Nanophotonics 2021; 10(8): 2249–2256

Research article

Zhifang Tan, Jincong Pang, Guangda Niu*, Jun-Hui Yuan, Kan-Hao Xue, Xiangshui Miao, Weijian Tao, Haiming Zhu, Zhigang Li, Hongtao Zhao, Xinyuan Du and Jiang Tang* Tailoring the and hole dimensionality to achieve efficient and stable metal halide perovskite scintillators

−1 https://doi.org/10.1515/nanoph-2020-0624 detection limit of 0.7 µGyair s . The Received November 25, 2020; accepted January 26, 2021; and could be maintained without any published online February 17, 2021 loss when immersing in water or after 480,000 Gy radia- tions, outperforming previous perovskite and traditional Abstract: Metal halide perovskites have recently been re- metal halides scintillators. ported as excellent scintillators for X-ray detection. How- ever, perovskite based scintillators are susceptible to Keywords: electron and hole dimensionality; metal halide moisture and oxygen atmosphere, such as the water solu- perovskite; scintillators; stable; tailoring. 2+ + bility of CsPbBr3, and oxidation vulnerability of Sn ,Cu .

The traditional metal halide scintillators (NaI: Tl, LaBr3, etc.) are also severely restricted by their high hygroscop- 1 Introduction icity. Here we report a new kind of lead free perovskite with excellent water and radiation stability, Rb2Sn1-xTexCl6. The Metal halide perovskites have emerged as a new class of equivalent of Te could break the in-phase bonding promising emitters for various applications of lumines- interaction between neighboring octahedra in Rb2SnCl6, cence, such as electroluminescence, , , and thus decrease the electron and hole dimensionality. scintillators etc [1–10]. The adjustable composition and The optimized Te content of 5% resulted in high photo- defect tolerance nature endow perovskites with wide quantum yield of 92.4%, and low X-ray spectral tunability and high quantum efficiency. Several

recent papers have demonstrated the use of CsPbBr3 Zhifang Tan and Jincong Pang contributed equally to this work. nanocrystals as promising scintillators with good X-ray attenuation coefficient, tunable emission wavelength and *Corresponding authors: Guangda Niu, Wuhan National Laboratory low temperature solution processing [11–13]. The self- for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074, China; and Jiang Tang, Wuhan National Laboratory for trapped exciton emitters of low dimensional perovskites Optoelectronics, Huazhong University of Science and Technology, (Rb2CuBr3, Bmpip2SnBr4) have also been utilized as scin- Wuhan 430074, China; and School of Optical and Electronic tillators and shown high radioluminescence, benefiting Information, Huazhong University of Science and Technology, Wuhan from the negligible self-absorption effect [14, 15]. For example, 430074, China, E-mail: [email protected] (G. Niu), Kovalenko and co-workers found that Bmpip SnBr exhibited [email protected] (J. Tang). https://orcid.org/0000-0002- 2 4 ∼ 9285-4147 (G. Niu), https://orcid.org/0000-0003-2574-2943 (J. Tang) 1.7 times higher radioluminescence intensity than commer- Zhifang Tan, Jincong Pang and Xinyuan Du, Wuhan National cial NaI:Tl scintillator [15]. Scintillators have wide applications Laboratory for Optoelectronics, Huazhong University of Science and in detection of high-energy radiations, including X-rays and Technology, Wuhan 430074, China gamma rays. During the detection, scintillators firstly convert Jun-Hui Yuan, Kan-Hao Xue and Xiangshui Miao, School of Optical and X-rayorgammarayintovisiblephotons,whicharethen Electronic Information, Huazhong University of Science and Technology, Wuhan 430074, China collected by photosensors to give spatial or temporal Weijian Tao and Haiming Zhu, Department of Chemistry, Zhejiang information. University, Hangzhou 310027, China However, the currently reported perovskite related Zhigang Li and Hongtao Zhao, Technical Physics Institute, scintillators are susceptible to moisture and oxygen at- Heilongjiang Academy of Sciences, Harbin, Heilongjiang Province mosphere, such as the water solubility of CsPbBr , and 150086, China; and College of Nuclear Science and Technology, 3 2+ + Harbin Engineering University, Harbin, Heilongjiang Province 150001, oxidation vulnerability of Sn ,Cu. The traditional scin- China tillators, NaI: Tl, LaBr3, are also severely restricted in

