Highly Emissive and Color-tunable Perovskite Crosslinkers for

Transcription

1 Highly Emissive and Color-tunable Perovskite Crosslinkers for Luminescent Polymer Networks Yumeng Xin 1, Wei Shen, 2 Zhengtao Deng, 2 Jiuyang Zhang 1 * 1 School of Chemistry and Chemical Engineering, Southeast University, Nanjing, , PR China; Jiangsu Hi-Tech Key Laboratory for Biomedical Research, , Nanjing, PR China 2 Department of Biomedical Engineering, College of Engineering and Applied Sciences, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing, Jiangsu , PR China S-1

2 Materials and Instrumentation Lead bromide (PbBr 2 ) (99%), butyl methacrylate (BMA) (99%) and methylamine solution (33 % in methyl alcohol) were purchased from Aladdin, hydrobromic acid (48 % in water) was purchased from Maya Reagent, 2-aminoethyl methacrylate hydrochloride (90%) was purchased from 9 Ding Chemistry, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) ( 98%) was purchased from Shanghai DiBai chemicals, methyl methacrylate (MMA) (99%) and butylacrylate (BA) (99%) were purchased from Macklin, dimethyl formamide (DMF) was purchased from Sinopharm Chemical Reagent, and all the liquid reagents purified through alumina oxide columns before using. Blue LED (454 nm, 300 ma, 22 ~ 38V, 10 W) was purchased from Xiaodan Company. Photoluminescence (PL) spectra of emissive bulk monomer and MAPbClxBr3-x-crosslinked polymer networks were collected with a FluoroMax-4 spectrometer (Horiba, Japan) at room temperature and the electrochemluminescence (ECL) emission spectra were obtained at the same spectrometer by additional coupling with a CHI400E electrochemical workstation (CHI, USA). Ultraviolet and visible absorption (UV-vis) spectra were recorded with from Cary 100 (Agilent, Singapore) with a diffuse reflectance accessory and BaSO4 was used as the reference sample (100% reflectance). Transmission electron microscopy (TEM) was performed on FEI Tecnai G2 T20. Scanning electron microscope (SEM) images were recorded by FEI Nova Nano SEM 450. The lifetimes of PL were detected by Nikon Ni-U Microfluoresce Lifetime system (confotec MR200, SOL, Belarus) with a 374 nm S-2

3 picoseconds lasers. X-ray photoelectron spectroscopy (XPS) was performed using Thermo ESCALAB 250XI (American Thermo Fisher Scientific). X-ray diffraction (XRD) was measured with Ultima IV. Emission spectrum and CIE diagram were measured on THEORLABS LED-Driver-LEDE1B. Synthesis Synthesis of methylammonium bromide (CH 3 NH 3 Br). 24 ml of methylamine solution (33 % in methyl alcohol) was diluted with 100 ml of absolute methyl alcohol in a 250 ml round-bottom flask. Under constant stirring, 8 ml hydrobromic acid (48 % in water) was added to the flask. After stirring for 2 h at room temperature, the solvent was evaporated. The obtained white solid was washed with dry diethyl ether and dried under vacuum (60 ºC, 6 h) for future use. Synthesis of methylammonium lead halide (MAPbCl x Br 3-x ) crosslinkers in bulk BMA solution. 2-aminoethyl methacrylate hydrochloride (0.043 mol/l), methylammonium bromide (0.089 mol/l) and lead bromide (0.027 mol/l) were prepared in DMF. Then, precursor solution were prepared by mixing 2-aminoethyl methacrylate hydrochloride, methylammonium bromide and lead bromide in DMF (MABr : AMHCl : PbBr 2 molar ratio were showed in Table S1) and stirred for 10 minutes. These precursor solutions (50 μl) were dropped into BMA solution (1 ml) and stirred for 1 minute. Strong color emission emerged immediately after the injection. All of experimental operations were performed at room temperature. Fabrication of MAPbCl x Br 3-x -crosslinked PBMA networks by UV-polymerization. MAPbCl x Br 3-x crosslinkers/bma solution (0.5 ml) with TPO (3.29 mg) were placed S-3

