• Photonics Research
  • Vol. 9, Issue 9, 1767 (2021)
Chenjing Quan1、2、†, Xiao Xing2、†, Sihao Huang2, Mengfeifei Jin3, Tongchao Shi2, Zeyu Zhang2、4、5, Weidong Xiang3、6、*, Zhanshan Wang1、7、*, and Yuxin Leng2、4、8、*
Author Affiliations
  • 1School of Physics Science and Engineering, Tongji University, Shanghai 200092, China
  • 2State Key Laboratory of High Field Laser Physics and CAS Center for Excellence in Ultra-intense Laser Science, Shanghai Institute of Optics and Fine Mechanics (SIOM), Chinese Academy of Sciences (CAS), Shanghai 201800, China
  • 3College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China
  • 4Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China
  • 5School of Physics and Electronics, Shandong Normal University, Jinan 250014, China
  • 6e-mail: xiangweidong001@126.com
  • 7e-mail: wangzs@tongji.edu.cn
  • 8e-mail: lengyuxin@mail.siom.ac.cn
  • show less
    DOI: 10.1364/PRJ.427155 Cite this Article Set citation alerts
    Chenjing Quan, Xiao Xing, Sihao Huang, Mengfeifei Jin, Tongchao Shi, Zeyu Zhang, Weidong Xiang, Zhanshan Wang, Yuxin Leng, "Nonlinear optical properties of CsPbClxBr3-x nanocrystals embedded glass," Photonics Res. 9, 1767 (2021) Copy Citation Text show less

    Abstract

    All-inorganic perovskite has attracted significant attention due to its excellent nonlinear optical characteristics. Stable and low-toxic perovskite materials have great application prospects in optoelectronic devices. Here, we study the nonlinear optical properties of CsPbClxBr3-x (x=1, 1.5, 2) nanocrystals (NCs) glass by open-aperture Z-scan. It is found that the two- (2PA) and three-photon absorption (3PA) intensity can be adjusted by the treatment temperature and the ratio of halide anions. The perovskite NCs glass treated at a high temperature has better crystallinity, resulting in stronger nonlinear absorption performance. In addition, the value of the 2PA parameter of CsPbCl1.5Br1.5 NCs glasses decreases when the incident pump intensity increases, which is ascribed to the saturation of 2PA and population inversion. Finally, the research results show that the 2PA coefficient (0.127 cm GW-1) and 3PA coefficient (1.21×10-5 cm3 GW-2) of CsPbCl1Br2 NCs glass with high Br anion content are larger than those of CsPbCl2Br1 and CsPbCl1.5Br1.5 NCs glasses. This is mainly due to the greater influence of Br anions on the symmetry of the perovskite structure, which leads to the redistribution of delocalized electrons. The revealed adjustable nonlinear optical properties of perovskite NCs glass are essential for developing stable and high-performance nonlinear optical devices.

    1. INTRODUCTION

    All-inorganic perovskite has received widespread attention recently, owing to its tunable light-emitting bandgap [1,2], large exciton binding energy [3], and other excellent photoelectric properties [4,5]. Hence, perovskite materials are mostly used in light-emitting diodes (LEDs) [6,7], solar cells [8], photodetectors [9,10], lasers [4,11], and other devices. Halide perovskite nanocrystals have become one of the most promising optoelectronic materials due to their low-cost and easy synthesis [1]. Compared with bulk and layered materials, the specific surface area of CsPbClxBr3x nanocrystals (NCs) is greatly increased, thereby enhancing the NC optical performance [1,2,12]. Due to the strong multiphoton absorption (MPA) characteristics of halide perovskite NCs, they are very promising as a material for the development of multiphoton pump lasers [13]. The spherical NCs not only overcome the difficulty of large area growth of thin films, but also can combine with a variety of substrates or solutions for incorporation into optoelectronic devices [14].

