Open Access
10 July 2023 Transparent glassy composites incorporating lead-free anti-perovskite halide nanocrystals enable tunable emission and ultrastable X-ray imaging
Yakun Le, Xiongjian Huang, Hao Zhang, Zhihao Zhou, Dandan Yang, Bozhao Yin, Xiaofeng Liu, Zhiguo Xia, Jianrong Qiu, Zhongmin Yang, Guoping Dong
Author Affiliations +
Abstract

Lead halide perovskite materials exhibit excellent scintillation performance, which, however, suffer from serious stability and toxicity problems. In contrast, the heavy metal-free anti-perovskite materials [ MX4 ] XA3 (A = alkali metal; M = transition metal; X = Cl, Br, I), a class of electron-inverted perovskite derivatives, exhibit robust structural and photophysical stability. Here, we design and prepare a lead-free [ MnBr4 ] BrCs3 anti-perovskite nanocrystal (NC)-embedded glass for efficient X-ray-excited luminescence with high-resolution X-ray imaging with a spatial resolution of 19.1 lp mm − 1. Due to the unique crystal structure and the protection of the glass matrix, the Cs3MnBr5 NC-embedded glass exhibits excellent X-ray irradiation stability, thermal stability, and water resistance. These merits enable the demonstration of real-time and durable X-ray radiography based on the developed glassy composite. This work could stimulate the research and development of novel metal halide anti-perovskite materials and open a new path for future development in the field of high-resolution and ultrastable X-ray imaging.

1.

Introduction

High-resolution and ultrastable X-ray imaging methods required in material inspection, medical diagnostics, astronomical discovery, and scientific research have stimulated extensive research on X-ray-responsive materials with high X-ray attenuation, efficient scintillation, fast light decay, and robust durability.14 Recently, lead halide-based perovskites have attracted growing attention in the field of X-ray imaging, due to their excellent high luminescence efficiency, high X-ray attenuation ability, and short fluorescence lifetime.58 However, they are restricted in the scintillation field due to the toxicity of heavy metal Pb, low photon yield caused by severe self-absorption effect, and poor X-ray irradiation stability.9,10 In order to solve the above problems, many types of lead-free zero-dimensional (0D) metal halides,11 such as Cu-based halides,1214 Ag-based halides,15 Zr-based halides,16 and Mn-based halides,17,18 have been developed as effective scintillators for X-ray detection and imaging on account of their high photon yield, diversity of composition and structure, and unique self-trapped excitons luminescence mechanism. Nevertheless, most of them are fabricated in thin-film form or wafers for X-ray imaging,11 which usually demonstrate low imaging resolution due to the light scattering by the large particles and crystal boundary.9 In addition, lead-free 0D metal halides suffer from poor stability, especially in a hot and humid environment.19 To improve the imaging resolution and durability, a more practical solution would be the encapsulation of the lead-free 0D metal halides with controllable size into a stable matrix. Recently, lead-free halide NCs have been crystalized in glass and exhibit potential in light-emitting devices,20 but the dynamic X-ray imaging in a high-temperature and humid environment is hard to realize.

Compared with lead halide perovskite materials, the configuration of anti-perovskite materials can be represented as ABX3, but electronically inverted (X is a cation, and A and B are anions or anionic groups).21,22 From the point of view of structural chemistry, anti-perovskite can accommodate a variety of elements, forming a large family of functional materials. Anti-perovskite materials have shown various interesting properties, such as magnetism,23 ionic conductivity,24 superconductivity,25 and negative thermal expansibility,26 but have rarely been reported as photoluminescent materials. One type of anti-perovskite is [MX4]XA3 (A = alkali metal; M = transition metal; X = Cl, Br, I), in which the luminescence center is the [MX4]2 tetrahedron filled in the three-dimensional (3D) XA6 octahedral anti-perovskite skeleton. This unique structure can effectively reduce the interaction of the luminescence center and increase the spatial confinement effect so that anti-perovskite materials generally have high quantum efficiency and luminescence stability.27 Recently, the specific requirements for performing X-ray imaging at high temperatures have increased dramatically. Nondestructive inspection of some high temperature industrial equipment can be done easily by X-ray imaging applications.28,29 In addition, some investigation of the effects of high temperature on a polymer electrolyte fuel cell also needs high temperature X-ray imaging technology.30,31 What is more, high-temperature X-ray microtomographic imaging can supply a new technique for studying mechanical behavior of multiphase composites.32 Most importantly, the specific requirements for detectors used in space aimed at achieving stunning elevated temperature stability.33,34 Therefore, it would be highly attractive to explore and design an anti-perovskite material for X-ray imaging applications in a high-temperature environment.

Here, we demonstrate state-of-the-art high-resolution and ultrastable X-ray imaging in a high-temperature and humid environment using the designed lead-free Cs3MnBr5 anti-perovskite nanocrystal (NC)-embedded glass. Mn2+ ions are transferred into Cs3MnBr5NCs through in situ crystallization in the glass matrix during annealing, therefore displaying tunable luminescence color from red to green controlled by the annealing schedule. With the protection of the transparent glass matrix, Cs3MnBr5 NCs show excellent optical properties, good machinability, and high stability. As expected, the Cs3MnBr5 NC-embedded glass exhibits X-ray detection limit of 767  nGyairs1, a high X-ray imaging spatial resolution of 19.1  lpmm1 and a high X-ray dose irradiation stability at 5.775  mGyairs1. More importantly, this transparent NC–glass composite enables high-resolution X-ray imaging even in a high-temperature and humid environment. Our results would have strong implications for the development of next-generation X-ray imaging devices.

2.

Results and Discussion

2.1.

