Stable Two-Photon Pumped Amplified Spontaneous Emission from

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Spectroscopy and Photochemistry; General Theory

Stable Two-Photon Pumped Amplified Spontaneous Emission from Millimeter-Sized CsPbBr Single Crystals 3

Chunyi Zhao, Wenming Tian, Junxue Liu, Qi Sun, Jiajun Luo, Hong Yuan, Baodong Gai, Jiang Tang, Jingwei Guo, and Shengye Jin J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.9b00734 • Publication Date (Web): 22 Apr 2019 Downloaded from http://pubs.acs.org on April 22, 2019

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The Journal of Physical Chemistry Letters

Stable Two-Photon Pumped Amplified Spontaneous Emission from Millimeter-Sized CsPbBr3 Single Crystals Chunyi Zhao,†,‡ Wenming Tian,*,† Junxue Liu,† Qi Sun,†,‡ Jiajun Luo,§ Hong Yuan,±,‡ Baodong Gai,± Jiang Tang,§ Jingwei Guo,*,± and Shengye Jin*,† AUTHOR ADDRESS †State

key laboratory of molecular reaction dynamics and the dynamic research center for energy

and environmental materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China ‡University

§Sargent

of Chinese Academy of Sciences, Beijing 100049, China

Joint Research Center, Wuhan National Laboratory for Optoelectronics (WNLO) and

School of Optical and Electronic Information, Huazhong University of Science and Technology (HUST), Wuhan, China ±Key

Laboratory of Chemical Lasers, Dalian Institute of Chemical Physics, Chinese Academy of

Sciences, Dalian, China

ACS Paragon Plus Environment

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ABSTRACT: Metal-halide perovskites are promising optical gain materials because of their excellent photophysical properties. Recently, large perovskite single crystals with phase purity, less defects and over millimeter dimensions have been successfully synthesized. However, the optical gain effect from these large-size single crystals has not yet been realized. Herein, we for the first time report efficient two-photon pumped amplified spontaneous emission (ASE) from millimeter-sized CsPbBr3 single crystals (SCs) with a low threshold of 0.65 mJ cm-2 and an optical gain of 38 cm-1. Furthermore, the CsPbBr3 SCs also exhibit ultrastable ASE under continuous laser irradiation for more than 40 hours (corresponds to 1.5108 laser shots) at ambient condition. This work suggests the potential application of large-size perovskite single crystals in practical nonlinear optical devices.

TOC GRAPHICS

Solution-processed metal-halide perovskites have caused a great research boom for their successful application in photovoltaics.1-11 The perovskite-based solar cells have reached a power conversion efficiency (PCE) of 23.6%.12 This remarkable achievement was attributed to its excellent photophysical properties, including high absorption coefficient, long carrier lifetime and diffusion length, and high photoluminescence (PL) quantum yield.13-18 Owing to the same


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properties, perovskites are also ideal optical gain materials. Efficient lasing or amplified stimulated emission (ASE) from thin films and nanostructures of CH3NH3PbX3 or CsPbX3 (X is halide) perovskites have been reported.19-30 These optical gain effects can be obtained by either single-photon or two/multiple-photon excitations. Yakunin et al. and Wang et al. first reported the low threshold single-photon pumped ASE and lasing from CsPbX3 perovskite nanocrystals (NCs).20, 31 Afterwards, lasers with low thresholds and high quality factors were realized from various CsPbX3 perovskite micro/nanostructures.22,

24, 27, 32-38

Compared to single-photon

excitations, two/multiple-photon excitations is a nonlinear process with distinct advantages such as large penetration depth, less Rayleigh scattering and less photo damage on the samples.39-42 In the past few years, efficient two-photon absorption was reported in perovskite materials. CsPbBr3 NCs were found to have a much larger two-photon absorption cross section than the conventional CdSe NCs. Since the first achievement of two-photon pumped ASE from CsPbBr3 quantum dots (QDs) thin films by Pan et al, 19 many stable two-photon pumped laser and ASE in CsPbX3 perovskite micro/nanostructures with thresholds from 4.84 J cm-2 to 12 mJ cm-2 have been reported.