4 into a flat-bottomed glass tube with a diameter of 20.0 mm and filled with nitrogen. The tube was placed under the UV light (wavelength: 365 nm) for 12 h. After being cooled to room temperature, disk samples were obtained. Synthesis of MAPbCl 0.60 Br 2.40 crosslinkers powder from bulk BMA solution for FTIR measurement or other using. 2-aminoethyl methacrylate hydrochloride (0.043 mol/l), methylammonium bromide (0.089 mol/l) and lead bromide (0.027 mol/l) were prepared in DMF. The precursor solution was prepared by mixing 2-aminoethyl methacrylate hydrochloride, methylammonium bromide and lead bromide in DMF (MABr: AMHCl: PbBr 2 molar ratio of 1.22:0.80:1) and stirred for 10 minutes. These precursor solutions were dropped into bulk BMA solution and stirred for 10 minutes. Strong emission was emerged immediately after the injection. Then, the solution was centrifuged at 8000 rpm for 10 minutes. The precipitate was collected and washed with 1-butanol for 3 ~ 5 times to remove the excess AMHCl ligands and dried under vacuum for 12 h. The solid powder was stored in nitrogen atmosphere for further using. Fabrication of MAPbCl 0.60 Br crosslinked PBMA network (using MAPbCl 0.60 Br 2.40 crosslinkers powder) by UV-polymerization. The MAPbCl 0.60 Br 2.40 crosslinkers powder was dispersed in BMA solution (0.5 ml) and maintained as colloidal dispersion. The solution was placed into a flat-bottomed glass tube with a diameter of 20.0 mm and filled with nitrogen. The tube was placed under the UV light (wavelength: 365 nm) for 12 h. After being cooled to room temperature, disk samples were obtained. S-4

5 Synthesis of MAPbCl 0.60 Br 2.40 crosslinkers in bulk MMA solution. 2-aminoethyl methacrylate hydrochloride (0.043 mol/l), methylammonium bromide (0.089 mol/l) and lead bromide (0.027 mol/l) were prepared in DMF. The precursor solution were prepared by mixing 2-aminoethyl methacrylate hydrochloride, methylammonium bromide and lead bromide in DMF (MABr : AMHCl : PbBr 2 = 1.22:0.80:1) and stirred for 10 minutes. These precursor solutions (50 μl) were dropped into MMA solution (1 ml) and stirred for 1 minute. Strong color emission was emerged immediately after the injection. All of experimental operations were performed at room temperature. Fabrication of MAPbCl 0.60 Br crosslinked PMMA networks by UV-polymerization. The preparation of MAPbCl 0.60 Br 2.40 crosslinkers in bulk BMA solution is the same as the synthsis of crosslinkers in BMA solution. MAPbCl 0.60 Br 2.40 crosslinkers/mma solution (0.5 ml) with TPO (5.19 mg) were placed into a flat-bottomed glass tube with a diameter of 20.0 mm and filled with nitrogen. The tube was placed under the UV light (wavelength: 365 nm) for 12 h. After being cooled to room temperature, disk samples were obtained. Synthesis of MAPbCl 0.60 Br 2.40 crosslinkers in bulk BA solution. The preparation of MAPbCl 0.60 Br 2.40 crosslinkers in bulk BA solution is the same as the synthsis of crosslinkers in BMA solution. 2-aminoethyl methacrylate hydrochloride (0.043 mol/l), methylammonium bromide (0.089 mol/l) and lead bromide (0.027 mol/l) were prepared in DMF. The precursor solution were prepared by mixing 2-aminoethyl methacrylate hydrochloride, methylammonium bromide and lead bromide in DMF S-5