Synthesis and Structural Characterization of Cs3MnBr5 NCs in the Glass

A precursor glass (PG) containing cesium, manganese, and bromine elements is designed and fabricated by the melt-quenching method, and Cs3MnBr5NCs are crystallized in the glass matrix by annealing above the glass transition (Tg) temperature (Fig. S1 in the Supplemental Material), as shown in Fig. 1(a). As a lead-free anti-perovskite material, the Cs3MnBr5 crystal consists of [MnBr4]2 tetrahedrons filled in the (3D) BrCs6 octahedral skeleton [Fig. 1(a)]. From the density functional theory (DFT) calculations of band structures and corresponding density of states [Figs. 1(b) and 1(c)], the direct bandgap of Cs3MnBr5 crystal is 3.367  eV, contributing to the absorption band in the ultraviolet (UV) region and high optical transmittance in the visible region.35 The diffraction peaks at 22.783 deg, 26.914 deg, and 29.454 deg corresponding to (004), (213), and (310) crystal facets of Cs3MnBr5 (PDF#27-0117) are observed in the X-ray diffraction (XRD) pattern after the glass was annealed at 570°C for 5 h [Fig. 1(d)]. In addition, X-ray photoelectron spectroscopy (XPS) was performed on the glass sample before and after annealing (Fig. S2 in the Supplemental Material). The characteristic peaks of Mn 2p1/2 (653.4 eV) and 2p3/2 (642.1 eV) are observed, which are higher than that in manganese halide (<640.7  eV), indicating that the electron density and covalent bond ratio of Cs3MnBr5NC-embedded glass are increased.36 This may result in stronger ionic bonding between manganese ions and bromine ions, which could enhance the stability under high-energy-ray irradiation.17 The electron paramagnetic resonance (EPR) spectra show a wide EPR signal with a line width of 609.4 G instead of six fine structures because of the high concentration in the glass (Fig. S3 in the Supplemental Material).37 The signal is more obvious after annealing, which is due to the stronger magnetic coupling caused by the decrease in the spacing of Mn2+ ions after the Cs3MnBr5 NCs crystallized in the glass.38 A transmission electron microscope (TEM) image shows dispersed NCs with an average size of 18.3 nm, indicating the formation of NCs with good crystal quality in the glass matrix [Figs. 1(e) and 1(f)]. The crystal lattice fringes with a spacing of 0.305 nm can be seen in the high-resolution transmission electron microscope (HRTEM) image, which corresponds to the (310) crystal facet of Cs3MnBr5 [Fig. 1(g)]. The above results confirm the successful precipitation of Cs3MnBr5 NCs in the glass after annealing.

Fig. 1

Structural properties of Cs3MnBr5 NCs crystallized in the glass. (a) Schematic diagram of glass network structure before (left) and after (middle) annealing and the anti-perovskite structure of the Cs3MnBr5 crystal (right). (b) DFT-calculated band structures and (c) electronic density of states of the Cs3MnBr5 crystal. (d) XRD patterns of the PG and the glass sample after annealing at 570°C for 5 h. (e) TEM image, (f) corresponding size distribution, and (g) HRTEM image of the glass annealed at 530°C for 5 h. The inset in (g) is the fast Fourier transform pattern corresponding to the (310), (213), and (004) crystal facet. The scale bars in (e) and (g) are 100 and 10 nm, respectively.

AP_5_4_046002_f001.png

2.2.

Photoluminescence Properties of Cs3MnBr5 NCs in the Glass

As a typical transition metal ion, the optical properties of Mn2+ ions are influenced by the strong interactions between electrons in their outermost d orbitals and their ligands, which can be described by the crystal field strength (10Dq) and the Racah parameter (B), respectively.39,40 The Tanabe–Sugano diagram in Fig. 2(a) reveals the change in the energy level of Mn2+ as the electronic configuration of 3d5 is sensitive to local perturbations. The 10Dq and B for Mn (IV) in Cs3MnBr5 NCs are calculated to be 8192 and 811  cm1, and for Mn (VI) in glass are 11,306 and 732  cm1, respectively (see note 1 in the Supplemental Material). These calculations confirm that the 3d5 electronic configuration of Mn2+ doped in the glass was significantly changed after the crystallization of the glass.

Fig. 2

PL properties of Cs3MnBr5 NCs in the glass. (a) Tanabe–Sugano diagram of 3d5 electronic configuration of Mn2+ ions. (b) Absorption and (c) PL spectra of the PG and samples annealed at different temperatures for 5 h. The inset in (b) shows the photographs of the glass samples taken under daylight (top) and 365 nm UV light (bottom). (d) PLE mapping spectra of the glass sample annealed at 570°C for 5 h. (e) Fluorescence decay curves of Cs3MnBr5 NCs and (f) Mn2+ in glass annealed at different temperatures. The fitting curves are fitted with (e) single-exponential and (f) double-exponential, respectively. The excitation wavelength used in (c), (e), (f) is 365 nm.

AP_5_4_046002_f002.png

The absorption spectra of the PG and the glass samples annealing at different temperatures are recorded in the wavelength region of 300 to 800 nm [Fig. 2(b)]. The narrow peak at 413 nm is attributed to the electronic transition of A61(S)A41, E4(G) of Mn2+ ions. Under the excitation of 365 nm UV light, a green emission band peaking at 523 nm emerges after crystallization, which originates from Mn2+ in the tetrahedron of Cs3MnBr5 NCs [Fig. 2(c)]. It is worth noting that there are two luminescence centers in the glass after annealing, attributed to Cs3MnBr5 NCs and the remaining Mn2+ ions in the glass matrix. Thus, the luminescence color can also be adjusted by controlling the excitation wavelength due to the two different luminescence centers, as shown in Fig. 2(d) and Figs. S4(a, b) in the Supplemental Material. The variation of two different emission bands in the time-resolved emission spectrum (1 to 10 ms) shows two different coordination environments around Mn2+ in the annealed glass sample (Fig. S5 in the Supplemental Material). With the increase of annealing temperature, the fluorescence lifetimes of the green and red emission change a little [Figs. 2(e) and 2(f)]. This is because Mn2+ is in a stable tetragonal and hexagonal field environment, respectively. Due to the crystal coordination environment of Cs3MnBr5 NCs, the green emission lifetime reaches the microsecond range, which is often required for dynamical X-ray imaging.