Open Access. © 2021 Zhifang Tan et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution 4.0 International License. 2250 Z. Tan et al.: Tailoring the electron and hole dimensionality

practical applications by their high hygroscopicity [16]. It is applications as scintillators for radiography and radio- of great significance to explore lead-free perovskite scin- sensitizers for in vivo radiodynamic therapy. tillators with excellent stability toward oxygen and mois- ture, as well as high radioluminescence intensity.

We speculate A2SnX6 (A=Cs, Rb; X=Cl, Br, I) as a 2 Results and discussions possible candidate considering its negligible water sol- 4+ ubility and stable valence states of Sn .However, The series of products Rb2Sn1−xTexCl6 were synthesized by although each Sn–X octahedron is completely separated dissolving designed stoichiometric ratio of RbCl, SnCl4, from the neighbors, previous studies have illustrated TeCl4 into HCl solution in a hydrothermal autoclave. The that the band structure of A2SnX6 does not follow the solution was heated and then slowly cooled down to room same behavior and no luminescence could be observed temperature. The resulting powder crystals were washed by

[17]. Taking Cs2SnI6 as an example, the conduction band isopropanol to remove surface-adsorbed ions. Figure 1a minimum (CBM) is from the antibonding of Sn 5s and I 5p shows the schematic crystal structure of Rb2Sn1−xTexCl6. orbitals [18]. At the Γ point, the antibonding orbital is Each Sn4+ (Te4+) is coordinated with six Cl− ions, and the inphasewiththatofadjacentcell,resultinginabond- formed Sn(Te)–Cl octahedra are completely separated from ing interaction between neighboring octahedra and each other by the presence of Rb+. Such structure could also disperse projection of halide p orbital into the inter- be viewed as vacancy ordered double perovskites. Figure 1b octahedral voids. shows the powder X-ray diffraction (PXRD) patterns of

We note that for efficient emissions, the CBM and Rb2Sn1−xTexCl6 samples. The diffraction patterns of all valence band maximum (VBM) should both have low Rb2Sn1−xTexCl6 follow the structure type of K2PtCl6 (space electronic dimensionality. Otherwise, the electron and hole group: Fm3m), where a = b = c and α = β = γ =90°.The orbital overlap and transition dipole moment will be calculated lattice constant (a)ofpureRb2SnCl6 is 10.088 Å ’ μ = 〈φ |μ̂|φ 〉 decreased according to Fermi s golden rule, h e , and that of Rb2TeCl6 is 10.148 Å, consistent with the ionic μ̂ φ φ 4+ 4+ where is the electric dipole operator, h and e are the radius of Sn (0.69 Å) and Te ion (0.97 Å). From the peaks hole and electron wavefunctions, respectively [19]. The with asterisks in the right panel, as Te4+ increases, the (111) delocalized CBM in above case of Cs2SnI6 is responsible for diffraction peak moves to the left. The alloys exhibit pure its negligible luminescence. Thereby it is desired to intro- phase and the lattice constant gradually increases upon the duce equivalent ions to partially replace Sn4+ for reduced introduction of Te4+, demonstrating the random replace- electronic dimensionality to boost emissions, and such ment of Sn4+ by Te4+ to yield solid solutions. study has not been reported as far as we are concerned. The tetravalent oxidation state of Te and Sn were In this work, we report a new lead-free double perov- confirmed by X-ray photoelectron spectroscopy (XPS) skite Rb2Sn1-xTexCl6 with efficient X-ray scintillation, and measurements (Figure 1c and Figure S1). The peaks at 4+ ultra-high stability against moisture and high energy ra- 576.36 and 586.66 eV are attributed to Te 3d5/2 and 3d3/2, 4+ 4+ 4+ diations. Te could partially substitute Sn in the struc- and those at 486.86 and 496.36 eV correspond to Sn 3d5/2 ture. At the CBM, Te 5p orbital interacts with Cl 3p orbital, and 3d3/2, respectively. Also, the energy dispersive spec- which could break the in-phase bonding interaction be- trometer (EDS) mapping of Rb2Sn0.8Te0.2Cl6 in Figure 1d tween neighboring octahedra in Rb2SnCl6. The electronic shows the homogeneous distributions of rubidium (Rb), tin dimensionality is thereby reduced, and we experimentally (Sn), tellurium (Te) and chlorine (Cl) elements in the observed the self-trapped exciton emission in the alloy product, also confirming the random occupation of Te4+ on 4+ Rb2Sn1−xTexCl6. When the Te content is 5%, the products Sn lattice sites. exhibited wide emission spectra (peak at ∼580 nm), high UV–vis absorption and photoluminescence (PL) photoluminescence quantum yield of 92.4%, and photo- spectra are shown in Figure 2a and b. It is clearly observed luminescence lifetime of 1.16 µs. Under X-ray excitation, that the absorption within the region of 300–500 nm is the radioluminescence intensity is 39% of commercial enhanced with the increase of Te contents. The origin of −1 Gd2O2S: Tb scintillators (66,500 MeV ) and the band gap change will be discussed later. As shown in −1 detection limit is as low as 0.7 µGyair s . The photo- Figure 2b, for photoluminescence upon excitation at luminescence and radioluminescence could be maintained 380 nm, Rb2Sn1-xTexCl6 shows a broad yellow emission. without any loss when immersing in water or after Upon increasing the Te content, the emission peak red 480,000 Gy radiations, outperforming previous perovskite shifted from 566 to 586 nm, which are caused by the and traditional metal halides scintillators. Considering decreased band gaps [17]. In addition, the full-width-at- its excellent stability, Rb2Sn1−xTexCl6 may find vast half-maximum (FWHM) increased from 108 to 122 nm. Z. Tan et al.: Tailoring the electron and hole dimensionality 2251