    Owing to the poor stability of bare perovskite and toxicity of lead halide perovskite, the application of perovskite materials in optoelectronic devices is greatly restricted [15,16]. So far, diverse approaches to improve the stability of perovskite materials have been reported, such as bonding of the organic ligands [17], establishing core/shell nanostructure [18], Mn-doping [19], silica coating [20,21], and infiltrating CsPbX3 NCs into mesoporous matrices [22]. However, combining the thermal, chemical, and mechanical stability of the glass has been proved an effective method to improve the stability of perovskite NCs [2325]. Hu et al. reported the well-designed arrangement of CsPbBr3 NCs glasses with reduced self-absorption emission and enhanced the quantum efficiency of solar cells [26]. Ye et al. investigated the versatile precipitation of CsPbX3 NCs glasses, in which photoluminescence (PL) covering the whole visible range with high efficiency could be achieved [24]. Meanwhile, some researches indicated that the relative PL intensity of CsPbBr3 quantum dots glass is still 85%90% after being immersed in water for 120 h or exposed to UV light for 100 h, and even about 60% of PL intensity still remained for storage up to 45 days [27,28]. All these previous studies reveal that embedding CsPbX3 quantum dots or NCs into glass has a great potential in improving its stability and fluorescence performance [2628].

    However, the nonlinear optical aspect of perovskite glass, especially the study of MPA, which is important to the application of these optoelectronic devices, has been rarely investigated [13,29,30]. Many studies have been reported on the nonlinear optical properties of pure perovskite [31]. For example, a two-photon absorption (2PA) cross section of CsPbBr3 NCs in toluene as high as 106  GW has been reported [32]. Chen et al. demonstrated that the 2PA cross section of CsPbBr3 NCs depends on the particle size [33]. Furthermore, due to the symmetry breaking of the perovskite octahedron structure, Li et al. confirmed that all-inorganic perovskites with different proportions of halogen atoms show greater MPA intensity than CsPbCl3 and specially designed organic molecules [34,35]. Not only that, Chen et al. reported that the five-photon absorption cross section of Type-I core-shell halide perovskite NCs is 9 orders of magnitude higher than that of specially designed organic molecules [30]. However, the nonlinear optical aspect of perovskite glass, which is highly desired for applications in low-threshold lasing [36], optical data storage [37], photodetectors [38], and other nonlinear optical photoelectric devices [32], has been rarely investigated.

    In the present work, the three-order nonlinear optical characteristics of CsPbClxBr3x (x=1, 1.5, 2) NCs glasses have been investigated by open-aperture (OA) Z-scan measurements using femtosecond laser pulses. We observe the 2PA and three-photon absorption (3PA) phenomena of CsPbClxBr3x (x=1, 1.5, 2) NCs glasses at wavelengths of 800 and 1300 nm. The magnitude of the 2PA coefficient (β) of CsPbClxBr3x (x=1, 1.5, 2) NCs glasses is about 101102  cmGW1, and the magnitude of the 3PA coefficient (γ) is 105106  cm3GW2. The observed MPA behavior of CsPbClxBr3x (x=1, 1.5, 2) NCs glasses could play a great role in the development of perovskite-based optoelectronic devices.

    2. EXPERIMENT SETUP

    In the OA Z-scan measurement, as shown as Fig. 1, the perovskite NCs glasses with thickness L are moved along the Gaussian light propagation direction, and the laser beam transmittance after the sample is measured. For 2PA measurement, we used a Ti:sapphire femtosecond laser (Spectra-Physics) operating at a central wavelength of 800 nm with a repetition frequency of 1 kHz and a pulse width of 35 fs. For 3PA measurements, the laser source consisted of an optical parametric amplifier (TOPAS-Prime), delivering a wavelength of 1300 nm with a pulse width of 200 fs. The repetition frequency of laser was 1 kHz. In order to amplify weak signals, a chopper (Thorlabs MC2000B) is inserted into the optical path. The focal length of the front lens of the sample is 10 cm, and the spot radius at the focal point is about 30 μm. The transmitted intensity of each pulse after passing through the sample is measured by a Si-biased detector (Thorlabs DET10A2) using the lock-in amplifier (Signal Recovery Model 7270) technique.

    Experimental setup for the Z-scan technique.

    Figure 1.Experimental setup for the Z-scan technique.