To further increase the concentration of Cs3MnBr5 NCs, we also investigated the effect of annealing duration on the luminescence properties of the samples. The glass samples were treated at 570°C for 5 to 40 h, respectively, and a series of photoluminescence (PL) spectra and lifetime decay curves were recorded [Figs. S6(a–d) in the Supplemental Material]. It can be found that with the increase in annealing duration, the green emission of the samples is gradually enhanced due to the increase in the concentration of Cs3MnBr5 NCs. However, the scattering caused by the increase in crystal size also leads to a large optical loss of the glass samples. Thus, the sample treated at 570°C for 10 h has the highest PL quantum yield of 35.5% (Fig. S7 in the Supplemental Material). Depending on the annealing temperature and duration, the emission color of the glass samples can be precisely adjusted from red to green (Fig. S8 in the Supplemental Material). In contrast to the typical CsPbX3 (X = Cl, Br, I) materials, which have poor thermal and optical stability, the stability of Cs3MnBr5 NC-embedded glass has been greatly improved. At 503 K, the green emission of the sample retains 66% of the intensity recorded at room temperature [Fig. S9(a, b) in the Supplemental Material]. In addition, under the continuous irradiation of a 375 nm laser with 6.4  W/cm2 for 60 min, the PL intensity of Cs3MnBr5 remained unchanged (Fig. S10(a, b) in the Supplemental Material). These characteristics can be attributed to the unique restriction of the high-density luminescent center in the Cs3MnBr5 anti-perovskite configuration and their larger binding energies.

2.3.

Radioluminescence Properties of Cs3MnBr5 NCs in the Glass

The tunable PL, excellent stability, and large Stokes shift (negligible self-absorption) demonstrate the large potential of Cs3MnBr5 NC-embedded glass for applications in the field of X-ray detection applications. In contrast to the PL mechanism, the radioluminescence (RL) mechanism involves an additional photoelectron conversion process that converts high-energy electrons to low-energy ones for radiative recombination [Fig. 3(a)].15 The X-ray is absorbed by heavy atoms, such as Cs, Mn, Ge from Cs3MnBr5 NC-embedded glass through photoelectric effect and Compton scattering. Then, a large number of hot electrons are released and captured by the luminescence center after being thermalized. We investigate the X-ray absorption coefficient of the Cs3MnBr5 NC-embedded glass from 1 to 1000 keV. The absorption coefficient of Cs3MnBr5 NC-embedded glass is comparable with the typical scintillators, such as Bi4Ge3O12 (BGO) and CsPbBr3 [Fig. 3(b)].41 The light yield of Cs3MnBr5 NC-embedded glass is 5200  photonsMeV1 estimated by using commercial scintillator BGO as a standard sample (Fig. S11 in the Supplemental Material).42 Due to the dual-emission centers, the glass samples demonstrate RL with an adjustable red–green ratio under X-ray excitation by adjusting the annealing temperature and duration [Fig. 3(c) and Fig. S12 in the Supplemental Material]. It is shown in Fig. 3(c) that with the increase of annealing duration, the emission color of glass samples changes from light yellow to yellow-green under X-ray irradiation. The Cs3MnBr5 NC-embedded glass shows the similar PL and RL spectra, indicating that they originate from the same radiative recombination channel upon X-ray and UV excitation. Interestingly, from the RL spectra recorded under X-ray excitation with different dose rates, we observe that Cs3MnBr5 NCs have a better linear response to the dose rate of X-rays than that of Mn2+ ions in the glass sample (Fig. S13 in the Supplemental Material). In Fig. 3(d), we show the RL spectra of a series of low-dose X-ray excitations. For scintillation materials, the detection limit is one of the most important parameters for medical examination. Here, the detection limit of the X-ray dose rate is 787  nGyairs1 for Cs3MnBr5 NC-embedded glass when the signal-to-noise ratio is 3. This value is significantly lower than the dose rate used in X-ray medical diagnosis (5.5  μGyairs1 dose rate), as shown in Fig. 3(e).43 Therefore, these merits of Cs3MnBr5 NC-embedded glass make it possible to achieve high-performance X-ray detection and real-time X-ray imaging.

Fig. 3

RL properties of Cs3MnBr5 NCs in the glass. (a) Schematic diagram of X-ray-induced luminescence mechanism of Cs3MnBr5 NCs and Mn2+ ions in the glass. (b) X-ray attenuation efficiency of Cs3MnBr5 NC-embedded glass, BGO, and CsPbBr3 crystal. (c) RL spectra of Cs3MnBr5 NC-embedded glass annealed at 570°C for different durations recorded under X-ray excitation with a dose rate of 4.814  mGyairs1. The inset shows the photographs of the corresponding samples taken under X-ray irradiation. (d) RL spectra of the sample annealed at 570°C for 40 h recorded under different low X-ray dose rates. (e) Linear relationship between the low dose rate and RL intensity of the sample annealed at 570°C for 40 h.

AP_5_4_046002_f003.png

2.4.