a) b) *

* * * *

2 theta (degree)

Te-raw c)Sn 3d 5/2 Te-fit d) Rb Sn Sn-raw ) ) Sn-fit . . u u Te 3d 5/2 . . Sn 3d 3/2 a a ( ( Te 3d 3/2 y y t t i i s s n n e e t

t Te Cl n n I I

485 490 495 570 575 580 585 590 BindingBinding Energy Energy (eV)

2− Figure 1: (a) Schematic crystal structure of Rb2Sn1−xTexCl6 double perovskites. (Dark green octahedron: [SnCl6] ; purple octahedron: 2− [TeCl6] ). (b) Powder X-ray diffraction (PXRD) for the series of Rb2Sn1−xTexCl6, and the peaks with asterisks in the left picture are displayed with enlarged abscissa on the right. (c) X-ray photoelectron spectroscopy (XPS) and peak fitting for Sn 3d and Te 3d orbitals, respectively. (d) Energy dispersive mapping of elements Rb, Sn, Te and Cl for the prepared powders.

Furthermore, the photoluminescent quantum yields estimated around 140 nm. The negligible overlap between (PLQYs) were also recorded. As shown in Figure 2c, the PL and PLE indicates that the self-absorption effect is not reference (black curve) of a quartz plate and Rb2Sn1-xTexCl6 significant for the products, which is ideal for efficient were put in an integrating sphere and excited by 380 nm out-coupling and achieving high radioluminescence. For light. The PLQY value was obtained via dividing integrated the time-resolved PL spectrum (Figure 3b), we could fit the emission intensity by the absorbance. Figure 2d shows the curve through a double exponential function. The two PLQYs for the series of solid solution. PLQY gets enhanced lifetimes are 0.19 and 3.32 µs, and the average decay time is upon introducing higher Te content, and reaches its 1.16 µs. The large Stokes shift and long lifetime imply the maximum value of 92.4% at 5% Te content. Such PLQY is possible formation of self-trapped excitons (STEs). among the highest values for all kinds of metal halide pe- We evaluate the electron-phonon coupling and self- rovskites [20–22]. trapped excitons by recording the temperature- In addition, to verify the mechanism of radiative dependent FWHM spectrum. The curve is fitted based recombination process, we also tested the photo- on the phonon broadening model, while the fitting luminescence (PL) and photoluminescence excitation function is shown in the inset of Figure 3c [23]. The