    3. RESULTS AND DISCUSSION

    In this work, CsPbClxBr3x (x=1, 1.5, 2) NCs are successfully embedded inside a glass sheet (radius=10  mm, thickness=0.56  mm) matrix via the melt-quenching and in situ crystallization method. The CsPbClxBr3x (x=1, 1.5, 2) NCs are spherical structures with a diameter of 3545  nm [see the Appendix A, Fig. 6(a)] [39]. Figure 2(a) shows the X-ray diffraction (XRD) patterns of CsPbCl1.5Br1.5 NCs glass under different treatment temperatures. The diffraction peaks of perovskite glass are at 15.5°, 22°, 31°, 38.5°, and 44.6°, corresponding to (100), (110), (200), (211), and (220) phase, respectively [40,41]. Referring to the previous research results, these narrow diffraction peaks demonstrate that the CsPbCl1.5Br1.5 NCs have good crystallization [25]. Figure 2(b) displays the PL emission spectra of CsPbCl1.5Br1.5 NCs glass. The PL emission peak of CsPbCl1.5Br1.5 NCs glass displays a slight redshift with the treatment temperature from 470°C to 530°C. The reason for the slight redshift of PL emission peak in the CsPbCl1.5Br1.5 NCs glass is the increase of the crystal grains size, which is caused by the increase of the heat treatment temperature [41]. However, the surface defects increase due to the continuous increase in temperature, which affects the fluorescence quantum yield and causes the PL emission intensity of the CsPbCl1.5Br1.5 NCs glass to decrease [41].

    (a) XRD patterns and (b) PL emission spectra of CsPbCl1.5Br1.5 NCs glasses under different treatment temperature excited by femtosecond pulses at 365 nm.

    Figure 2.(a) XRD patterns and (b) PL emission spectra of CsPbCl1.5Br1.5 NCs glasses under different treatment temperature excited by femtosecond pulses at 365 nm.

    Figures 3(a) and 3(b) show the OA Z-scan curves of the CsPbCl1.5Br1.5 NCs glass (bandgap2.58  eV) at the different treatment temperature excited by 800 nm (1.55  eV) with pump intensity of 25.5  GW/cm2 and by 1300 nm (0.95  eV) with pump intensity of 217  GW/cm2, respectively (see the Appendix A, Fig. 8). As shown in Figs. 3(a) and 3(b), the Z-scan curves are all valley shapes. When the CsPbCl1.5Br1.5 NCs glass is close to the focus, the normalized transmission of the incident laser decreases. As shown in Figs. 3(a) and 3(b), the CsPbCl1.5Br1.5 NCs glass with a heat treatment temperature of 530°C has the strongest nonlinear response.

    OA Z-scan results of CsPbCl1.5Br1.5 NCs glasses with different treatment temperatures. (a) Under pump intensity 25.5 GW/cm2 at a wavelength of 800 nm and (b) under pump intensity 217 GW/cm2 at a wavelength of 1300 nm. (The balls are the experimental data, and the solid lines are fitting curves.) The fitting results of (c) β and (d) γ of CsPbCl1.5Br1.5 NCs glass with different treatment temperatures. (Inset, the schematic of a two-level model.)

    Figure 3.OA Z-scan results of CsPbCl1.5Br1.5 NCs glasses with different treatment temperatures. (a) Under pump intensity 25.5  GW/cm2 at a wavelength of 800 nm and (b) under pump intensity 217  GW/cm2 at a wavelength of 1300 nm. (The balls are the experimental data, and the solid lines are fitting curves.) The fitting results of (c) β and (d) γ of CsPbCl1.5Br1.5 NCs glass with different treatment temperatures. (Inset, the schematic of a two-level model.)

    In theory, the measured normalized transmission (T) for OA Z-scan results is given by the expression [42,43] TOA(nPA)=1{1+(n1)αNLLeff{I0/[1+(z/z0)2]}n1}1/n1(n=1,2,3),where Leff is the effective length of the sample. αNL is the nonlinear optical coefficient. z is the position of the sample in the light path, z0=πω02/λ is the Rayleigh range of the Gaussian beam, and ω0 is the beam waist at the focal point (z=0).

