Full-color and time-valve controllable long-persistent luminescence from all-inorganic halide perovskites

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However, recently developed LPL materials – encompassing inorganics, organics and inorganic-organic hybrids – often display monochromatic afterglow with limited functionality. Furthermore, triplet exciton-based phosphors are prone to thermal quenching, significantly restricting their high emission efficiency. Here, we present a straightforward wet-chemistry approach for fabricating multimode LPL materials by introducing both anion (Br − ) and cation (Sn 2+ ) doping into hexagonal CsCdCl 3 all-inorganic perovskites. This process involves establishing new trapping centers from [CdCl 6 − n Br n ] 4− and/or [Sn 2 − n Cd n Cl 9 ] 5− linker units, disrupting the local symmetry in the host framework. These halide perovskites demonstrate obviously extended afterglow duration time (> 2,000 s), nearly full-color coverage, and high photoluminescence quantum yield (~ 84.47%). Moreover, they exhibit remarkable anti-thermal quenching properties within the temperature range of 297 to 377 K. Notably, the color-changed time valve of CsCdCl 3 : x %Br can be precisely controlled by manipulating the concentration of Br − ions, distinguishing them from conventional color-varying long-afterglow materials. Additionally, CsCdCl 3 : x %Br display time- and temperature-dependent luminescence, while CsCdCl 3 : x %Sn exhibit forward and reverse excitation-dependent Janus-type luminescence. These characteristics endow the LPL materials with dynamic tunability, offering new opportunities in high-security anti-counterfeiting and 5D information coding. Therefore, this work not only introduces a local-symmetry breaking strategy for simultaneously enhancing afterglow lifetime and efficiency, but also provides new insights into the multimode LPL materials for applications in luminescence, photonics, and information storage. Physical sciences/Materials science/Materials for optics Physical sciences/Chemistry/Materials chemistry/Optical materials Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction Long-persistent luminescence (LPL) is an intriguing optical phenomenon characterized by sustained luminescence for durations ranging from seconds to several days after the cessation of excitation. Its earliest documented observation date back to the 17th century 1 . However, significant advancements in this research field only materialized in the 20th century, notably with the discovery of LPL in copper-doped zinc sulfide, leading to its application in glow-in-the-dark materials 2 . A groundbreaking moment occurred in the mid-1990s when Matsuzawa et al . introduced the green inorganic LPL material SrAl 2 O 4 :Eu 2+ ,Dy 3+ , utilizing oxygen-vacancy traps 3 . Since then, a diverse array of afterglow phosphors, involving oxides, sulfides, and nitrides doped with various lanthanides or transition metals has been developed 4 , 5 . These materials find widespread applications in lighting 6 , 7 , displays 8 , bioimaging 9 – 11 , photocatalysis 12 , information storage and security encryption 13 – 15 . However, during this rapid expansion 16 , scientists recognized that the high-temperature synthesis process (1000 ~ 1500 o C) not only fails to meet the requirements of energy conservation and environmental protection requirements, but also poses a significant safety risk for manufacturers. In response to these challenges, new distinctive design concepts have recently emerged, involving molecule-based LPL through chemical synthesis and/or molecular self-assembly. In 2017, Adachi et al. utilized two simple organic molecules to achieve LPL by recombining long-lived charge-separated states, marking the advent of organic LPL (OLPL) 17 . In 2022, Tang et al. disrupted the pattern of multi-component synergies by employing a single-component molecular LPL system capable of detectable afterglow for more than 12 min under ambient conditions 18 . Our group has contributed to this field by developing LPL systems based on organic-inorganic halides 19 , 20 , which have emerged as promising and cost-effective semiconductor materials for sensor, optical waveguide, and information storage 21 . However, these hybrid perovskites have only exhibited short afterglow times, attributed to mechanisms such as room temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) 22 . In 2021, Zhang et al. reported a double halide perovskite system, Cs 2 Na x Ag 1 − x InCl 6 :y%Mn 23 . incorporating energy transfer (ET) processes and self-trapped excitons (STEs) mechanisms to obtain LPL. Despite significant efforts in the aforementioned