Abstract
1. Introduction
Lead halide perovskites hold great promises in the field of optoelectronic devices, due to their excellent optical and electrical properties including high optical gain, stable excitonic luminescence, fast carrier mobility and high fluorescence quantum efficiency[
In this work, ultrathin CsPbCl3 NW arrays on mica substrate are achieved by chemical vapor deposition (CVD) method. Power- and temperature-dependent photoluminescence (PL) spectroscopy is carried out to investigate emission dynamics of the as-prepared CsPbCl3 NWs. Strong PL peak is observed at ~ 3.02 eV with full width at half maximum (FWHM) of ~ 58 meV owing to the free exciton (FX) recombination. With temperature decreasing from 294 to 77 K, the PL peak shows a first blueshift and then redshift at a transition temperature of ~ 190 K. The temperature dependence of intensity and FWHM of FX peak is fitted by Arrhenius equation and Boson models with an exciton binding energy and average optical phonon energy of ~ 37.5 and ~ 48.0 meV, respectively. These results advance the understanding of exciton properties of CsPbCl3.
2. Experiment details
In this work, the atomically-flat muscovite mica KAl2(AlSi3O10)(OH)2 was used as growth substrate[
3. Results and discussions
The SEM image (Fig. 1(a)) shows that the as-grown NWs are well arranged along the [010] direction of the mica substrate. The NW length varies from tens to several hundreds of nanometers. The AFM image (Fig. 1(b)) shows that the NWs exhibit homogenous morphology along the long axis of NWs, suggesting the good crystallinity of the as-grown NWs. The heights of the two representative NWs (Fig. 1(c)) are ~ 6.6 and 7.4 nm, respectively, much smaller than that reported in the previous works[
Figure 1.(Color online) The structure and morphology characterization of ultrathin CsPbCl3 nanowires (NWs) epitaxial on mica. (a) Scanning electron microscopy (SEM) image of the ultrathin CsPbCl3 NWs grown on (001)-mica by chemical vapor deposition method. (b) Atomic force microscopy (AFM) image of the CsPbCl3 NWs, scale bar: 100 nm. (c) Corresponding data of CsPbCl3 NWs height extracted from (b). (d) X-ray diffraction pattern of the CsPbCl3 NWs on mica (red line) and mica (black line).
Fig. 2 shows PL spectra of CsPbCl3 NWs under the excitation of 360 nm continuous-wave laser at 294 and 78 K, respectively. At 294 K, two peaks can be resolved for both the as-grown CsPbCl3 thin NW (height: ~ 7 nm with a ~ ±2.0 nm; Fig. 2(a), upper panel) and the bulk-like wire (thick NW, height: ~ 8 μm; Fig. 2(a), lower panel). The high and low-energy peak can be well fitted by Lorentzian functions (solid black curves). For the thin NW, the high-energy peak locates at ~ 3.023 eV (FWHM, ~ 58 meV) and dominates the whole PL spectroscopy, which is primarily attributed to FX emission considering the high exciton binding energy of the CsPbCl3[
Figure 2.(Color online) Photoluminescence (PL) emission spectra of thin (height: ~ 7 nm; upper panel) and thick (height: ~ 8
Power-dependent PL spectroscopy is performed to further study the origin of PL peaks in the thin NW at 294 K (Fig. 3(a)). As the excitation power density Pex increases from ~ 0.3 to 61.1 kW/cm2, the FX emission primarily dominates the PL spectroscopy, suggesting that FX recombination is the major radiative transition channel for the thin NW. The integrated PL intensity IP versus Pex is extracted which can be well fitted by the equation of IP–Pexα (Fig. 3(b))[
Figure 3.(Color online) (a) Power-dependent emission spectra of thin CsPbCl3 NWs on mica at 294 K with
Fig. 4(a) shows the PL spectra of the ultrathin NWs as a function of temperature. The FX and X-band can be resolved among the temperature of 78–294 K. Owing to the research interest, we will focus on the temperature dependent behavior of FX emission. As temperature decreases from 294 to 190 K, the FX peak energy blueshifts from ~ 3.023 to ~ 3.025 eV (by ~ 2 meV,Fig. 4(b), pink scatters). While, as the temperature further decreases from 190 to 78 K, the PL peak exhibits redshift from ~ 3.025 to ~ 3.021 eV (by ~ 4 meV). Similar phenomenon has been observed in the PL spectroscopy of the nanocrystals and is attributed to two possible reasons[
Figure 4.(Color online) (a) Temperature-dependent PL spectra of CsPbCl3 NWs on mica in the range of 294 − 78 K. The red and blue dot lines are the fitting curves of the FX and X-band by Lorentzian function, respectively. Scatters: experimental data point;
4. Conclusion
In conclusion, single-crystal all-inorganic CsPbCl3 ultrathin NW arrays have been synthesized via CVD method in this work. Systematic optical spectroscopy study reveals that the FX emission with binding energy of 37.5 meV is the major radiation recombination channel. With the decreasing of temperature, the FX emission peak shows a first blueshift and then redshift with a transition temperature of ~ 190 K, possibly owing to the phase transition or the competition of lattice expansion and exciton–phonon scattering. We also demonstrate that the linewidth broadening of FX emission is mainly contributed from the exciton-optical phonon interaction with average phonon energy of 48.0 meV and the coupling coefficient of 203.9 meV. These results advance the understanding of exciton dynamics and fabrication of CsPbCl3 perovskite NWs.
Acknowledgements
The work is supported by National Natural Science Foundation of China (Nos. 61774003, 61521004, 51472080), National Key Research and Development Program of China (Nos. 2017YFA0205700, 2017YFA0304600), Open Research Fund Program of the State Key Laboratory of Low-dimensional Quantum Physics (No. KF201706) and Excellent Youth Foundation of Hubei Province (No. 2017CFA038).
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