X-Ray Imaging Performance of Cs3MnBr5 NCs in the Glass

Due to the high optical transparency of glass (Fig. S14 in the Supplemental Material) and the excellent RL properties, this Cs3MnBr5 NC-embedded glass is used for high-resolution X-ray imaging. Here, we construct a self-made X-ray imaging system [Fig. 4(a)], and a series of objects, such as an AI chip, a charging cable, and a circuit board, were imaged by Cs3MnBr5 NC-embedded glass under X-ray and captured by a commercial digital camera. As shown in Fig. 4(b), the internal structures are directly observed, indicating that Cs3MnBr5 NC-embedded glass is promising for electronics inspection and damage imaging. To further demonstrate the X-ray imaging capability of Cs3MnBr5 NC-embedded glass, images of the standard X-ray resolution pattern plate with different thicknesses of glasses were used (Fig. S15 in the Supplemental Material). The highest resolution of the X-ray image was achieved while the glass thickness is 0.6 mm (Fig. S16 in the Supplemental Material). The observation down-limit is between 18 and 20  lpmm1, which is consistent with the calculated results of modulation transfer functions (MTFs) according to the slanted-edge method [Fig. 4(d) and Fig. S17 in the Supplemental Material]. Due to the high transparency of the glass, the high X-ray luminescence efficiency and the negligible self-absorption effect of Cs3MnBr5 NCs, the spatial resolution of our glass sample reaches 19.1  lpmm1 at MTF=0.2, which exceeds most recently reported materials for X-ray imaging [Fig. 4(e)]. In addition, real-time radiography was successfully performed by recording the rotation procedure of an iron spring with an angular velocity of π/12  rads1. As shown in Fig. 4(f) and Video 1, we can see the image of the rotary spring, further confirming the high-quality and rapid X-ray imaging based on the Cs3MnBr5 NC-embedded glass.

Fig. 4

Demonstrations for real-time radiography. (a) The schematic of the X-ray imaging system. (b) Photographs of an AI chip (left), charging cable (middle), and circuit board (right) under daylight and X-ray irradiation. Scale bars, 1 cm. (c) Bright-field and X-ray images of the standard X-ray resolution pattern plate with the Cs3MnBr5 NC-embedded glass. (d) MTF of X-ray images obtained from the Cs3MnBr5 NC-embedded glass (the thickness is 0.6 mm). (e) Comparisons of spatial resolutions in representative scintillators.9,1618,4446 (f) Real-time dynamic X-ray images recording the procedure of two-dimensional rotation of an iron spring; the speed of angular velocity is π/12  rads1 (Video 1, MP4, 14 MB [URL: https://doi.org/10.1117/1.AP.5.4.046002.s1]). Scale bar, 5 mm.

AP_5_4_046002_f004.png

2.5.

Ultrastable X-Ray Imaging Application

Owing to the encapsulation by the glass medium and the stability of the anti-perovskite structures, the Cs3MnBr5 NC-embedded glass is expected to be used for X-ray imaging applications in medical fields and space stations. Moreover, we are surprised to find that the Cs3MnBr5 NC-embedded glass has very stable X-ray-excited optical properties when tested in a variety of harsh environments. The temperature-dependent RL spectra of Cs3MnBr5 NC-embedded glass are shown in Figs. 5(a) and 5(b). It can be found that at temperature up to 563 K, the RL intensity of red emission from Mn2+ in the glass drops sharply, while the green emission from Cs3MnBr5 NCs retains 73% of the room temperature intensity. In addition, the high thermal stability is further supported by the periodic change in emission intensity under repeated heating/cooling from 303 to 563 K for six cycles, as shown in Fig. 5(c). The excellent RL stability of Cs3MnBr5 NC-embedded glass in high-temperature environment exceeds most recently reported materials for X-ray imaging (Table S1 in the Supplemental Material). These results indicate that Cs3MnBr5 NC-embedded glass possesses strong thermal stability.

Fig. 5

Ultrastable X-ray imaging. (a) Temperature-dependent RL spectra and (b) emission mapping of the glass sample under X-ray irradiation with a dose rate of 4.814  mGyairs1. (c) RL intensity of the Cs3MnBr5 NCs in the glass sample upon six heating/cooling cycling processes over the temperature ranging from 303 to 563 K. (d) Photographs of a cylindrical ABS resin embedded with an iron spring in the air (top) and dimethyl silicone oil (bottom). (e) Thermal imaging photographs (top) and X-ray images (bottom) of the cylindrical ABS resin embedded with an iron spring immersed in dimethyl silicone oil at different temperatures. Scale bar, 1 cm. (f) RL intensity of Cs3MnBr5 NCs in the glass recorded over continuous 120 on/off cycles during 60 min. (g) Photograph (left) and X-ray images (right) of the chip taken under continuous irradiation for 2 h. Scale bar, 2 mm.