    Among them, the 2PA coefficient is represented by β. The imaginary part of third-order nonlinear susceptibility [44,45], Imχ(3)=c2ε0n02βω,where c is the speed of light, n0 is the linear refractive index, and ε0 and ω are the vacuum permittivity and angular frequency of the laser beam, respectively. The figures of merit (FOMs) are used to describe nonlinear absorption characteristics: FOM=|Imχ(3)/α0|, where α0 is the linear absorption coefficient. The 3PA coefficient is represented by γ. The effective thicknesses of 2PA and 3PA are Leff=(1eα0L)/α0 and Leff=(1e2α0L)/2α0, respectively [42,43].

    Figures 3(c) and 3(d) display the 2PA and 3PA coefficients of CsPbCl1.5Br1.5 NCs glasses at the different treatment temperatures obtained by fitting Eq. (1). The insets in Figs. 3(c) and 3(d) show the schematic diagram of the 2PA and 3PA processes, respectively. When CsPbCl1.5Br1.5 NCs glass is excited by the femtosecond laser, electrons in the valence band need to absorb two (or three) photons at the same time to transition to the conduction band. By fitting with a Z-scan theory, 2PA coefficients of CsPbCl1.5Br1.5 NCs glass with different treatment temperatures were calculated: β=0.87  cmGW1 for 470°C treatment temperature, β=0.97  cmGW1 for 500°C treatment temperature, and β=1.23  cmGW1 for 530°C treatment temperature, respectively. Under the pump intensity of 25  GW/cm2, the Imχ(3) for CsPbCl1.5Br1.5 NCs glasses are in the range of (1.992.81)×103  esu and the magnitudes of FOM are all at 103  esu cm obtained by fitting Eq. (2) (see the Appendix A, Table 1). 3PA coefficients of CsPbCl1.5Br1.5 NCs glasses with different treatment temperatures were calculated: γ=2×105  cm3GW2 for 470°C, γ=2.17×105  cm3GW2 for 500°C, and γ=2.86×105  cm3GW2 for 530°C, respectively. As the processing temperature increases, the crystallinity is better. The larger the nanocrystal particles, the stronger the 2PA and 3PA performance of the CsPbCl1.5Br1.5 NCs glasses [39].

    Furthermore, the nonlinear properties of CsPbCl1.5Br1.5 NCs glasses with different pump intensities are measured. The OA Z-scan curves of CsPbCl1.5Br1.5 NCs glass under 500°C treatment temperature with various incident pump intensities at the wavelength of 800 nm are shown in Fig. 4(a). The normalized transmittance decreases when either increasing the pump intensity or placing the CsPbCl1.5Br1.5 NCs glass closer to the focus point, z=0, while as the pump intensity increases, the normalized transmittance curve deepens. These results suggest the potential application of CsPbCl1.5Br1.5 NCs glass in optoelectronic devices, such as optical limiting devices [46]. Figure 4(b) summarizes the dependence of 2PA fitting results as a function of pump intensity. (Fitting results are summarized in Table 2). The β is 0.096 cm/GW of CsPbCl1.5Br1.5 NCs glass at the pump intensity of 255  GW/cm2 and 0.089 cm/GW at the pump intensity of 332  GW/cm2, respectively. The result of the 2PA coefficient we obtained is with the same order of magnitude as the CsPbBr3 NCs [36] and CsPbClxBr3x (x=1, 2) quantum dots [47]. The perovskite NCs encapsulated in perovskite glass are isolated from the external environment. This gives them better stability and greatly improves the service life of perovskite NCs. The Imχ(3) for CsPbCl1.5Br1.5 NCs glasses are in the range of (2.032.88)×102  esu and the FOM is in the range of (2.33.2)×102  esucm. It is shown that as the pump intensity increased, the value of β, Imχ(3), and FOM decreased. The same phenomenon has been observed in other materials, such as PbS/glue nanocomposite [48] and few-layer WS2 films [49]. As the incident light energy increases, a large number of carriers gather in the excited state, resulting in population inversion [50]. Hence, the electrons in the ground state cannot further absorb the photon and transition to the excited state [51]. The β of CsPbCl1.5Br1.5 NCs decreases as the pump intensity increases.

    (a) OA Z-scan curves and (b) corresponding fitting results of β (black ball), Imχ(3) (pink), and FOM (blue) of the CsPbCl1.5Br1.5 NCs glass at the wavelength of 800 nm with different incident pump intensity.