25, 26, 29, 37, 40-44

These discoveries indicate that the CsPbX3 perovskites are

promising materials as an optical gain media for nonlinear optical devices. Lasing or ASE from individual perovskite nanostructures (e.g. nanowires or nanoplates) usually targets the applications for nanophotonics devices. Instead, ASE from perovskite thin films or other large size perovskite materials might be more likely to realize practical applications in light of their feasibility of device integration. However, films made of polycrystalline perovskites or perovskite nanocrystals suffer a large density of defects. The defect is associated with the polycrystalline grain boundaries or surface of nanocrystals and is usually inevitable in solution-processed fabrications. The performance of ASE was thus found to


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highly depend on the film crystallinity and morphology.

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Alternatively, large ( ≥ millimeter

scale) perovskites single crystals (SC) with phase purity and less defects provides another ideal platform to realize optical gain effect. However, lasing or ASE from large perovskite SCs with dimensions ≥ millimeter scale has not yet been reported, though such large perovskite crystals have been fabricated in the past few years. Due to the large size of SCs, realizing ASE by single photon pump is challenging because of the limited excitation photon penetration depth. However, the large two-photon absorption cross section of CsPbBr3 perovskites makes two-photon pumped ASE very possible from millimeter-sized single crystals. Herein, we for the first time report an efficient two-photon pumped ASE from millimeter-sized CsPbBr3 SCs with a low threshold of 0.65 mJ cm-2. Furthermore, the CsPbBr3 SCs exhibit high photostability for at least 40 hours (1.5 ×108 laser shots) under continuous laser irradiation at ambient conditions. We grew the millimeter-sized CsPbBr3 SCs by mixing the CsBr and PbBr2 precursors with a molar ratio of 2:1. The dimethyl sulfoxide (DMSO) was added into the mixture of CsBr and PbBr2 precursors in the culture dish. The mixture was then heated to 180 °C and stirred until the solids dissolved into solution. The solution was then cooled down to the room temperature, and the CsPbBr3 single crystals grew slowly to the millimeter size within a week. After reaction, the crystals were rinsed with isopropanol to remove the residual salt and then dried in a vacuum oven at 60 °C for 24 hours. The obtained CsPbBr3 perovskites are rod-like single crystals with a length of 2 ~7 mm and a width and thickness of 0.2 ~ 0.6 mm (Figure 1a and b). The SEM images of the CsPbBr3 SCs (Figure S1) show that these large SCs have smooth surfaces and exhibit high uniformity and good crystal quality. Figure 1c presents the UV-Vis absorption and PL spectra of CsPbBr3 SCs collected at ambient condition. The absence of excitonic signature in the absorption spectrum implies a insignificant number of in-gap defect states, which also


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confirms the high quality of the SCs.15 The energy band gap (Eg) of the CsPbBr3 SC is calculated to be 2.22 eV (the inset in Figure 1c). The PL of the crystals centers at 540 nm with 405 nm excitation (single-photon excitation). The large overlap between PL and absorption spectrum illustrates the reabsorption effect in these materials. The powder X-ray diffraction pattern of CsPbBr3 SCs shown in Figure 1d confirms the pure monoclinic perovskite phase (a = 5.827 Å, b= 5.827 Å, c = 5.891 Å). The diffraction peaks of high-index lattice plane illustrate the high quality of the SC.

Figure 1. (a) and (b) Photographs of the synthesized CsPbBr3 SCs with millimeter dimensions. (c) UV-Vis absorption and PL spectra of a typical CsPbBr3 SC. Inset: Tauc plot shows the determination of optical band gap energy of the SC. (d) A typical powder XRD profile of CsPbBr3 SCs, confirming their phase purity. Trap state density has been well recognized as a key factor affecting the ASE performance by causing the loss of photon-generated carriers through fast nonradiative recombination. In


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CsPbBr3 SCs, the trap states can be caused by many factors, such as impurities, dangling of chemical bonds, atomic vacancy, deformation of lattice structure and surface defects. To calculate the trap state density in CsPbBr3 SCs, we measured the dark current-voltage (I-V) response using a device structure of Au-CsPbBr3-Au displayed in Figure 2a (see SI for details). There are two kink points dividing the dark I-V curve into three parts. The first part below the first kink point is the ohmic region, where the current increases slowly and linearly with the applied voltage. Beyond the first kink point voltage, the current increases rapidly with the applied voltage after all trap states are filled with the injected charges. This region is the trapfilled limit region and the first kink point is designated as the trap-filled limit voltage (VTFL). Since the trap state density is proportional to VTFL, the quantity of the trap state density can be calculated according to the following equation: 45

𝑉𝑇𝐹𝐿 =

𝑒𝑛𝑡𝑟𝑎𝑝𝑑2

2𝜀𝜀0

(1)

where ntrap is the trap state density, ε is the relative dielectric constant, ε0 is the constant of permittivity in free space, d is the thickness of single crystals, and e is electronic charge. The VTFL for the examined CsPbBr3 SCs is 25 V, leading to the calculation of ntrap= 8.5  109 cm-3, This value is close to the reported values in MAPbBr3 microcrystals.15 Such low trap state density makes the CsPbBr3 SCs to be an excellent candidate for semiconductor lasing or highpurity ASE.