(PLE) spectra of Rb2Sn0.95Te0.05Cl6 as a function of the electron-phonon coupling could be quantitatively excitation and emission wavelengths, respectively. As studied by Huang-Rhys factor S,wherealargevalueofS exhibited in Figure 3a, both PL and PLE spectra show means strong electron-phonon coupling and favor- identical shapes. Above phenomenon indicates that the able formation of STEs. The obtained Huang-Rhys factor emission comes from the same excited states, excluding S is 30.7, and ћωphonon is 18.5 meV. The S value of the influence of defect emissions. The Stokes shift is Rb2Sn0.95Te0.05Cl6 is one order of magnitude higher than 2252 Z. Tan et al.: Tailoring the electron and hole dimensionality

1.4 ) .

a) b) u .

1.2 x=0 a x=0.005 (

x=0.05 )

x=0.005 y . t

i x=0.2 u 1.0 x=0.05 . s

a x=1 x=0.2 n (

e

0.8 x=0.5 t e n c x=1 I

n L a 0.6 P b

r d o e

s 0.4 z b i l A 0.2 a m r

0.0 o N 300 350 400 450 500 550 600 650 700 450 500 550 600 650 700 Wavelength (nm) Wavelength (nm) c) 10-5 d) 100 Reference -6 10 Rb2Sn0.95Te0.05Cl6 80 ) s

t -7 %

n 10 60 (

u o Y c

-8 Q Figure 2: (a) UV–vis absorption spectra of L 10 L 40 P P Rb2Sn1−xTexCl6. (b) PL spectra of 10-9 20 Rb2Sn1−xTexCl6, while no emission could be observed for Rb2SnCl6. (c) The PL spectra of -10 10 0 Rb2Sn0.95Te0.05Cl6 for PLQY measurement. 400 500 600 700 110100 (d) The PLQY values of Rb2Sn1−xTexCl6 with Wavelength (nm) Te contents (%) various x values.

Figure 3: (a) Wavelength-dependent PLE and

PL spectra for Rb2Sn0.95Te0.05Cl6. (b) PL

decay and fitting curve of Rb2Sn0.95Te0.05Cl6 powders. (c) Fitting results of full width at half maximum (FWHM) as a function of temperature from 83 to 353 K derived from the PL spectra. For the fitting equation, S is

Huang-Rhys factor, ћωphonon is the phonon

frequency (ћ, reduced Planck constant), kB is the boltzmann constant. (d) Transient

absorption spectra of Rb2Sn0.95Te0.05Cl6 ( pulse of 400 nm and 4 µJ cm−2), while the decay curve is for the wavelength of 456 nm ΔT/T is the transmittance change.

traditional emitters like CdSe(1),ZnSe(0.3),CsPbBr3 The transient absorption measurements on Rb2Sn0.95

(3.2), and slightly lower than Cs2Ag0.16Na0.84InCl6 (51.0) Te0.05Cl6 provide the formation kinetics of STEs (Figure 3d). [24–26]. Hence, we infer that the large electron-phonon Upon excitation at 400 nm, the sample showed a broad coupling could promptly transform the excited excitons featureless photo-induced absorption (PIA) signal from into the self-trapped states, which then radiatively 430 to 480 nm. The PIA signal rises within ∼300 fs, sug- recombine to produce broad emissions. gesting an ultrafast exciton self-trapping process. According Z. Tan et al.: Tailoring the electron and hole dimensionality 2253