    Figure 4.(a) OA Z-scan curves and (b) corresponding fitting results of β (black ball), Imχ(3) (pink), and FOM (blue) of the CsPbCl1.5Br1.5 NCs glass at the wavelength of 800 nm with different incident pump intensity.

    To further explore the influence of different doped halogen anion ratios on the MPA and consider the influence of treatment temperature on the PL performance of all-inorganic perovskite glasses, we choose CsPbClxBr3x (x=1, 1.5, 2) NCs glasses with a treatment temperature of 500°C to explore their nonlinear response [52]. Figures 5(a) and 5(b) display the OA Z-scan response of CsPbClxBr3x (x=1, 1.5, 2) NCs glasses under femtosecond laser of 800 nm and 1300 nm, respectively.

    OA Z-scan results of CsPbClxBr3−x (x=1, 1.5, 2) NCs glasses. (a) Under pump intensity 178 GW/cm2 at a wavelength of 800 nm and (b) under pump intensity 535 GW/cm2 at a wavelength of 1300 nm. (The balls are the experimental data, and the solid lines are fitting curves.) (c) PL emission spectra of CsPbClxBr3−x (x=1, 1.5, 2) NCs glasses for 500°C treatment temperature excited by femtosecond pulses at 365 nm; (d) fitting the results of 2PA coefficient (β, purple bar) and 3PA coefficient (γ, red bar) obtained in (a) and (b), respectively.

    Figure 5.OA Z-scan results of CsPbClxBr3x (x=1, 1.5, 2) NCs glasses. (a) Under pump intensity 178  GW/cm2 at a wavelength of 800 nm and (b) under pump intensity 535  GW/cm2 at a wavelength of 1300 nm. (The balls are the experimental data, and the solid lines are fitting curves.) (c) PL emission spectra of CsPbClxBr3x (x=1, 1.5, 2) NCs glasses for 500°C treatment temperature excited by femtosecond pulses at 365 nm; (d) fitting the results of 2PA coefficient (β, purple bar) and 3PA coefficient (γ, red bar) obtained in (a) and (b), respectively.

    Figure 5(a) shows the OA Z-scan curves of CsPbClxBr3x (x=1, 1.5, 2) NCs glasses under pump intensity 178  GW/cm2 at a wavelength of 800 nm. Comparing the normalized transmittance curves of CsPbClxBr3x (x=1, 1.5, 2) NCs glasses with different Cl and Br ion ratios, it is found that the CsPbClxBr3x (x=1, 1.5, 2) NCs glasses with higher Br ions doping ratio have a greater nonlinear response in the process of 2PA and 3PA. The bandgap width of CsPbCl1Br2 NCs glasses is 2.46 eV, slightly smaller than that of CsPbCl1.5Br1.5 (2.58 eV) and CsPbCl2Br1 (2.7 eV) (see the Appendix A, Fig. 8). Due to the increase of Br ion content, the bandgap is narrowed, thereby promoting the carrier transition rate [34,53]. CsPbCl1Br2 NCs glasses exhibit a large MPA phenomenon. Correspondingly, the PL emission peak of CsPbCl2Br1, CsPbCl1.5Br1.5, and CsPbCl1Br2 NCs glasses with emission wavelength peaks at 454, 470, and 490 nm is shown in Fig. 5(c), respectively. The PL peak shifts to the lower energy direction as the proportion of Br ions increases. It is shown that the luminescence can be effectively tuned by introducing the Cl and Br ion ratios. The width of CsPbClxBr3x (x=1, 1.5, 2) NCs glasses at half-height (FWHM) of the PL emission is less than 30 nm (see the Appendix A, Fig. 7).