AP_5_4_046002_f005.png

We continue with a series of demonstrations of the imaging performance of the Cs3MnBr5 NC-embedded glass in different environments. First, an iron spring is encapsulated in an ABS cylindrical resin and placed together with the Cs3MnBr5 NC-embedded glass in a 1  cm×1  cm×10  cm colorimetric dish filled with dimethyl silicone oil [Fig. 5(d)]. The spring inside is not visible under daylight but can be imaged by Cs3MnBr5 NC-embedded glass under X-ray irradiation. In addition, the X-ray images of the spring can be detected at different temperatures, benefited by the stable thermal RL property of Cs3MnBr5 NC-embedded glass [Fig. 5(e)]. In this experiment, the temperature of the Cs3MnBr5 NC-embedded glass is detected by using an infrared camera. The X-ray image at the temperature up to 121.6°C is still clear, indicating that the Cs3MnBr5 NC-embedded glass can be used for high-temperature X-ray imaging. In another experiment, we place an integrated circuit chip and the Cs3MnBr5 NC-embedded glass in deionized water and recorded the underwater X-ray imaging for 24 h [Fig. S18(a, b) in the Supplemental Material]. After the Cs3MnBr5 NC-embedded glass was immersed in deionized water for 0, 5, 15, and 24 h, the X-ray images of the internal structure of the chip are still clear. Moreover, the underwater X-ray images remain unchanged at different temperatures (Fig. S19 in the Supplemental Material). Figure 5(f) presents the RL intensity of Cs3MnBr5 NC-embedded glass recorded under repeated high-dose X-ray (5.775  mGyairs1) excitation. It can be seen that after 120 on–off cycles, the RL intensity remains unchanged, showing good long-term X-ray irradiation stability. Moreover, even under a higher dose rate up to 9.66  mGairs1, its luminescence was only slightly affected for a short time (Fig. S20 in the Supplemental Material). In addition, the X-ray images from Cs3MnBr5 NC-embedded glass can still be observed after continuous X-ray irradiation for 2 h at a high dose rate up to 5.775  mGyairs1 [Fig. 5(g)]. Considering the above X-ray imaging demonstrations in different environments, the Cs3MnBr5 NC-embedded glass is expected to be applied for the next generation of scintillation materials.

3.

Conclusion

In summary, we have successfully prepared an ultrastable monolithic scintillator based on a lead-free Cs3MnBr5 anti-perovskite NC-embedded glass. The experimental results show that the Cs3MnBr5 NC-embedded glass has high optical transmittance, excellent tunable optical properties, and durable stability. Therefore, the Cs3MnBr5 NC-embedded glass can achieve an X-ray detection limit of 767  nGyairs1, high X-ray imaging spatial resolution of 19.1  lpmm1, and excellent stability under high-dose X-ray irradiation. The Cs3MnBr5 NC-embedded glass can be made into optical fibers, so the X-ray imaging performance and resolution may be further improved by using the pixelated dual tapered fiber arrays method.47 More importantly, with the protection of the glass matrix and the stability of the anti-perovskite structure, we demonstrate high-resolution X-ray imaging under a high-temperature and humidity environment by using Cs3MnBr5 NC-embedded glass. Our findings not only provide an effective strategy for achieving ultrastable X-ray-excited luminescence in a harsh environment but also broaden the applications of lead-free anti-perovskite materials in the applications of advanced X-ray radiography.

4.

Appendix A: Sample Preparation

The glass samples were fabricated by using the melting-quenching method. Reagent-grade raw materials including GeO2, B2O3, ZnO, CaCO3, NaBr, Cs2CO3, and MnO (glass composition: 37GeO2-31B2O3-3CaO-2ZnO-3MnO-6Cs2O-18NaBr) were mixed and then melted at 1100°C. The PG was made by pouring the melt into a mold. Then the glass was annealed at 350°C for 5 h and cooled for 10 h to room temperature to release the thermal stress. The PG samples were cut after removal from the mold and well-polished for crystallization of Cs3MnBr5 anti-perovskite NCs by annealing at 490°C, 530°C, and 570°C.

5.

Appendix B: Sample Characterization

Differential scanning calorimetry was measured by an STA449C Jupiter (Netzsch, Bavaria, Germany) in an air atmosphere with a heating rate of 10°Cmin1. The XRD patterns were recorded by a D8 ADVANCE X-ray diffractometer (Bruker, Faellanden, Switzerland) with Cu/Kα (λ=0.1541  nm) radiation. Absorption spectra were measured on a Lambda 900 (Perkin Elmer, Waltham, MA) spectrophotometer. An Edinburgh FLS 920 instrument (Edinburgh Instruments Ltd., Livingston, United Kingdom) equipped with a photomultiplier tube for light detection (Hamamatsu, Japan) was used to measure the PL spectra, excitation spectra, and lifetime decay of bulk glass sample. A 450 W ozone‐free xenon lamp and a microsecond‐pulsed xenon flash lamp were used as excitation sources during PL and lifetime decay measurement, respectively. For thermal and optical stability tests, PL spectra were excited by a 375 nm laser and recorded by an Ocean Optics HR4000 spectrometer. XPS measurements were performed on an Axis Ultra DLD XPS instrument (Kratos, England) with a monochromatic Al Kα source (1486.6 eV). The morphology and size distribution of Cs3MnBr5 NCs were measured by transmission electron microscopy (TEM, JEM-2100F, JEOL, Japan). The glass sample after crystallization was put into an agate mortar and ground to powder in ethanol for 20 min, and then dispersed in ethanol with ultrasonic treatment for 10 min. Finally, three to five drops of supernatant were dropped on the copper net for the TEM image test. The model of the electric rotary displacement table used for real-time imaging was Thorlabs PRM1Z8. FLS1000 spectrofluorometer (Edinburgh Instruments Ltd., United Kingdom) equipped with an X-ray tube (MAGPRO, Moxtek, W target and tube voltage 50 kV) is used to measure the RL spectra. The digital camera used for X-ray imaging is a Nikon d610.

6.

Appendix C: Calculation of the X-Ray Attenuation Coefficients

The detail of calculation is fully described in the subsection entitled “Supplementary Note 2” in the Supplemental Material.

Code, Data, and Material Availability

Data underlying the results presented in this paper may be obtained from the corresponding author upon reasonable request. All software is also available from the corresponding author upon reasonable request.

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (62122027, 52002128, 62075063, 62205109, 12204179, 52202004), Key R&D Program of Guangzhou (202007020003), fellowship of the China Postdoctoral Science Foundation (2022M711185, 2021M691054), National Postdoctoral Program for Innovative Talents of China (BX20220113), Guangdong Basic and Applied Basic Research Foundation (2021A1515110911, 2021A1515110475, 2022A1515011289, 2023A1515012666), Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01X137), Fundamental Research Funds for the Central Universities (2022ZYGXZR030), Guangzhou Basic and Applied Basic Research Foundation (202201010428), and State Key Laboratory of Luminescent Materials and Devices, South China University of Technology. The authors declare no competing interests.

