Ligand Mediated Synthesis of Shape Controlled Cesium Lead Halide Perovskite Nanocrystals via Reprecipitation Process at Room Temperature

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Supporting Information for: Ligand Mediated Synthesis of Shape Controlled Cesium Lead Halide Perovskite Nanocrystals via Reprecipitation Process at Room Temperature Shibin Sun, Dan Yuan, Yuan Xu, Aifei Wang, and Zhengtao Deng* Department of Biomedical Engineering, College of Engineering and Applied Sciences, Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, Jiangsu, 210093, P. R. China *Address correspondence to: dengz@nju.edu.cn S1

Figure S1. Additional HRTEM image of CsPbBr3 spherical quantum dots synthesized using hexanoic acid and octylamine as ligands at room temperature. S2

Figure S2. Transmission electron microscopy image (A) and its corresponding size distribution histograph (B) of CsPbBr3 spherical quantum dots using hexanoic acid and octylamine as ligands grown at 40 C. S3

Equation y = a + b*x 6 5 Value Standard Error Intercept -11.9802 6.73125 Slope 0.03249 0.01401 Diameter (nm) 4 3 2 450 460 470 480 490 500 510 520 PL Emission Peak (nm) Figure S3. The plot for the mean diameter (with error bars) based on the transmission electron microscopy images versus the PL emission peak position (457, 465, 474, 505, 510, 515 nm) of the CsPbBr3 quantum dots synthesized at 20, 0, 20, 25, 40, 60 o C, respectively. Note that the experimental diameter values, D(x), measured from TEM images shown in Figure S4 can be fitted into a linear function of the PL emission peak position (x) of the CsPbBr3 quantum dots. The fitting results are as follows: 11.98 0.0325 S4

Figure S4. Transmission electron microscopy image (A) and its corresponding size distribution histograph (B) of CsPbI3 spherical quantum dots synthesized using hexanoic acid and octylamine as ligands at 25 o C. S5

Figure S5. XPS spectra corresponding to CsPbBr3 spherical quantum dots synthesized using hexanoic acid and octylamine as ligands at room temperature. (A) Survey x ray photoelectron spectrum and high resolution x ray photoelectron spectra of (B) Cs 3d, (C) Pb 4f, and (D) Br 3d. S6

Figure S6. Additional TEM image of CsPbBr3 nanocubes synthesized using oleic acid and dodec ylamine as ligands at room temperature. S7

Figure S7. (A D) additional PLE spectra of CsPbBr 3 nanocubes colloidal solutions with different dilutions (original, 10 time, 50 times, and 100 time dilutions) synthesized using oleic acid and dodecylamine as ligands at room temperature. (E, F) Graphical depictions of the pseudo colored PL intensity measured as a function of excitation wavelength with nanocubes colloidal solution (original and 100 time dilution). S8

Figure S8. Additional TEM image of CsPbBr 3 nanorods synthesized using acetate acid and dodecylamine as ligands at room temperature. S9

Figure S9. Additional HRTEM image of CsPbBr 3 nanorods synthesized using acetate acid and dodecylamine as ligands at room temperature. S10

Figure S10. Additional TEM (A), HRTEM (B) images and its FFTs (C) of the few unit cell thick CsPbBr3 nanoplatelets synthesized using oleic acid and octylamine as ligands at room tempera ture. Figure S11. Additional HRTEM image of the flat lying few unit cell thick CsPbBr3 nanoplatelets synthesized using oleic acid and octylamine as ligands at room temperature. S11

Figure S12. Additional HRTEM image of the stacked few unit cell thick CsPbBr 3 nanoplatelets synthesized using oleic acid and octylamine as ligands at room temperature. S12

Quantum Dots C-H bend Nanocubes C-H stretch C-H stretch O-H stretch C=O Stretch Nanorods C-O bend N-H Stretches C-N Stretches C-H stretch N-H bend Nanoplatelets N-H bend C-H stretch N-H Stretch 4000 3000 2000 1000 Wavenumber (cm -1 ) Figure S13. Fourier transform infrared (FTIR) spectrum of the product corresponding to CsPbBr3 spherical Quantum Dots (Red Line), Nanocubes (Blue Line), Nanorods (Black Line), and Nanoplatelets (Green Line) synthesized at room temperature, respectively. S13

Table S1. The summary of geometric shapes and sizes analysis from TEM and optical properties from PL characterization of the CsPbBr3 nanocrystals (NC1 NC9). The synthetic temperatures and the ligands are also listed. Sample # Ligands Synthetic temperature ( o C) Geometric Shape Size (nm) PL emission peak (nm) PL quantum yield (%) PL Decay Lifetime (ns) NC1 hexanoic acid and octylamine -20 Spherical quantum dots 3.1±0.6 457 40.3 5.91 NC2 hexanoic acid and octylamine 0 Spherical Quantum dots 3.5±0.7 465 51.7 8.59 NC3 hexanoic acid and octylamine 20 Spherical Quantum dots 4.1±0.7 474 69.5 10.8 NC4 hexanoic acid and octylamine 25 Spherical Quantum dots 4.3±0.8 505 81.1 11.5 NC5 hexanoic acid and octylamine 40 Spherical Quantum dots 4.5±0.9 510 83.2 12.7 NC6 hexanoic acid and octylamine 60 Spherical Quantum dots 5.0±1.1 515 65.6 19.9 NC7 oleic acid and dodecylamine 25 Nanocubes 9.0±1.0 (edge length) 514 67.9 24.2 NC8 acetate acid and dodecylamine 25 Nanorods 200 (length) 10 (diameter) 515 13.2 50.5 NC9 oleic acid and octylamine 25 Nanoplatelets 100 (edge length) 5.2±1.3 (thickness) 510 0.7 954 S14