/Al 2016 NPs ITO/PEDOT/Pe/TPBI&B3PYMPM /CsCO 3 /Al NR NPs ITO/PEIE/Pe/TPBi/LiF/Al ~278 a)ce:current efficiency; b)lu:luminance;. NR-No reported REFERENCES (1). Meng, L.; Yao, E. P.; Hong, Z. R.; Chen, H. J.; Sun, P. Y.; Yang, Z. L.; Li, G.; Yang, Y., Pure Formamidinium-Based Perovskite Light-Emitting Diodes with High Efficiency and Low Driving Voltage. Adv. Mater. 2017, 29, (2). Zhang, X. L.; Liu, H.; Wang, W. G.; Zhang, J. B.; Xu, B.; Karen, K. L.; Zheng, Y. J.; Liu, S.; Chen, S. M.; Wang, K.; Sun, X. W., Hybrid Perovskite Light-Emitting Diodes Based on Perovskite Nanocrystals with Organic-Inorganic Mixed Cations. Adv. Mater. 2017, 29, (3). Kumar, S.; Jagielski, J.; Kallikounis, N.; Kim, Y. H.; Wolf, C.; Jenny, F.; Tian, T.; Hofer, C. J.; Chiu, Y. C.; Stark, W. J.; Lee, T. W.; Shih, C. J., Ultrapure Green Light-Emitting Diodes Using Two-Dimensional Formamidinium Perovskites: Achieving Recommendation 2020 Color S-10
11 Coordinates. Nano Lett. 2017, 17, (4). Perumal, A.; Shendre, S.; Li, M.; Tay, Y. K.; Sharma, V. K.; Chen, S.; Wei, Z.; Liu, Q.; Gao, Y.; Buenconsejo, P. J.; Tan, S. T.; Gan, C. L.; Xiong, Q.; Sum, T. C.; Demir, H. V., High brightness formamidinium lead bromide perovskite nanocrystal light emitting devices. Sci. Rep. 2016, 6, (5). Kim, Y. H.; Lee, G. H.; Kim, Y. T.; Wolf, C.; Yun, H. J.; Kwon, W.; Park, C. G.; Lee, T. W., High efficiency perovskite light-emitting diodes of ligand-engineered colloidal formamidinium lead bromide nanoparticles. Nano Energy 2017, 38, S-11
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