References

1. 

J. A. Rowlands, “Material change for X-ray detectors,” Nature, 550 (7674), 47 –48 https://doi.org/10.1038/550047a (2017). Google Scholar

2. 

J. Pang et al., “Vertical matrix perovskite X-ray detector for effective multi-energy discrimination,” Light Sci. Appl., 11 (1), 105 https://doi.org/10.1038/s41377-022-00791-y (2022). Google Scholar

3. 

J. Jiang et al., “Synergistic strain engineering of perovskite single crystals for highly stable and sensitive X-ray detectors with low-bias imaging and monitoring,” Nat. Photonics, 16 (8), 575 –581 https://doi.org/10.1038/s41566-022-01024-9 NPAHBY 1749-4885 (2022). Google Scholar

4. 

J. Perego et al., “Composite fast scintillators based on high-Z fluorescent metal–organic framework nanocrystals,” Nat. Photonics, 15 (5), 393 –400 https://doi.org/10.1038/s41566-021-00769-z NPAHBY 1749-4885 (2021). Google Scholar

5. 

S. Cho et al., “Hybridisation of perovskite nanocrystals with organic molecules for highly efficient liquid scintillators,” Light Sci. Appl., 9 (1), 156 https://doi.org/10.1038/s41377-020-00391-8 (2020). Google Scholar

6. 

Q. Chen et al., “All-inorganic perovskite nanocrystal scintillators,” Nature, 561 (7721), 88 –93 https://doi.org/10.1038/s41586-018-0451-1 (2018). Google Scholar

7. 

X. Huang et al., “Reversible 3D laser printing of perovskite quantum dots inside a transparent medium,” Nat. Photonics, 14 (2), 82 –88 https://doi.org/10.1038/s41566-019-0538-8 NPAHBY 1749-4885 (2020). Google Scholar

8. 

H. Zhang et al., “Reproducible X‐ray imaging with a perovskite nanocrystal scintillator embedded in a transparent amorphous network structure,” Adv. Mater., 33 (40), 2102529 https://doi.org/10.1002/adma.202102529 ADVMEW 0935-9648 (2021). Google Scholar

9. 

W. Ma et al., “Highly resolved and robust dynamic X-ray imaging using perovskite glass-ceramic scintillator with reduced light scattering,” Adv. Sci., 8 (15), 2003728 https://doi.org/10.1002/advs.202003728 (2021). Google Scholar

10. 

J. Yuan et al., “How to apply metal halide perovskites to photocatalysis: challenges and development,” Nanoscale, 13 (23), 10281 –10304 https://doi.org/10.1039/D0NR07716J NANOHL 2040-3364 (2021). Google Scholar

11. 

M. Li and Z. Xia, “Recent progress of zero-dimensional luminescent metal halides,” Chem. Soc. Rev., 50 (4), 2626 –2662 https://doi.org/10.1039/D0CS00779J CSRVBR 0306-0012 (2021). Google Scholar

12. 

S. Cheng et al., “Ultrabright and highly efficient all‐inorganic zero‐dimensional perovskite scintillators,” Adv. Opt. Mater., 9 (13), 2100460 https://doi.org/10.1002/adom.202100460 2195-1071 (2021). Google Scholar

13. 

M. Hunyadi et al., “Scintillator of polycrystalline perovskites for high‐sensitivity detection of charged‐particle radiations,” Adv. Funct. Mater., 32 (48), 2206645 https://doi.org/10.1002/adfm.202206645 AFMDC6 1616-301X (2022). Google Scholar

14. 

B. Yang et al., “Lead-free halide Rb2CuBr3 as sensitive X-ray scintillator,” Adv. Mater., 31 (44), 1904711 https://doi.org/10.1002/adma.201904711 ADVMEW 0935-9648 (2019). Google Scholar

15. 

W. Zhu et al., “Low-dose real-time X-ray imaging with nontoxic double perovskite scintillators,” Light Sci. Appl., 9 (1), 112 https://doi.org/10.1038/s41377-020-00353-0 (2020). Google Scholar

16. 

F. Zhang et al., “Thermally activated delayed fluorescence zirconium-based perovskites for large-area and ultraflexible X-ray scintillator screens,” Adv. Mater., 34 (43), 2204801 https://doi.org/10.1002/adma.202204801 ADVMEW 0935-9648 (2022). Google Scholar

17. 

K. Han et al., “Seed-crystal-induced cold sintering toward metal halide transparent ceramic scintillators,” Adv. Mater., 34 (17), 2110420 https://doi.org/10.1002/adma.202110420 ADVMEW 0935-9648 (2022). Google Scholar

18. 

B. Li et al., “Zero‐dimensional luminescent metal halide hybrids enabling bulk transparent medium as large‐area X‐ray scintillators,” Adv. Opt. Mater., 10 (10), 2102793 https://doi.org/10.1002/adom.202102793 2195-1071 (2022). Google Scholar

19. 

Q. Kong et al., “Phase engineering of cesium manganese bromides nanocrystals with color-tunable emission,” Angew. Chem. Int. Ed. Engl., 60 (36), 19653 –19659 https://doi.org/10.1002/anie.202105413 ACIEAY 0570-0833 (2021). Google Scholar

20. 

K. Li et al., “Ultra-stable and color-tunable manganese ions doped lead-free cesium zinc halides nanocrystals in glasses for light-emitting applications,” Nano Res., 15 (10), 9368 –9376 https://doi.org/10.1007/s12274-022-4607-9 1998-0124 (2022). Google Scholar

21. 