progress, achieving high luminescent efficiency in halide perovskite engineering or OLPL systems remains a formidable task 24 . Notably, the majorities of LPL materials tend to exhibit monochromatic (solitary color) afterglow, lacking proficiency in multifarious stimulated-response skills. The recent extensive exploration of stimuli-responsive luminescent materials 25 – 27 underscores their excitation-wavelength-dependence (Ex-De) 28 , as well as their intelligent response to mechanical force 29 , pH 30 , electric field 31 , and temperature 32 in various application scenarios. In addition to advancing the development of various molecules and manipulating their lifetimes and emission efficiency, it is crucial to establish a versatile platform for LPL materials to ensure their practical utility. Simultaneously, the burgeoning field of materials exhibiting time-dependent, color-varying afterglow holds promising prospects in optoelectronic devices and high-end anti-counterfeiting products 33 . In this context, two primary strategies exist for creating such exquisite materials. One involves incorporating fluorescent dyes as acceptors (guests) into a rigid polymer matrix donor (host), facilitating Förster resonance energy transfer (FRET) in the host-guest system 34 , 35 . Commonly, their color-varying afterglow is shifted from long to short wavelengths, while the occurrence of afterglow changing towards longer wavelengths is a rare and huge task. The other entails constructing multiple luminescence centers through the regulation of the triplet and singlet energy levels 36 , 37 . Nevertheless, these advanced schemes have several drawbacks, including potential cross-chromaticity with multiple similar fluorescent dyes, short lifetimes at the millisecond to second level, challenges in tailoring a single component, and difficulty in controlling the discoloration time point during the afterglow process. Notably, the controllable time valve at the color change point is a significant gap in this field. To overcome these challenges through halide perovskite engineering, several requirements must be met: a) achieving ultralong persistent luminescence, b) demonstrating multimode luminescence, c) exhibiting a wide range of afterglow color variability, d) allowing for easy determination by the naked eye, and e) enabling an adjustable time valve for afterglow discoloration based on specific variables. In the pursuit of performance breakthroughs for typical ABX 3 all-inorganic perovskites, the focus primarily revolves around the regulation of B or X sites 38 . We propose that introducing doped ions into the all-inorganic skeleton can disrupt the original symmetry, forming new trap states and luminescence centers. Here, we present a dually positive design strategy to achieve color-tunable LPL by introducing Br − or Sn 2+ ions into the hexagonal phase CsCdCl 3 through a modified wet-chemistry method. This involves a) ensuring the Br − or Sn 2+ ion radius is comparable to that of Cl − and Cd 2+ ions, b) leveraging the 4 p orbital effects of Br − ions on the band gap and the 5 s 2 electronic configuration of Sn 2 ⁺ ions to distort the lattice, and c) using doping to break the local symmetry in the main framework, thereby establishing different trapping centers to compensate for forbidden energy transitions. Our findings indicate that disrupting geometric symmetry may generate multimode luminescence in Br − or Sn 2+ -doped perovskites at both face-shared (C 3v symmetry) and corner-shared (D 3d symmetry) [CdCl 6 ] 4− octahedrons. Thermoluminescence (TL) curves demonstrate the coexistence of shallow and deep trapping centers in both Br − or Sn 2+ -doped perovskites, contributing to their anti-thermal quenching ability up to 377 K. Ultimately, CsCdCl 3 : x %Br and CsCdCl 3 : x %Sn exhibit long afterglow durations (2,000 s), with optimized photoluminescence quantum yields (PLQY) of 84.47% and 65.71%, respectively, representing cutting-edge levels among current LPL perovskites and inorganic-organic hybrids. Significantly, CsCdCl 3 : x %Br demonstrate remarkable color-varying long-afterglow properties, with color alteration at different time points precisely regulated by varying concentrations of Br − ions. Moreover, CsCdCl 3 : x %Br display wide-range (97K-377K) temperature-dependent PL properties, enabling full-color adjustability. Specifically, CsCdCl 3 : x %Sn exhibit a unique optical behavior analogous to Janus-type emission 39 , including forward and reverse excitation-dependent LPL at low or room temperature, respectively. These multifunctional LPL perovskites hold substantial potential for high-level anti-counterfeiting and information security in extreme