6 (MABr : AMHCl : PbBr 2 = 1.22:0.80:1) and stirred for 10 minutes. These precursor solutions (50 μl) were dropped into BA solution (1 ml) and stirred for 1 minute. Strong color emission was emerged immediately after the injection. All of experimental operations were performed at room temperature. Fabrication of MAPbCl 0.60 Br crosslinked PBA networks by UV-polymerization. MAPbCl 0.60 Br 2.40 crosslinkers/ba solution (0.5 ml) with TPO (3.29 mg) were placed into a flat-bottomed glass tube with a diameter of 20.0 mm and filled with nitrogen. The tube was placed under the UV light (wavelength: 365 nm) for 12 h. After being cooled to room temperature, disk samples were obtained. Synthesis of methylammonium lead bromide nanoparticles (MAPbCl 0.72 Br 2.28 NPs) by using OA and OAm as capping ligand in bulk BMA solution. CH 3 NH 3 Br, PbBr 2, CH 3 NH 3 Cl and PbCl 2 were dissolved in DMF (5 ml). Oleyl amine (10 μl) and Oleic acid (250 μl) were added to stabilize the precursor solution in sequence. Then, 20 μl of the precursor solution was quickly added into the mixture of solution with BMA (1.5 ml), EDMA (18 μl) and TPO (5.19 mg) under stirring. Strong green emission was emerged immediately after the injection. All of experimental operations were performed at room temperature. Fabrication of the MAPbCl 0.72 Br 2.28 /PBMA composite by UV-polymerization. MAPbCl 0.72 Br 2.28 NPs/BMA solution (0.5 ml) were placed into a flat-bottomed glass tube with a diameter of 20.0 mm and filled with nitrogen. The tube was placed under the UV light (wavelength: 365 nm) for 12 h. After being cooled to room temperature, disk samples were obtained. S-6

7 Transmission electron microscopy (TEM) measurement. MAPbCl 0.60 Br 2.40 crosslinkers/bma solution (0.5 ml) with TPO (3.29 mg) were placed into a flat-bottomed glass tube and filled with nitrogen. The tube was placed under the UV light (wavelength: 365 nm) and the emissive BMA solution became viscous liquid after UV-polymerization for 2 h. Then the viscous liquid was dissolved in toluene to form the dilute solution for the TEM measurement. Fabrication of white LED devices. The red emissive rare-earth phosphor K 2 SiF 6 :Mn 4+ (KSF) powder was blended with UV-cured adhesive and coated on the surface of quartz plate ( cm). The composite was placed under the UV light (wavelength: 365 nm) for 1 h. The MAPbCl 0.36 Br crosslinked PBMA networks sample for LED device was fabricated by the following process: MAPbCl 0.60 Br 2.40 crosslinkers/ba solution (1.5 ml) with TPO (9.87 mg) were placed into a rectangular glass tube (bottom size: cm) and filled with nitrogen. The tube was placed under the UV light (wavelength: 365 nm) for 12 h. After being cooled to room temperature, disk samples were obtained. The KSF composite and MAPbCl 0.36 Br crosslinked PBMA networks sample were placed on the surface of blue LED, respectively. S-7

8 Figure S1. Photos of MAPbBr 3 without ligands (a1, a2) and MAPbCl 0.60 Br 2.40 crosslinkers (b1, b2) obtained from bulk BMA solution under ambient room light and UV illumination. S-8

9 Table S1. Precursor solutions were prepared by mixing 2-aminoethyl methacrylate hydrochloride, methylammonium bromide and lead bromide in DMF (the molar ratio of three compounds and Cl/Br were shown in the table). MAPbCl x Br 3-x MABr AMHCl PbBr 2 molar ratio Cl: Br MAPbCl 0.83 Br μl (2.4 μmol) 70 μl (3.0 μmol) 100 μl (2.7 μmol) 0.89:1.11:1 0.38:1 MAPbCl 0.72 Br μl (2.8 μmol) 60 μl (2.6 μmol) 100 μl (2.7 μmol) 1.05:0.96:1 0.31:1 MAPbCl 0.60 Br μl (3.2 μmol) 50 μl (2.2 μmol) 100 μl (2.7 μmol) 1.22:0.80:1 0.25:1 MAPbCl 0.48 Br μl (3.7 μmol) 40 μl (1.7 μmol) 100 μl (2.7 μmol) 1.38:0.64:1 0.19:1 MAPbCl 0.36 Br μl (4.1 μmol) 30 μl (1.3 μmol) 100 μl (2.7 μmol) 1.55:0.48:1 0.14:1 S-9

10 Table S2. The atomic ratios of Br and Cl for the MAPbCl x Br 3-x crosslinker powders obtained from BMA solution by XPS measurement. MAPbCl x Br 3-x atomic ratios of Cl/Br MAPbCl 0.83 Br :1 MAPbCl 0.72 Br :1 MAPbCl 0.60 Br :1 MAPbCl 0.48 Br :1 MAPbCl 0.36 Br :1 Table S3. Detailed PL information, including emission peaks, FWHM and PL-QYs of MAPbCl x Br 3-x crosslinkers formed in bulk BMA solution. MAPbCl x Br 3-x -PBMA Emission Peak (nm) FWHM (nm) PL-QYs (%) MAPbCl 0.83 Br MAPbCl 0.72 Br MAPbCl 0.60 Br MAPbCl 0.48 Br MAPbCl 0.36 Br S-10