to the previously obtained phonon frequency (18.5 meV), we the charges at VBM are completely isolated. In contrast, could estimate the self-trapping time as τ = 2π = 223 fs. although Sn–Cl octahedra are isolated from each other, ωphonon The consistency of the observed and estimated self-trapping dispersive CBM states are observed, indicating that the time also confirms the self-trapped exciton emissions. at the CBM tend to be delocalized. Neilson and fi The electronic band structures have been theoreti- co-workers previously utilized the simpli ed orbital cally calculated. As shown in Figure 4a, using a self- bonding picture to explain the above abnormal phe- energy corrected shGGA-1/2 method [27, 28], the band nomenon, which can also be applied in this work (Figure 4d) [15]. For CBM, the Sn 5s orbital hybridizes gap of Rb2SnCl6 was determined as 3.71 eV, consistent σ with the experimental results (∼3.9 eV). By introducing a with Cl 3p orbital with a bonding type, while the A1g certain amount (6 Te per 64 Sn, 9.375%) of Te, the antibonding orbital is in phase with the neighboring A1g calculated band gap decreased to 2.89 eV. One could orbital in the adjacent cell. Thereby there is a bonding identify the origin of the band structure through partial interaction between adjacent Sn–Cl octahedra. Due to the density of states analysis. Considering the electronic dispersive projection of halide p orbitals, the bonding configuration of Sn4+ (5s0 5p0), the VBM comes from the interaction extends to the inter-octahedral void. As non-bonding Cl 3p orbitals for pure Rb2SnCl6,whilethe stated in the introduction part, such behavior would CBM consists of the antibonding states between Sn 5s and decrease the electron and hole orbitaloverlap,lowering Cl 3p orbitals. In order to differentiate the degree of the emission efficiency accordingly. localization for carriers, we further performed 4 × 4 × 1 The influence of Te4+ doping over the electronic supercell calculations. The charge density isosurfaces dimensionality especially for CBM is further studied. 2 0 shown in Figure 4c, evaluated at the Γ point, reveal that Firstly, for pure Rb2TeCl6, the 5s 5p electron configuration ) V e (

y g r e n E

W L X W K DOS ) V e (

y g r e n E

X R M R DOS

Figure 4: Theoretical calculation results of Rb2SnCl6 (a–d) and Rb2Sn1−xTexCl6 (e–h). (a, e) Band structures and density of states. (b, f) Charge density isosurface of CBM. (c, g) Charge density isosurface of VBM. (d, h) Simplified molecular orbital picture. 2254 Z. Tan et al.: Tailoring the electron and hole dimensionality

of Te4+ adds two more electrons to occupy the antibonding be separately confined onto Sn–Cl octahedra and Te–Cl states from Te 5s and Cl 3p, and the higher binding energy octahedra, respectively, which nevertheless would of Te 5s orbital also lowers the energy level of the anti- decrease the overlap of electrons and holes again, bonding states. Hence, the CBM is composed of high- explaining the worsened PLQY when Te contents in energy antibonding state of Te 5p and Cl 3p orbitals. excessive.

For the case of Rb2Sn1-xTexCl6, we introduced six Te Figure 5a depicts the schematic process of X-ray scin- atoms into the supercell, corresponding to a doping con- tillation. The high energy X-rays interact with the inner tent of 9.37%. The CBM consists of Sn 5s and Cl 3p orbitals, shell electrons through photoelectric ionization. The and the presence of Te will create barriers for the delocal- generated energetic electrons can excite other secondary or ization of electrons. It is straightforward that the electronic tertiary electrons, which thermally relax to the conduction dimensionality will be reduced, as the yellow circle in band edge via interaction with optical and acoustic pho- Figure 4f indicates. Moreover, the VBM is then comprised nons. Then the electrons and holes could radiatively by antibonding states of Te 5s and Cl 3p orbitals, and we recombine to emit visible photons. The radioluminescence could clearly observe that the holes are strongly confined spectrum of Rb2Sn0.95Te0.05Cl6 has been measured under around Te–Cl octahedra (Figure 4g). The simultaneous 50 kV X-ray excitation (Figure S2). The spectrum is similar decrease of electronic dimensionality for electrons and to that under 380 nm UV-light, which demonstrates that holes contribute to the emission enhancement. Provided the same radiative recombination channel is taken under that the Te content is too large, the electrons and holes will either X-ray or UV excitation.