scenarios. Results Synthesis and structure. A straightforward synthesis method is essential for achieving LPL. In the elevated temperature solid state method (1000 ~ 1500℃) for afterglow phosphors 40 , the high-temperature melting process towards OLPL materials heavily depends on the melting/boiling point similarity of each component to prevent bond breakage and reorientation 41 . Conventional solution chemistry methods have been employed for short-lived afterglow of organic-inorganic halides and crystalline/polymeric organic materials 22 – 23 , 42 . In this work, single crystals of CsCdCl 3 can be grown using a modified hydrothermal reaction (details in Methods, Fig. 1 f), and its crystal lattice adapts a space group P6 3 /mmc (CCDC No. 2313854). The 3D asymmetric unit, as shown in Fig. 1 a and Supplementary Fig. 1, is constructed with [CdCl 6 ] 4− octahedrons. Two of these share a triangular face to form [Cd 2 Cl 9 ] 5− in C 3v symmetry, which then connected with six additional [CdCl 6 ] 4− octahedra to achieve corner-shared D 3d symmetry. This unique packing arrangement offers numerous coordination sites for diverse halides and divalent metal cations, allowing for the arbitrarily anchoring of Br − or Sn 2+ ions at the Cl − or Cd 2+ ion sites, potentially leading to distinct optical properties. Upon alternation by Br − or Sn 2+ ions, the powdered X-ray diffraction (PXRD) patterns of CsCdCl 3 : x %Br and CsCdCl 3 : x %Sn closely agree with the pattern in the PDF#18–0337, confirming the single-phase purity of the synthesized Br − or Sn 2+ -doped CsCdCl 3 (Fig. 1 , b to c and Supplementary Figs. 2 and 3). This leads to the expansion of the host lattice, manifested by the shifting of Bragg positions at [104] and [110] to lower angles (Supplementary Figs. 2 and 3). The ion radius values of Br − (r = 1.96 Å) and Sn 2+ (r = 1.02 Å, CN = 6) are larger than those of Cl − (r = 1.81 Å) and Cd 2+ (r = 0.95 Å, CN = 6), respectively, contributing to the observed lattice expansion. X-ray photoelectron spectroscopy (XPS) profiles describe Br − - and Sn 2+ -doped samples, with the characteristic peaks of Br − 3 d and Sn ion 3 d 3/2 and 3 d 5/2 becoming more pronounced with increasing guest-doped concentration (Supplementary Figs. 4 and 5). Particularly, the peaks centered at 3 d 3/2 = 496.02 eV and 3 d 5/2 = 487.02 eV correspond to Sn 2 + 43,44 , suggesting that a tiny amount of Sn 2+ doping can preserve its stability (Supplementary Fig. 5b, 5d). Scanning electron microscope (SEM) images show a typical spindle shape of Br − or Sn 2+ -doped CsCdCl 3 crystals, with uniform distribution of elemental constituents (Cs, Cd, Cl, Br or Sn) in element mapping images, confirming the successful dopant engineering of Br − or Sn 2+ ions (Fig. 1 d, 1 e). The standard Rietveld refinement technique reveals a poor linear relationship between the nominal concentrations of Br or Sn and the distance of the (110) planes, somewhat deviating from the Vegard's law. To investigate this deviation, energy dispersive spectroscopy (EDS) was employed to determine the actual concentrations of Br − or Sn 2+ ions in crystals (Supplementary Figs. 2b and 3b, Supplementary Table S2 and S3). Interestingly, the actual concentrations exhibit perfect linearity with respect to the d 110 plane and strictly adhere to Vegard's law 45 . These results suggest that the concentrations of Br-doping slightly exceed the nominal value, while the opposite holds true for Sn-doping, which can be attributed to differences in solubility and solvent boiling points. Photophysical Properties The optical characteristics of CsCdCl 3 single crystals were initially investigated. As depicted in Supplementary Fig. 8a to 8c, the optimal excitation wavelength for the photoluminescence excitation (PLE) center of pure CsCdCl 3 is 254 nm, inducing a broad emission peak at 595 nm with a full width at half-maximum (FWHM) of 88 nm in both prompt and delayed spectra (collected after 1 ms of excitation). CsCdCl 3 displays robust excitonic absorption, aligning well with the PLE spectrum (Supplementary Figs. 7a, 8c). Given the substantial Stokes shift (341 nm) and wide FWHM, the observed orange emission is attributed to the self-trapping excitons (STEs) emission, consistent with the prior report 46 . Nevertheless, the low emission intensity (PLQY∼25.47%) significantly restricts its applicability (Fig. 2 i, Supplementary Fig. 30a). One strategy to modulate PL properties is introducing different halide cations with tunable band gaps, as observed in lead-based perovskites to achieve nanosecond luminescent lifetimes 47 . Doping a series of Br − ions produces noticeable changes in the corresponding optical spectra. As shown