11 Table S4. Detailed PL information, including emission peaks, FWHM and PL-QYs of MAPbCl x Br 3-x -crosslinked PBMA networks. MAPbCl x Br 3-x -PBMA Emission Peak (nm) FWHM (nm) PL-QYs (%) MAPbCl 0.83 Br MAPbCl 0.72 Br MAPbCl 0.60 Br MAPbCl 0.48 Br MAPbCl 0.36 Br S-11

12 Figure S2. XRD patterns of MAPbCl 0.83 Br 2.17, MAPbCl 0.72 Br 2.40, MAPbCl 0.48 Br 2.52 and MAPbCl 0.36 Br 2.64 crosslinkers formed in bulk BMA solution. S-12

13 Table S5. The signals of X-ray diffraction (XRD) patterns of MAPbCl 0.83 Br 2.17, MAPbCl 0.72 Br 2.40, MAPbCl 0.60 Br 2.40, MAPbCl 0.48 Br 2.52 and MAPbCl 0.36 Br 2.64 crosslinkers formed in bulk BMA solution. 2θ (degree) {h k l} {100} {110} {200} {210} {220} {300} MAPbCl 0.83 Br MAPbCl 0.72 Br MAPbCl 0.60 Br MAPbCl 0.48 Br MAPbCl 0.36 Br Signals of FTIR spectra: MAPbCl 0.60 Br 2.40 crosslinkers-ir (neat): 3037 cm -1 (N-H str), 1722 cm -1 (C=O), 1631 cm -1 (C=C str), 1479 cm -1 (-NH + 3, N H bend), 1297 cm -1 (C O), 1255 cm -1 (C N str, MABr), 1159 cm -1 (C N str, AMHCl), 925 cm 1 (CH 3 -NH + 3, C-H bend). AMHCl-IR (neat): 3037 cm -1 (N-H str), 1722 cm -1 (C=O), 1631 cm -1 (C=C str), 1492 cm -1 (-NH + 3, N H bend), 1295 cm -1 (C O), 1166 cm -1 (C N str). MABr-IR (neat): cm 1 (Br-H), 1253 cm -1 (C N str), 1002 cm 1 (CH 3 -NH + 3, C-H bend), 923 cm 1 (CH 3 -NH + 3, C-H bend). S-13

14 Figure S3. TEM images of MAPbCl 0.83 Br 2.17 (a), MAPbCl 0.72 Br 2.28 (b), MAPbCl 0.48 Br 2.52 (c) and MAPbCl 0.36 Br 2.64 (d) crosslinkers formed in bulk BMA solution. S-14

15 Figure S4. a) Transmission electron microscopy (TEM) image of MAPbCl 0.60 Br 2.40 crosslinkers obtained from bulk BMA solution. b) TEM image of MAPbCl 0.60 Br crosslinked PBMA networks. Figure S5. Normalized absorption spectra of MAPbCl x Br 3-x -crosslinked PBMA networks. S-15

16 Figure S6. XPS patterns of the Pb element in MAPbCl 0.60 Br 2.40 crosslinkers. Figure S7. XPS patterns of the N element in MAPbCl 0.60 Br 2.40 crosslinkers. S-16

17 Figure S8. XPS patterns of the Br element in MAPbCl 0.60 Br 2.40 crosslinkers. Figure S9. XPS patterns of the Cl element in MAPbCl 0.60 Br 2.40 crosslinkers. S-17

18 Figure S10. Photos of transparent disks (diameter: 3 cm) from MAPbCl 0.60 Br crosslinked PBMA networks fabricated by in situ polymerization under ambient room light (a1) and UV illumination (a2), MAPbCl 0.72 Br crosslinked PBMA network fabricated by using crosslinker powder under ambient room light (b1) and UV illumination (b2). S-18

