Zinc-Phosphorus Complex Working as Atomic Valve for Colloidal Growth of Monodisperse Indium Phosphide Quantum Dots

Transcription

1 Supporting Information Zinc-Phosphorus Complex Working as Atomic Valve for Colloidal Growth of Monodisperse Indium Phosphide Quantum Dots Sungjun Koh, Taedaehyeong Eom, Whi Dong Kim, Kangha Lee, Dongkyu Lee, Young Kuk Lee, Hyungjun Kim*,, Wan Ki Bae*,, and Doh C. Lee*, Department of Chemical and Biomolecular Engineering, KAIST Institute for the Nanocentury and Graduate School of Energy, Environment, Water, and Sustainability (EEWS), Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea Advanced Materials Division, Korea Research Institute of Chemical Technology (KRICT), Daejeon 34114, Republic of Korea Photoelectronic Hybrids Research Center, Korea Institute of Science and Technology (KIST), Seoul 02792, Republic of Korea 1

2 Content Figure S1 Page 31 P{ 1 H} NMR spectra of P(SiMe3)3 3 Figure S2 Proton-coupled 31 P NMR spectra of precursor mixtures 3 Figure S3 UV-vis absorption spectra and 2 nd derivatives of exemplary 4 samples Figure S4 XPS spectra in P 2p region of InP QDs and In(Zn)P QDs 4 Figure S5 Mass spectra of Zn + P sample, Zn(St)2 and dithranol matrix 5 Figure S6 Absorption spectra and XRD patterns of Zn + P sample 5 Figure S7 TEM images and size histograms of InP QDs and In(Zn)P QDs 6 Figure S8 XRD patterns of InP QDs and In(Zn)P QDs 7 Figure S9 Mass spectra of samples obtained using DCTB matrix 7 Figure S10 Magnetic property curves of InP sample prepared at room 8 temperature Figure S11 1 H NMR spectra of InP sample prepared at room temperature 9 for 30 min Figure S12 XRD patterns of In(Zn)P QDs with different precursor mixing 10 Figure S13 PL QY of In(Zn)P QDs 10 Figure S14 PL emission spectra of In(Zn)P QDs 11 Table S1 Optical properties of In(Zn)P QDs 12 Table S2 ICP-MS results of In(Zn)P QDs and Zn + P sample 13 References 14 2

3 Figure S1. 31 P{ 1 H} NMR spectra of P(SiMe3)3. Two peaks around -240 ppm correspond to protonated P(SiMe3)3. 1 Figure S2. Proton-coupled 31 P NMR spectra of mixtures of metal and phosphorus precursors at room temperature. The quartet represents PH3 with 182 Hz of J coupling constant in accordance with a previous report. 1 3

4 Figure S3. UV-vis absorption spectra of InP QDs (left) and In(Zn)P QDs (right) with reaction time of 10 min and their second derivatives to determine 1S excitonic transition wavelengths. Figure S4. XPS spectra in P 2p region of InP QDs and In(Zn)P QDs. 4

5 Figure S5. Mass spectra of Zn + P sample precursor mixture, Zn(St)2 and dithranol matrix at room T within a range that metal-phosphorus intermediates were observed. Figure S6. UV-vis absorption spectra (left) and XRD patterns (right) of Zn + P sample with reaction time of 60 min. XRD patterns of Zn + P samples do not correspond to any zinc phosphide crystalline but a hemimorphite structure. 2 5

6 Figure S7. TEM images and size histograms for 300 particles of (A) and (B) InP QDs, and (C) and (D) In(Zn)P QDs with reaction time of 20 min at 300 C. (E) UV-vis absorption spectra of samples in (A) and (C). 6

7 Figure S8. XRD patterns of InP and In(Zn)P QDs described in Figure 1. Figure S9. MALDI-TOF mass spectra of samples taken at room temperature. (A) and (D) Low and high mass scale spectra for InP QDs synthesis; (B) and (E) Low and high mass scale spectra for Zn + P sample; and (C) and (F) Low and high mass scale spectra for In(Zn)P QDs synthesis. In the low mass scale spectra, peaks of DCTB, In(My)3 or Zn(St)2 overlaps the mass range of metal-phosphorus complexes. No higher order species such as polymers or clusters are observed in high mass scale spectra. 7

8 Figure S10. (A) Magnetization-temperature curve and (B) magnetization-magnetic field curve measured at 10 K of InP sample (In(My)3 + P(SiMe3)3) prepared at room temperature. Lack of hysteresis in field-sweep scan indicates paramagnetism of InP sample. 8

9 Figure S11. 1 H NMR spectra of InP sample prepared at room temperature 30 min before measurement, In(My)3, and P(SiMe3)3. (a) Triplet is observed only in the case of InP sample indicating that the peak is from (SiMe3)-carboxylate, but not in the case of In(My)3 due to the paramagnetism. (b) Singlet corresponding to (SiMe3)-carboxylate evolves. (c) Doublet with 6.5 Hz of J coupling constant evolves, which is attributed to myristate hydrocarbon of In-P complex. 9

10 Figure S12. XRD patterns of In(Zn)P QDs with 20 min reaction and zinc to indium precursor ratio of 5 synthesized from Zn-P complex (blue) or In-P complex (red). The peak shift to higher 2 theta with higher zinc content is in accordance with a previous report. 2 Figure S13. PL QY of In(Zn)P QDs with various zinc to indium precursor ratio synthesized from In-P complex (red) or Zn-P complex (blue). Error bars of PL QY indicate the range from three different batches. 10

11 Figure S14. PL emission spectra of In(Zn)P QDs with various zinc to indium precursor ratio from three different batches in the case of In-P complex (left) or Zn-P complex (right) was formed at room temperature before heat-up synthesis. 11

12 Table S1. Optical properties of In(Zn)P QDs with various zinc to indium precursor ratio and different precursor mixing sequences (In-P + Zn: In-P complex was formed beforehand; Zn-P + In: Zn-P complex was formed beforehand.) 1 st experiment 2 nd experiment 3 rd experiment Average Std. dev. Zn /In PL peak FWHM PL peak FWHM PL peak FWHM PL peak FWHM PL peak FWHM In-P + Zn Zn-P + In

13 Table S2. ICP-MS results of In(Zn)P QDs with various zinc to indium precursor ratio and Zn + P sample Zn/In precursor ratio Concentration (mg/kg) Atomic fraction P Zn In P Zn In In-P + Zn Zn-P + In Zn + P

14 References (1) Gary, D. C.; Cossairt, B. M., Role of Acid in Precursor Conversion During InP Quantum Dot Synthesis. Chem. Mater. 2013, 25, (2) Pietra, F.; De Trizio, L.; Hoekstra, A. W.; Renaud, N.; Prato, M.; Grozema, F. C.; Baesjou, P. J.; Koole, R.; Manna, L.; Houtepen, A. J., Tuning the Lattice Parameter of InxZnyP for Highly Luminescent Lattice-Matched Core/Shell Quantum Dots. ACS nano 2016, 10,