Supporting Information
Supporting Information
Ultrabroad Photoluminescence and Electroluminescence at New Wavelengths from Doped Organometal Halide Perovskites Yang Zhou,† Zi-Jun Yong,† Kai-Cheng Zhang,† Bo-Mei Liu,† Zhao-Wei Wang,† Jing-Shan Hou,‡ Yong-Zheng Fang, ‡ Yi Zhou,† Hong-Tao Sun,*, † and Bo Song*,† †
College of Chemistry, Chemical Engineering and Materials Science, Soochow
University, Suzhou 215123, China ‡
School of Materials Science and Engineering, Shanghai Institute of Technology,
Shanghai 201418, China
Corresponding Author *Email:[email protected] (H.-T. Sun); [email protected] (B. Song)
1
Experimental Section Materials : Unless specified otherwise, all materials were purchased from either Alfa Aesar or Aladdin and used as received. CH3NH3I was purchased from Xi’an Polymer Light Technology Corp..
Fabrication of Bi-doped MAPbI3, MAPbBr3 and MASnI3 Films:
The perovskite
precursor solution was prepared by mixing MAI and PbI2 in a 1:1 molar ratio in DMF, which was stirred overnight at 60 ºC in a nitrogen-filled glovebox (0.1 ppm H2O; 0.1 ppm O2). The additional BiI3 in DMF was added to the mixture to achieve desired ratios at room temperature, finally obtaining a 40 wt% solution that was then filtered and spin-coated at 3000 rpm for 45 s to give a film. The films were thermally treated at 100 ºC for different duration of 1~10 min. Bi-doped MASnI3 and MAPbBr3 was prepared by the same process as above, by using respective precursors (i.e., MAI, SnI2 and BiI3 for MASnI3, MABr, PbBr2 and BiBr3 for MAPbBr3).
Fabrication of Bi-doped MAPbI2.4Br0.6: The MAPbI2.4Br0.6 perovskite precursor solution was prepared by mixing MAI, MABr, PbI2 and PbBr2 in a 0.8:0.2:0.8:0.2 molar ratio in DMF. The precursor solution were stirred overnight at 60 ºC in a nitrogen-filled glovebox (0.1 ppm H2O; 0.1 ppm O2). The additional BiI3 in DMF were added to the MAPbI2.4Br0.6 precursor solutions to achieve desired ratios at room temperature, finally obtaining a 40 wt% solution that was then filtered and
2
spin-coated at 3000 rpm for 45 s to give a film. The films were thermally treated at 100 ºC for 1 min.
Fabrication of Bi-doped MAPbBr2.4Cl0.6: The synthesis of Bi-doped MAPbBr2.4Cl0.6 was performed via a modified method reported previously for the synthesis of MAPbBr2.4Cl0.6.[1] In brief, MAPbBr3 precursor solution was synthesized by mixing MABr and Pb(CH3COO)2·3H2O in a 3:1:0.0001 molar stoichiometric ratio in DMF to get a 0.8 M solution. The MAPbCl3 precursor solution was synthesized by mixing MACl and Pb(CH3COO)2·3H2O in a 3:1:0.0001 molar stoichiometric ratio in a mixed solvent comprising DMSO and DMF in the ratio of 40:60 (v/v) to get a 0.8 M solution. The MAPbBr2.4Cl0.6 precursor solution was prepared by mixing the above-mentioned MAPbBr3 and MAPbCl3 precursor solutions in a molar ratio of 4:1, which were then spin-coated on the glass substrates and finally thermally treated at 100 ºC for 5 min.