19 Table S6. Details of MAPbCl 0.72 Br crosslinked PBMA network fabricated by in situ polymerization and MAPbCl 0.72 Br crosslinked PBMA network fabricated by using crosslinker powder. MAPbCl 0.60 Br PBMA network (in situ) MAPbCl 0.60 Br PBMA network (crosslinker powder) Emission Peak (nm) FWHM (nm) PLQY (%) Air stability (after exposing in air atmosphere for 30 days) Water resistance (after immersing in water for 60 h) 83% 80% 67% 59% S-19

20 Figure S11. Photos of transparent disks (diameter: 3 cm) from MAPbCl 0.60 Br crosslinked PMMA networks under ambient room light (a1) and UV illumination (a2). Figure S12. Photos of transparent gels (diameter: 3 cm) from MAPbCl 0.60 Br crosslinked PBA networks under ambient room light (a1 and a3) and UV illumination (a2 and a4). As a control, viscous liquid PBA (glass transition temperature: 20 o C, viscous liquid under room temperature) without MAPbCl 0.60 Br 2.40 crosslinkers was also prepared under ambient room light (b). S-20

21 Table S7. Triexponential fitting results of emissive bulk BMA solution and MAPbCl 0.72 Br crosslinked PBMA networks. Sample Emissive bulk BMA solution MAPbCl 0.72 Br crosslinked PBMA networks A 1 a) (ns) b) A 2 a) (ns) b) avg (ns) c) Time-resolved PL decay curves were fitted by a diexponential (eqs 1 and 2) function. a) A 1 and A 2 represents weight, [A(t) = A 0 + A 1 exp-(t-t 0 )/ 1 + A 2 exp-(t-t 0 )/ 2 (eqs 1)] ; b) 1 and 2 represents PL lifetime; c) The average lifetime were calculated using [ avg = (A A )/( A A 1 1 ) (eqs 2)]. S-21

22 Table S8. Remaining PL intensity of MAPbCl x Br 3-x -crosslinked PBMA networks after exposing in air atmosphere for 30 days. MAPbCl x Br 3-x -crosslinked PBMA networks MAPbCl 0.83 Br % MAPbCl 0.72 Br % MAPbCl 0.60 Br % MAPbCl 0.48 Br % MAPbCl 0.36 Br % Figure S13. Time-dependent PL intensity of MAPbCl x Br 3-x -crosslinked PBMA networks in water for 60 hours. S-22

23 Table S9. Remaining PL intensity of MAPbCl x Br 3-x -crosslinked PBMA networks after immersing in water for 60 hours. MAPbCl x Br 3-x -crosslinked PBMA networks MAPbCl 0.83 Br % MAPbCl 0.72 Br % MAPbCl 0.60 Br % MAPbCl 0.48 Br % MAPbCl 0.36 Br % Figure S14. The color coordinates (gray dot) of obtained white LED in CIE diagram. The CCT of white LED was achieved at K. S-23

24 Figure S15. The color coordinates (gray dot) of obtained color LED in CIE diagram. a) Green color: MAPbCl 0.36 Br crosslinked PBMA networks (double content than the white LED), b) Blue color: MAPbCl 0.36 Br crosslinked PBMA networks combine with MAPbCl 0.83 Br crosslinked PBMA networks, c) Purple color: MAPbCl 0.36 Br crosslinked PBMA networks (one half content than the white LED). S-24

25 Figure S16. Photos of transparent disks (diameter: 3 cm) from MAPbCl 0.60 Br crosslinked PBMA networks (AMHCl as capping ligands) under ambient room light (a1) and UV illumination (a2), MAPbCl 0.72 Br PBMA composite (OA and OAm as capping ligands) under ambient room light (b1) and UV illumination (b2). S-25

26 Table S10. Details of MAPbCl 0.60 Br crosslinked PBMA network (AMHCl as capping ligands) and MAPbCl 0.72 Br PBMA composite (oleic acid (OA) and oleylamine (OAm) as capping ligands). MAPbCl 0.72 Br crosslinked PBMA network (AMHCl) MAPbCl 0.72 Br PBMA composite (OA and OAm) Emission Peak (nm) FWHM (nm) PLQY (%) Air stability (after exposing in air 91% 73% atmosphere for 30 days) Water resistance (after immersing in water for 72% 58% 60 h) S-26