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Figure 2. (a) Schematic diagram of the Dark I-V measurement for the determination of trap state density in CsPbBr3 SCs. (b) The current-voltage trace from a typical CsPbBr3 SC, showing three different regimes. The solid lines are the linear fits of each regime, by which the trap-filled limit voltage (VTFL) is determined. The trap state density in the crystal is calculated according to Eq. 1. We next examined the two-photon pumped ASE from the large CsPbBr3 SCs. In the ASE experiment, the samples were placed on a glass slide. We performed the two-photon pumped ASE by using Ti:sapphire laser system from Coherent (800 nm, 35 fs, 1 kHz repetition rate) and a fiber optic spectrometer to detect the PL spectra (see Figure S2 in SI for details). The laser beam is a nearly uniform pump source with a diameter larger than the samples. Figure 3a shows the pump-intensity-dependent emission spectra from a typical crystal. The corresponding changes of integrated emission intensity (Light-in-light-out: L-L) and the full width at half maxima (FWHM) as a function of pump intensity are plotted in Figure 3b. When the pump intensity is < 0.65 mJ cm-2, the emission spectra is dominated by the spontaneous emission (SPE) with a broad peak (FWHM = ~ 17 nm) centered at around 550 nm (Figure 3a). Compared to the emission (PL peak at 540 nm) under one-photon excitation at 405 nm, the PL peak under twophoton excitation is red-shifted by 10 nm, which is attributed to the enhanced reabsorption effect due to the larger optical penetration depth in CsPbBr3 SCs when excited at 800 nm.26, 46 As the pump intensity increases over 0.65 mJ cm-2, a sharp ASE peak centered at 543 nm in


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combination with a sharp decrease in FWHM to ~7 nm emerges and the ASE intensity grows rapidly with increase of pump intensity. The transition from SPE to ASE is further confirmed by the emission images under excitation intensity below and above the ASE threshold (Figure 3c). Fitting the L-L plot to the expected S-curve model yields an ASE threshold (Pth) of ~0.65 mJ cm2.

The Pth is comparable with that of CsPbBr3 NCs thin film (~0.8 mJ cm-2)

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and MAPbBr3

MWs (~0.674 mJ cm-2) 23 and much smaller than that of CdSe-based QD thin films (~5 mJ cm-2) 47

under two-photon excitation. Such a low ASE threshold is attributed to the large two-photon

absorption coefficient and the low trap state density in the CsPbBr3 SCs. We also measured the PL decay dynamics of CsPbBr3 SCs below and above the ASE Pth. The CsPbBr3 SC shows a PL lifetime of SPE = 8 ns with excitation intensity of 0.35 mJ cm-2 (< Pth). When the excitation intensity exceeds Pth (3 mJ cm-2), a fast PL decay component limited by the instrument response function (IRF) of ~100 ps is observed, as a result of the ASE process.


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Figure 3. Two-photon pumped ASE in CsPbBr3 SC with a length of 5 mm and a width and thickness of 0.2 mm. (a) Pump-fluence-dependent emission spectra from a typical CsPbBr3 SC. (b) The plots of PL intensity and FWHM as a function of pump intensity, showing the ASE threshold of ~0.65 mJ cm-2. (c) Photographs of the CsPbBr3 SC in panel a under excitations below and above the ASE threshold. The scale bar is 2 mm. (d) The comparison of PL decay kinetics under excitation intensities below (0.35 mJ cm-2, blue) and above the ASE threshold (3 mJ cm-2, red). The dash line is the Instrument Response Function (IRF) and the solid lines are the exponential fits of PL decay kinetics that yield lifetimes of 8 ns for SPE and ≤ 100 ps for ASE.