Vacuum

Conduction Band

Valence Band

N M h L3

L2

L1

Inner ShellX-ray

K

Figure 5: (a) Schematic diagram of the scintillation mechanism. (b) Absorption coefficients of Rb2Sn0.95Te0.05Cl6, Si, Lu1.8Y0.2SiO5: Ce (LYSO),

CsI: Tl and Gd2O2S: Tb (GOS) as a function of energy, from 1 keV (soft X-rays) to 100 MeV (gamma radiation) (c) Response voltage of

Rb2Sn0.95Te0.05Cl6 and GOS as a linear function of dose rate. The inset is the photograph of Rb2Sn0.95Te0.05Cl6 under neutral light and X-ray irradiation, separately. (d) Statistics of Rb2Sn0.95Te0.05Cl6 scintillation response before and after radiation dose of 480,000 Gy. Z. Tan et al.: Tailoring the electron and hole dimensionality 2255

The absorption coefficient of Rb2Sn0.95Te0.05Cl6 was radiation, we separated the pristine scintillator powder plotted in Figure 5b, with comparison to other typical into two parts, one was for radiation and the other one scintillators (Si, LYSO, CsI:Tl and GOS) in a wide photon served as the control. After radiation for 480,000 Gy, the energy range, according to the photon cross-section two samples were weighted equivalently and pressed into database [29]. Considering the density as 3.24 g cm−3 and pellets with exactly the same size. It should be noted that the light element composition, the absorption coeffi- the adopted total radiation dose is large enough, 107 times cient is lower than LYSO, CsI:Tl and GOS, but higher higher than the dose for computed tomography (10 mGy for than silicon. each inspection). Then the scintillation response of these To evaluate the radioluminescence intensity, we pellets was measured. The control samples (six pellets for assembled an integrating sphere into the system in statistics) exhibited an average response of 98.6 ± 6.2 mV, FigureS3.Wenotethatsuchsystemwillexcludethein- and the samples after radiation exhibited almost un- fluence of photon out-coupling effect, compared with our changed response of 95.6 ± 3.0 mV. Such good stability previously adopted method without integrating sphere benefits from the all-inorganic composition and no hy-

[12]. Moreover, to strictly compare the scintillation per- groscopicity of Rb2Sn0.95Te0.05Cl6. formance, we strongly recommend to pay attention to the area, geometry and position of the samples. As shown in Figure S3, the reference and samples should have the 3 Conclusions same thickness, area and shapes. Here we pressed com- mercial GOS and our Rb Sn Te Cl powders into 2 0.95 0.05 6 In summary, this work establishes the tailoring of electron small pellets. During the measurement, we posited these and hole dimensionality as an effective strategy to enhance two pellets onto the same position to avoid the influence photoluminescence and radioluminescence. The equiva- of nonuniformity and anode effect of X-ray tubes. lent substitution of Sn4+ by Te4+ ions can break the in-phase Considering the nonlinearity of Si-PM in high response bonding interaction between neighboring octahedra in range, we decreased the radiation dose rates. As shown in Rb SnCl , and induce the formation of self-trapped exci- Figure 5c, the response voltage was measured at different 2 6 tons via strong electron-phonon coupling effect. As a dose rates for determining the linear response range to the result, Rb Sn Te Cl exhibited wide emission spectra X-ray dose rate. The linear response of Rb Sn Te Cl 2 0.95 0.05 6 2 0.95 0.05 6 (peak at ∼580 nm), high photoluminescence quantum covers a wide range from 0.97 μGy /s to at least air yield of 92.4%, and photoluminescence lifetime of 1.16 µs. 6.79 μGyair/s. When SNR is 3, we can get the detection The scintillation response is 39% of commercial Gd2O2S: Tb limit of Rb Sn Te Cl is 700.5 nGy /s from the linear − 2 0.95 0.05 6 air scintillators (66,500 photons MeV 1) and the detection limit fitting curve, which is about eight times lower than the is 0.7 µGy s−1. More importantly, the excellent stability requirementofX-raydiagnosis(5.5μGy /s). The inset of air air toward water and large dose radiations render this material Figure 5c shows the photograph of Rb Sn Te Cl 2 0.95 0.05 6 with great promise in the field of X-ray imaging panels and under neutral light and X-rays irradiation. Upon the radiosensitizers for in vivo radiodynamic therapy. irradiation of X-rays, the sample emits clear yellow-green light in the dark. At last, in terms of the stability, we immersed Acknowledgment: The authors thank the Analytical and

Rb2Sn0.95Te0.05Cl6, CsPbBr3 and Rb2CuBr3 separately into Testing Center of HUST and the facility support of the three bottles with water. Rb2Sn0.95Te0.05Cl6 could hardly Center for Nanoscale Characterization and Devices, WNLO. dissolve into water and we can still observe the photo- Author contributions: All the authors have accepted luminescence and radioluminescence of Rb2Sn0.95Te0.05Cl6 responsibility for the entire content of this submitted after several hours. In sharp contrast, CsPbBr3 and manuscript and approved submission.