Y. Wang et al., “Antiperovskites with exceptional functionalities,” Adv. Mater., 32 (7), 1905007 https://doi.org/10.1002/adma.201905007 ADVMEW 0935-9648 (2020). Google Scholar

22. 

D. Han et al., “Design of high-performance lead-free quaternary antiperovskites for photovoltaics via ion type inversion and anion ordering,” J. Am. Chem. Soc., 143 (31), 12369 –12379 https://doi.org/10.1021/jacs.1c06403 JACSAT 0002-7863 (2021). Google Scholar

23. 

H. K. Singh et al., “High-throughput screening of magnetic antiperovskites,” Chem. Mater., 30 (20), 6983 –6991 https://doi.org/10.1021/acs.chemmater.8b01618 CMATEX 0897-4756 (2018). Google Scholar

24. 

J. Zheng et al., “Antiperovskite K3OI for K-ion solid state electrolyte,” J. Phys. Chem. Lett., 12 (30), 7120 –7126 https://doi.org/10.1021/acs.jpclett.1c01807 JPCLCD 1948-7185 (2021). Google Scholar

25. 

N. Hoffmann et al., “Superconductivity in antiperovskites,” NPJ Comput. Mater., 8 (1), 150 https://doi.org/10.1038/s41524-022-00817-4 (2022). Google Scholar

26. 

S. Tan et al., “An antiperovskite compound with multifunctional properties: Mn3PdN,” Int. J. Heat. Mass. Transf., 302 122389 https://doi.org/10.1016/j.jssc.2021.122389 IJHMAK 0017-9310 (2021). Google Scholar

27. 

S. Yan et al., “Light-emitting diodes with manganese halide tetrahedron embedded in anti-perovskites,” ACS Energy Lett., 6 (5), 1901 –1911 https://doi.org/10.1021/acsenergylett.1c00250 (2021). Google Scholar

28. 

M. Kogia et al., “High temperature shear horizontal electromagnetic acoustic transducer for guided wave inspection,” Sensors, 16 (4), 582 https://doi.org/10.3390/s16040582 SNSRES 0746-9462 (2016). Google Scholar

29. 

T. Fukuchi et al., “Nondestructive inspection of thermal barrier coating of gas turbine high temperature components,” IEEJ Trans. Electr. Electron. Eng., 11 (4), 391 –400 https://doi.org/10.1002/tee.22255 (2016). Google Scholar

30. 

R. Kuhn et al., “Measuring device for synchrotron X-ray imaging and first results of high temperature polymer electrolyte membrane fuel cells,” J. Power Sources, 196 (12), 5231 –5239 https://doi.org/10.1016/j.jpowsour.2010.11.025 JPSODZ 0378-7753 (2011). Google Scholar

31. 

F. Akitomo et al., “Investigation of effects of high temperature and pressure on a polymer electrolyte fuel cell with polarization analysis and X-ray imaging of liquid water,” J. Power Sources, 431 205 –209 https://doi.org/10.1016/j.jpowsour.2019.04.115 JPSODZ 0378-7753 (2019). Google Scholar

32. 

Y. Wang et al., “In situ high-pressure and high-temperature X-ray microtomographic imaging during large deformation: a new technique for studying mechanical behavior of multiphase composites,” Geosphere, 7 (1), 40 –53 https://doi.org/10.1130/GES00560.1 (2011). Google Scholar

33. 

M. Yao et al., “High-temperature stable FAPbBr3 single crystals for sensitive X-ray and visible light detection toward space,” Nano Lett., 21 (9), 3947 –3955 https://doi.org/10.1021/acs.nanolett.1c00700 NALEFD 1530-6984 (2021). Google Scholar

34. 

V. S. Devahdhanush et al., “Experimental heat transfer results and flow visualization of vertical upflow boiling in Earth gravity with subcooled inlet conditions: in preparation for experiments onboard the international space station,” Int. J. Heat. Mass. Transf., 188 122603 https://doi.org/10.1016/j.ijheatmasstransfer.2022.122603 IJHMAK 0017-9310 (2022). Google Scholar

35. 

L. Shao et al., “Broadband ultraviolet photodetectors based on cerium doped lead-free Cs3MnBr5 metal halide nanocrystals,” ACS Sustain. Chem. Eng., 9 (14), 4980 –4987 https://doi.org/10.1021/acssuschemeng.0c07911 (2021). Google Scholar

36. 

Y. Wu et al., “New photoluminescence hybrid perovskites with ultrahigh photoluminescence quantum yield and ultrahigh thermostability temperature up to 600 K,” Nano Energy, 77 105170 https://doi.org/10.1016/j.nanoen.2020.105170 (2020). Google Scholar

37. 

R. Baran, L. Valentin and S. Dzwigaj, “Incorporation of Mn into the vacant T-atom sites of a BEA zeolite as isolated, mononuclear Mn: FTIR, XPS, EPR and DR UV-Vis studies,” Phys. Chem. Chem. Phys., 18 (17), 12050 –12057 https://doi.org/10.1039/C6CP01713D PPCPFQ 1463-9076 (2016). Google Scholar

38. 

L. Q. Guan et al., “All-inorganic manganese-based CsMnCl3 nanocrystals for X-ray imaging,” Adv. Sci., 9 (18), 2201354 https://doi.org/10.1002/advs.202201354 (2022). Google Scholar

39. 

S. Lv et al., “Transition metal doped smart glass with pressure and temperature sensitive luminescence,” Adv. Opt. Mater., 6 (21), 1800881 https://doi.org/10.1002/adom.201800881 2195-1071 (2018). Google Scholar

40. 