    By fitting the Z-scan data in Figs. 5(a) and 5(b), the β of CsPbCl1Br2 NCs glass is 0.087  cmGW1, 0.1  cmGW1 for CsPbCl1.5Br1.5 NCs glass, and 0.127  cmGW1 for CsPbCl2Br1 NCs glass. The 2PA coefficient of CsPbCl1Br2 NCs glass is 1 order of magnitude higher than that of CsPbCl1Br2 quantum dots [47]. Combined with Eq. (2), the Imχ(3) for CsPbClxBr3x NCs glasses is in a range of (1.992.9)×102  esu, which is larger than that of CsPbBr3 NC (see the Appendix A). The FOM value used to describe the nonlinear absorption characteristics is in the range of (2.22.53)×102  esucm (see the Appendix A, Table 3). Meanwhile, we obtained the γ: 0.54×105  cm3GW2 is for CsPbCl2Br1 NCs glass, 0.82×105  cm3GW2 is for CsPbCl1.5Br1.5 NCs glass, and 1.21×105  cm3GW2 is for CsPbCl1Br2 NCs glass. The 3PA coefficient of CsPbCl1Br2 NCs glass is over 1 order of magnitude larger than that of the CsPbCl1.5Br1.5 and CsPbCl2Br1 NCs glasses. This is mainly because the CsPbCl1Br2 NCs glass has a narrower bandgap and higher structural destabilization that will lead to the easier carrier transition and delocalized electrons redistribution compared with CsPbCl1.5Br1.5 and CsPbCl2Br1 NCs glasses [24]. Due to the narrower bandgap and structural destabilization of the perovskite, the electron cloud is distorted, which promotes the transition of electrons from the ground state to the excited state [34]. Therefore, the carrier transition rate is further increased.

    4. CONCLUSION

    In summary, we measure the 2PA and 3PA properties of CsPbClxBr3x (x=1, 1.5, 2) NCs glasses using the OA Z-scan method. The CsPbCl1.5Br1.5 NCs glass under 530°C treatment temperature exhibited the strongest 2PA and 3PA coefficients, which is mainly due to the better crystallization properties of perovskite NCs at higher temperatures. Furthermore, the dependence of incident pump intensity shows that the nonlinear coefficient decreases when the incident pump intensity increases. We also found that the larger the proportion of Br anions, the stronger the MPA performance. These results for CsPbClxBr3x NCs glass may guide designs for their potential use in applications.

    Appendix A

    The CsPbClxBr3-x (x = 1, 1.5, 2) nanocrystals are spherical structures with a diameter of ∼35–45 nm enclosed in a glass sheet, as shown in Fig. 6(a).

    (a) Transmission electron microscopy (TEM) images of CsPbClxBr3-x (x = 1, 1.5, 2) NCs and (b) high-resolution TEM images of CsPbCl1.5Br1.5 NCs.

    Figure 6.(a) Transmission electron microscopy (TEM) images of CsPbClxBr3-x (x = 1, 1.5, 2) NCs and (b) high-resolution TEM images of CsPbCl1.5Br1.5 NCs.

    (a) Amplified spontaneous emission (ASE) measurement on CsPbCl1.5Br1.5 NCs glass under an 800 nm pulsed laser at room temperature and (b) corresponding full-width at half-maxima (FWHM) and output as a function of incident pump intensity.

    Figure 7.(a) Amplified spontaneous emission (ASE) measurement on CsPbCl1.5Br1.5 NCs glass under an 800 nm pulsed laser at room temperature and (b) corresponding full-width at half-maxima (FWHM) and output as a function of incident pump intensity.

    (αhυ)2-hυ plot of CsPbClxBr3-x (x=1, 2, 3) NCs glass.

    Figure 8.(αhυ)2-hυ plot of CsPbClxBr3-x (x=1,2,3) NCs glass.

    Open-aperture Z-scan curves of the (a) CsPbCl1Br2 and (b) CsPbCl2Br1 NCs glasses at the wavelength of 800 nm with different incident pump intensity.

    Figure 9.Open-aperture Z-scan curves of the (a) CsPbCl1Br2 and (b) CsPbCl2Br1 NCs glasses at the wavelength of 800 nm with different incident pump intensity.

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    Chenjing Quan, Xiao Xing, Sihao Huang, Mengfeifei Jin, Tongchao Shi, Zeyu Zhang, Weidong Xiang, Zhanshan Wang, Yuxin Leng, "Nonlinear optical properties of CsPbClxBr3-x nanocrystals embedded glass," Photonics Res. 9, 1767 (2021)
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