Figure 4. The gain coefficient measured by VSL model. (a) Stripe-length-dependent emission spectra from a typical CsPbBr3 SC. The pump intensity is 2.3 mJ cm-2 (b) The plot of ASE intensity as a function of stripe length. Solid line is the fit of the plot by Eq. 2, yielding an optical gain coefficient of 38 cm-1. In addition to ASE threshold, optical gain is also an important character reflecting the efficiency of light amplification. We evaluated the optical gain of CsPbBr3 SCs by using variable strip length (VSL) method (see Figure S3 in SI for details). 49 The 800 nm femtosecond laser beam was focused by a cylindrical lens into a stripe-shape. Figure 4 presents the stripe-length-


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dependent emission spectra and the corresponding plot of ASE peak intensity as a function of the stripe length measured from a ~0.3 mm thick CsPbBr3 SC under a pump intensity of 2.3 mJ cm-2. The ASE peak appears and increases rapidly when the strip length is > 0.1 cm, We adopt the VSL model to evaluate the optical gain by the following equation:49 𝐼 = A(𝑒𝑔𝑙 ―1)/g

(2)

where I is the emission intensity, g is the optical gain coefficient and l is the strip length. Fitting the measured data yields an optical gain coefficient of 38 cm-1. In CsPbBr3 NCs, the optical gain effect was found to generate through the stimulated emission from biexcitons with ASE redshifted to the spontaneous emission peak.50 However, in CsPbBr3 bulk crystals, the ASE peak appears on the higher energy side of the observed spontaneous emission peak. This abnormal phenomenon is because that the observed spontaneous emission from large SCs is red-shifted to their intrinsic one, caused by the reabsorption effect. Figure S4 shows the emission spectrum collected from a CsPbBr3 powder sample obtained by grinding the large SCs. The spectrum from powder sample should be less affected by the reabsorption, and in relative to this spectrum the ASE from the SCs is indeed at the lower-energy region.


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Figure 5. Time-dependent ASE intensity of a typical CsPbBr3 SC under a continuous irradiation (2.3 mJ cm-2) over 40 hours at ambient condition. The inset is the comparison of ASE spectra measured at 400 minutes and 2400 minutes. For practical applications, the photostability is also an important character of an optical gain material. We further test the ASE stability of the large CsPbBr3 SC at ambient condition (24 ℃, 30 % relative humidity) under a continuous laser irradiation. The ASE peak intensity was monitored continuously within the operation time under an uninterrupted laser pump at 800 nm and 2.3 mJ cm-2. As shown in Figure 5, the CsPbBr3 SC shows an excellent optical stability with the ASE peak intensity sustained for more than 40 hours, corresponding to 1.5108 laser shots. The ASE spectra measured at 400 minutes and 2400 minutes, shows almost identical ASE shape and intensity (the inset in Figure 4). The stability of CsPbBr3 SCs is better than that of other semiconductor QD films and CsPbBr3 nanostructures, which were usually examined in a dry N2 atmosphere. We believe the smaller specific surface are and less amount of defects in the CsPbBr3 SCs are the key points that make it more stable than other nanostructured perovskite materials. The above results demonstrate that the large CsPbBr3 SCs are of great potential for practical applications in nonlinear optical devices. In summary, we have reported the synthesis of millimeter-sized CsPbBr3 SCs with low trap state density of 8.5109 cm-3. We, for the first time, realized efficient two-photon-pumped ASE from millimeter-sized CsPbBr3 SCs with a low ASE threshold of 0.65 mJ cm-2 and an optical gain of 38 cm-1. Furthermore, the CsPbBr3 SCs exhibited great photostability under continuous laser irradiation for more than 40 hours (corresponds to 1.5108 laser shots) at ambient condition. This study indicates that the millimeter-sized CsPbBr3 SCs are promising materials for up-


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conversion laser and nonlinear optics devices in macroscopic application. Further optimizations in crystal dimensions, surface treatment and, ultimately, integration in a laser cavity are currently undergoing in our laboratory toward the development of realistic laser devices using large perovskite single crystals. ASSOCIATED CONTENT Supporting Information Experimental details of the PL and UV-Vis absorption spectra, I-V response, time-resolved PL decay dynamics, two-photon pumped ASE, optical gain coefficient measurements and additional results of measurements. The Supporting Information is available free of charge on the ACS Publications website. AUTHOR INFORMATION Corresponding Author [email protected]; [email protected]; [email protected] ACKNOWLEDGMENT S. Jin acknowledges the funding support from the MOST (2018YFA0208704, 2016YFA0200602) and NSFC (21725305). W. Tian acknowledges the funding support from the NSFC (21703241). Notes


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