Rb2CuBr3 completely dissolved and no RL could be Research funding: This work was financially supported by observed in seconds (Figure S4). National Key R&D Program of China (2016YFB0700702, Moreover, we also record the radiation stability 2018YFA0703200), National Natural Science Foundation of of Rb2Sn0.95Te0.05Cl6 (Figure 5d). The scintillator pow- China (51761145048, 51702107, 61905082, 61725401, ders were unencapsulated and directly exposed to 60Co 51902113), China Post-doctoral Science Foundation ( 60 → 60 + ( . )+ radiation source 27 Co 28 Ni beta rays 0 317 MeV (2018M632843) and the Innovation Fund of WNLO. gamma rays(1.17, 1.33 MeV)). In order to accurately Conflict of interest statement: The authors declare no compare the scintillation response before and after conflicts of interest regarding this article. 2256 Z. Tan et al.: Tailoring the electron and hole dimensionality

References [16] C. Dujardin, E. Auffray, E. Bourret-Courchesne, et al., “Needs, trends, and advances in inorganic scintillators,” IEEE Trans. Nucl. Sci., vol. 65, pp. 1977–1997, 2018. [1] K. Lin, J. Xing, L. N. Quan, et al., “Perovskite light-emitting diodes [17] A. E. Maughan, A. M. Ganose, D. O. Scanlon, and J. R. Neilson, with external quantum efficiency exceeding 20 per cent,” Nature, “Perspectives and design principles of vacancy-ordered double vol. 562, pp. 245–248, 2018. perovskite halide ,” Chem. Mater., vol. 31, [2] Z. Tan, J. Li, C. Zhang, et al., “Highly efficient blue-emitting Bi- pp. 1184–1195, 2019. doped Cs2SnCl6 perovskite variant: photoluminescence induced [18] A. E. Maughan, A. M. Ganose, M. M. Bordelon, et al., “Defect by impurity doping,” Adv. Funct. Mater., vol. 28, p. 1801131, tolerance to intolerance in the vacancy-ordered double