Film Characterization: XRD patterns were carried out at room temperature using a Bruker D2 PHASER (λ = 1.54178 Å) or a D8 ADVANCE diffractometer with Cu Kα radiation (λ = 1.54056 Å). The absorption spectra were taken by a double-beam UV-Vis-NIR spectrophotometer (Cary 5000, Agilent) equipped with an integrated sphere. The absorption intensities were estimated by the Kubelka–Munk analysis of the diffuse reflectance spectra of the films. The XPS and UPS measurements were recorded on a Kratos AXIS UltraDLD ultrahigh vacuum surface analysis system, consisting of a multiport carousel chamber (base pressure
Ultrabroad Photoluminescence and Electroluminescence at New Wavelengths from Doped Organometal Halide Perovskites Yang Zhou,† Zi-Jun Yong,† Kai-Cheng Zhang,† Bo-Mei Liu,† Zhao-Wei Wang,† Jing-Shan Hou,‡ Yong-Zheng Fang, ‡ Yi Zhou,† Hong-Tao Sun,*, † and Bo Song*,† †
College of Chemistry, Chemical Engineering and Materials Science, Soochow
University, Suzhou 215123, China ‡
School of Materials Science and Engineering, Shanghai Institute of Technology,
Shanghai 201418, China
Corresponding Author *Email:[email protected] (H.-T. Sun); [email protected] (B. Song)
1
Experimental Section Materials : Unless specified otherwise, all materials were purchased from either Alfa Aesar or Aladdin and used as received. CH3NH3I was purchased from Xi’an Polymer Light Technology Corp..
Fabrication of Bi-doped MAPbI3, MAPbBr3 and MASnI3 Films:
The perovskite
precursor solution was prepared by mixing MAI and PbI2 in a 1:1 molar ratio in DMF, which was stirred overnight at 60 ºC in a nitrogen-filled glovebox (0.1 ppm H2O; 0.1 ppm O2). The additional BiI3 in DMF was added to the mixture to achieve desired ratios at room temperature, finally obtaining a 40 wt% solution that was then filtered and spin-coated at 3000 rpm for 45 s to give a film. The films were thermally treated at 100 ºC for different duration of 1~10 min. Bi-doped MASnI3 and MAPbBr3 was prepared by the same process as above, by using respective precursors (i.e., MAI, SnI2 and BiI3 for MASnI3, MABr, PbBr2 and BiBr3 for MAPbBr3).
Fabrication of Bi-doped MAPbI2.4Br0.6: The MAPbI2.4Br0.6 perovskite precursor solution was prepared by mixing MAI, MABr, PbI2 and PbBr2 in a 0.8:0.2:0.8:0.2 molar ratio in DMF. The precursor solution were stirred overnight at 60 ºC in a nitrogen-filled glovebox (0.1 ppm H2O; 0.1 ppm O2). The additional BiI3 in DMF were added to the MAPbI2.4Br0.6 precursor solutions to achieve desired ratios at room temperature, finally obtaining a 40 wt% solution that was then filtered and
2
spin-coated at 3000 rpm for 45 s to give a film. The films were thermally treated at 100 ºC for 1 min.
Fabrication of Bi-doped MAPbBr2.4Cl0.6: The synthesis of Bi-doped MAPbBr2.4Cl0.6 was performed via a modified method reported previously for the synthesis of MAPbBr2.4Cl0.6.[1] In brief, MAPbBr3 precursor solution was synthesized by mixing MABr and Pb(CH3COO)2·3H2O in a 3:1:0.0001 molar stoichiometric ratio in DMF to get a 0.8 M solution. The MAPbCl3 precursor solution was synthesized by mixing MACl and Pb(CH3COO)2·3H2O in a 3:1:0.0001 molar stoichiometric ratio in a mixed solvent comprising DMSO and DMF in the ratio of 40:60 (v/v) to get a 0.8 M solution. The MAPbBr2.4Cl0.6 precursor solution was prepared by mixing the above-mentioned MAPbBr3 and MAPbCl3 precursor solutions in a molar ratio of 4:1, which were then spin-coated on the glass substrates and finally thermally treated at 100 ºC for 5 min.
Film Characterization: XRD patterns were carried out at room temperature using a Bruker D2 PHASER (λ = 1.54178 Å) or a D8 ADVANCE diffractometer with Cu Kα radiation (λ = 1.54056 Å). The absorption spectra were taken by a double-beam UV-Vis-NIR spectrophotometer (Cary 5000, Agilent) equipped with an integrated sphere. The absorption intensities were estimated by the Kubelka–Munk analysis of the diffuse reflectance spectra of the films. The XPS and UPS measurements were recorded on a Kratos AXIS UltraDLD ultrahigh vacuum surface analysis system, consisting of a multiport carousel chamber (base pressure