S. Lin et al., “High-security-level multi-dimensional optical storage medium: nanostructured glass embedded with LiGa5O8: Mn2+ with photostimulated luminescence,” Light Sci. Appl., 9 (1), 22 https://doi.org/10.1038/s41377-020-0258-3 (2020). Google Scholar

41. 

T. Jiang et al., “Highly efficient and tunable emission of lead‐free manganese halides toward white light‐emitting diode and X‐ray scintillation applications,” Adv. Funct. Mater., 31 (14), 2009973 https://doi.org/10.1002/adfm.202009973 AFMDC6 1616-301X (2021). Google Scholar

42. 

T. Ji et al., “Ce3+‐doped yttrium aluminum garnet transparent ceramics for high‐resolution X‐ray imaging,” Adv. Opt. Mater., 10 (6), 2102056 https://doi.org/10.1002/adom.202102056 2195-1071 (2022). Google Scholar

43. 

H. Wei et al., “Sensitive X-ray detectors made of methylammonium lead tribromide perovskite single crystals,” Nat. Photonics, 10 (5), 333 –339 https://doi.org/10.1038/nphoton.2016.41 NPAHBY 1749-4885 (2016). Google Scholar

44. 

W. F. Wang et al., “Sensitive X-ray detection and imaging by a scintillating lead(II)-based metal-organic framework,” Chem. Eng. J., 430 133010 https://doi.org/10.1016/j.cej.2021.133010 (2022). Google Scholar

45. 

M. Zhang et al., “Oriented-structured CsCu2I3 film by close-space sublimation and nanoscale seed screening for high-resolution X-ray imaging,” Nano Lett., 21 (3), 1392 –1399 https://doi.org/10.1021/acs.nanolett.0c04197 NALEFD 1530-6984 (2021). Google Scholar

46. 

X. Ou et al., “High-resolution X-ray luminescence extension imaging,” Nature, 590 (7846), 410 –415 https://doi.org/10.1038/s41586-021-03251-6 (2021). Google Scholar

47. 

L. Yi et al., “A double-tapered fibre array for pixel-dense gamma-ray imaging,” Nat. Photonics, 17 494 –500 https://doi.org/10.1038/s41566-023-01204-1 NPAHBY 1749-4885 (2023). Google Scholar

48. 

A. K. Mehra, “Trees correction matrices for d5 configuration in cubic symmetry,” J. Chem. Phys., 48 (10), 4384 –4386 https://doi.org/10.1063/1.1668005 JCPSA6 0021-9606 (1968). Google Scholar

49. 

J. L. Rao and K. Purandar, “Electronic absorption spectrum of Mn2+ ions doped in diglycine barium chloride monohydrate,” Solid State Commun., 37 (12), 983 https://doi.org/10.1016/0038-1098(81)91200-X SSCOA4 0038-1098 (1981). Google Scholar

50. 

F. Cao et al., “Shining emitter in a stable host: design of halide perovskite scintillators for X-ray imaging from commercial concept,” ACS Nano, 14 (5), 5183 –5193 https://doi.org/10.1021/acsnano.9b06114 ANCAC3 1936-0851 (2020). Google Scholar

51. 

J. Jin et al., “Zn2+ doping in organic manganese(II) bromide hybrid scintillators toward enhanced light yield for X‐ray imaging,” Adv. Opt. Mater., 2300330 https://doi.org/10.1002/adom.202300330 (2023). Google Scholar

52. 

T. C. Wang et al., “High thermal stability of copper-based perovskite scintillators for high-temperature X-ray detection,” ACS Appl. Mater. Interfaces, 15 (19), 23421 –23428 https://doi.org/10.1021/acsami.3c02041 AAMICK 1944-8244 (2023). Google Scholar

53. 

X. Li et al., “Mn2+ induced significant improvement and robust stability of radioluminescence in Cs3Cu2I5 for high-performance nuclear battery,” Nat. Commun., 12 (1), 3879 https://doi.org/10.1038/s41467-021-24185-7 NCAOBW 2041-1723 (2021). Google Scholar

Biography

Yakun Le is pursuing his PhD under the supervision of Prof. Guoping Dong, at the School of Materials Science and Engineering from the South China University of Technology (SCUT). His research focuses on metal halide nanocrystal-in-glass composite and their advanced optical applications.

Guoping Dong received his MS (2007) and PhD (2010) from Wuhan University of Technology and Shanghai Institute of Optics and Fine Mechanics (CAS), respectively. Then he worked in South China University of Technology (SCUT) as a research assistant (2010) and associate professor (2011). He is currently a full professor (2014) in State Key Laboratory of Luminescent Materials and Devices at SCUT. His research focuses on design, preparation, and optoelectronic properties of optical functional materials and devices.

Biographies of the other authors are not available.

CC BY: © The Authors. Published by SPIE and CLP under a Creative Commons Attribution 4.0 International License. Distribution or reproduction of this work in whole or in part requires full attribution of the original publication, including its DOI.
Yakun Le, Xiongjian Huang, Hao Zhang, Zhihao Zhou, Dandan Yang, Bozhao Yin, Xiaofeng Liu, Zhiguo Xia, Jianrong Qiu, Zhongmin Yang, and Guoping Dong "Transparent glassy composites incorporating lead-free anti-perovskite halide nanocrystals enable tunable emission and ultrastable X-ray imaging," Advanced Photonics 5(4), 046002 (10 July 2023). https://doi.org/10.1117/1.AP.5.4.046002
Received: 11 April 2023; Accepted: 12 June 2023; Published: 10 July 2023
Lens.org Logo
CITATIONS
Cited by 13 scholarly publications.
Advertisement
Advertisement
KEYWORDS
Glasses

Cesium

X-ray imaging

X-rays

Annealing

Manganese

Crystals

Back to Top