2018. perovskite semiconductors Cs2SnI6 and Cs2TeI6,” J. Am. Chem. [3] S. A. Veldhuis, P. P. Boix, N. Yantara, et al., “Perovskite materials Soc., vol. 138, pp. 8453–8464, 2016. for light-emitting diodes and lasers,” Adv. Mater., vol. 28, [19] J. Luo, X. Wang, S. Li, et al., “Efficient and stable emission of pp. 6804–6834, 2016. warm-white light from lead-free halide double perovskites,” [4] J. H. Heo, D. H. Shin, J. K. Park, et al., “High-performance next- Nature, vol. 563, pp. 541–545, 2018. generation scintillator for nondestructive [20] J. J. Luo, M. C. Hu, G. D. Niu, and J. Tang, “Lead-free halide X-ray imaging,” Adv. Mater., vol. 30, p. e1801743, 2018. perovskites and perovskite variants as phosphors toward light- [5] J. Liu, B. Shabbir, C. Wang, et al., “Flexible, printable soft-X-ray emitting applications,” ACS Appl. Mater. Interfaces, vol. 11, detectors based on all-inorganic perovskite quantum dots,” Adv. pp. 31575–31584, 2019. Mater., vol. 31, p. e1901644, 2019. [21] C. K. Zhou, H. R. Lin, Y. Tian, et al., “Luminescent zero- [6] S. Pathak, N. Sakai, F. Wisnivesky Rocca Rivarola, et al., dimensional organic metal halide hybrids with near-unity “Perovskite crystals for tunable white light emission,” Chem. quantum efficiency,” Chem. Sci., vol. 9, pp. 586–593, 2018. Mater., vol. 27, pp. 8066–8075, 2015. [22] M. V. Kovalenko, L. Protesescu, and M. I. Bodnarchuk, [7] N. Wang, L. Cheng, R. Ge, et al., “Perovskite light-emitting diodes “Properties and potential optoelectronic applications of lead based on solution-processed self-organized multiple quantum halide perovskite nanocrystals,” Science, vol. 358, pp. 745–750, wells,” Nat. Photonics, vol. 10, pp. 699–704, 2016. 2017. [8] M. A. Becker, R. Vaxenburg, G. Nedelcu, et al., “Bright triplet [23] G. Blasse and G. J. Dirksen, “The influence of distortion of the Te excitons in caesium lead halide perovskites,” Nature, vol. 553, (IV) coordination octahedron on its luminescence,” Chem. Phys. pp. 189–193, 2018. Lett., vol. 136, pp. 460–464, 1987. + [9] Y. Jing, Y. Liu, X. Jiang, et al., “Sb3 dopant and halogen [24] V. Turck, S. Rodt, O. Stier, et al., “Effect of random field substitution triggered highly efficient and tunable emission in fluctuations on excitonic transitions of individual CdSe quantum lead-free metal halide single crystals,” Chem. Mater., vol. 32, dots,” Phys. Rev. B, vol. 61, pp. 9944–9947, 2000. p. 5327, 2020. [25] H. Zhao and H. Kalt, “Energy-dependent Huang-Rhys factor of [10] G. Zhou, B. Su, J. Huang, Q. Zhang, and Z. Xia, “Broad-band free excitons,” Phys. Rev. B, vol. 68, p. 5, 2003. emission in metal halide perovskites: mechanism, materials, [26] X. Z. Lao, Z. Yang, Z. C. Su, et al., “Luminescence and thermal and applications,” Mater. Sci. Eng. R,vol.141,p.100548, behaviors of free and trapped excitons in cesium lead halide 2020. perovskite nanosheets,” Nanoscale, vol. 10, pp. 9949–9956, [11] Y. Zhang, R. Sun, X. Ou, et al., “Metal halide perovskite 2018. nanosheet for X-ray high-resolution scintillation imaging [27] K.-H. Xue, J.-H. Yuan, L. R. C. Fonseca, and X.-S. Miao, “Improved screens,” ACS Nano, vol. 13, pp. 2520–2525, 2019. LDA-1/2 method for band structure calculations in covalent [12] Q. Chen, J. Wu, X. Ou, et al., “All-inorganic perovskite nanocrystal semiconductors,” Comput.Mater.Sci.,vol.153,pp.493–505, 2018. scintillators,” Nature, vol. 561, pp. 88–93, 2018. [28] L. G. Ferreira, M. Marques, and L. K. Teles, “Approximation to [13] S. Shrestha, R. Fischer, G. J. Matt, et al., “High-performance density functional theory for the calculation of band gaps of direct conversion X-ray detectors based on sintered hybrid lead semiconductors,” Phys. Rev. B, vol. 78, 2008, https://doi.org/ triiodide perovskite wafers,” Nat. Photonics, vol. 11, 10.1103/physrevb.78.125116. pp. 436–440, 2017. [29] M. J. Berger, J. H. Hubbell, S. M. Seltzer, et al., XCOM: Photon [14] B. Yang, L. Yin, G. Niu, et al., “Lead-free halide Rb2 CuBr3 as Cross Sections Database: NIST Standard Reference Database 8, sensitive X-ray scintillator,” Adv. Mater., vol. 31, p. e1904711, 2013. Available at: https://www.nist.gov/pml/xcom-photon- 2019. cross-sections-database. [15] V. Morad, Y. Shynkarenko, S. Yakunin, et al., “Disphenoidal zero- dimensional lead, tin, and germanium halides: highly emissive singlet and triplet self-trapped excitons and X-ray scintillation,” Supplementary Material: The online version of this article offers J. Am. Chem. Soc., vol. 141, pp. 9764–9768, 2019. supplementary material (https://doi.org/10.1515/nanoph-2020-0624).