in Fig. 2 a and Supplementary Fig. 8a, under 254 nm excitation, CsCdCl 3 : x %Br ( x = 0.2–15) crystals exhibit a blue-shifted and progressively stronger broad emission peak at 482 nm compared to the pristine CsCdCl 3 crystals. The delayed spectra reveal that intensities peaking at 482 and 595 nm are both enhanced with increasing Br − doping concentration (Fig. 2 a, Supplementary Fig. 8b), resulting in a merging into a single large peak spanning from 350 to 800 nm, akin to the behavior observed in the prompt spectra. CsCdCl 3 possesses both C 3v and D 3d symmetries 48 , with the a 1 →e transition allowed in C 3v symmetry and the a 1g →e g transition in D 3d symmetry undergoing an S-T-splitting route 49 . The radiative transition in both symmetries originates from the triplet exciton, with the energy gap of D 3d tending to be larger than that of C 3v 49 . Previous studies have indicated that D 3d symmetry's PL is in the UV region at low temperatures due to constrained molecular vibrations accelerating the S-T splitting process 49 , 50 . However, CsCdCl 3 : x %Br ( x = 0.2–15) crystals show robust emission centered at 482 nm without the need for low temperatures. To comprehend this behavior, we analyze the structure-luminescence relationship: replacing Cl − ions with Br − ions distorts the [CdCl 6 ] 4− octahedron into [CdCl 6 − n Br n ] 4− due to distinct Cd–Cl (2.66 Å) and Cd–Br (2.71 Å) bond lengths 51 . The emission peak at 482 nm, with a large Stokes shift (228 nm) and wide FWHM, is attributed to STEs, consistent with previous reports 52 – 54 . All the PLE spectra of CsCdCl 3 : x %Br show gradually red-shifting and broadening peaks beyond 300 nm, aligning well with the absorption spectrum (Fig. 2 a, Supplementary Figs. 7a, 8c to 8d). This further suggests that transitions involving [e + a 1 ] →a 1 and [e + a 1 ] →e, a 1 in C 3v , as well as [e u + a 2u ] →a 1g in D 3d are all activated. Therefore, CsCdCl 3 : x %Br samples exhibit a significantly enhanced PLQY up to 84.47% without relying on rare-earth metals (Fig. 2 i, Supplementary Fig. 30), signifying a resource-saving approach for high-efficiency luminescence. To understand the PL mechanism, temperature-dependent PL spectra for the representative of CsCdCl 3 :0.8%Br and CsCdCl 3 :10%Br were conducted. As illustrated in Supplementary Fig. 9a, the PL peak (band 3) emerges at low temperatures, followed by band 2 as temperature increases to room level, and then band 3 becomes more prominent at higher temperatures. Obviously, because of the low doping concentration of Br − ions, both D 3d and C 3v exist in [CdCl 6 ] 4− and [CdCl 6 − n Br n ] 4− forms, with band 3 assigned to pure [CdCl 6 ] 4− in D 3d symmetry at low temperature 49 , and band 2 with broad emission corresponding to the Br-doped of [CdCl 6 − n Br n ] 4− in both D 3d and C 3v symmetry, while band 1 represents the undoped [CdCl 6 ] 4− unit in C 3v symmetry 52 , 53 . For the delayed spectra (Supplementary Fig. 9b), bands 3 and 2 have maintained long-lived photoemission owing to the triplet exciton arising from D 3d and C 3v symmetry to cause phosphorescence. The increased FWHM by photon-phonon coupling in a specific temperature range of 217 to 277 K (Supplementary Fig. 9a, 9b), along with the large Stokes-shift, provides direct evidence that band 2 emission is associated with STEs 51 , 54 – 55 . Upon 10% Br − ion doping, the prompt spectra show that band 3 blends into band 2 at low temperatures due to the transformation of [CdCl 6 ] 4− into [CdCl 6 − n Br n ] 4− in D 3d (Supplementary Fig. 9c), again confirming the band 3 originates from D 3d symmetry. The corresponding luminescence mechanism is depicted in Fig. 5 e. It is noteworthy that band 1 in both samples becomes stronger with increasing temperature up to 377 K (Supplementary Fig. 9), illustrating its anti-thermal quenching ability, which will be further discussed below. Intriguingly, both the prompt and delayed spectra of CsCdCl 3 :0.8%Br and 10%Br exhibit excellent temperature-dependent luminescent properties (Fig. 2 e and 2 f, Supplementary Fig. 10). Of that, CsCdCl 3 :0.8%Br displays remarkable color variation, ranging from blue to cyan, then across yellow-green and finally to orange-red, observable with naked eyes (Fig. 4 d), in good agreement with CIE coordination (Fig. 4 b, 4 c). Such a wide range of full-color tunable luminescence and the anti-thermal quenching properties are still rare, particularly in state-of-the-art LPL materials (Supplementary Table 4). Remarkably, CsCdCl 3 : x %Br samples exhibit substantial LPL with distinctive time-dependent afterglow alterations. As illustrated in Fig. 4 a, the pristine CsCdCl 3 host manifests an orange-red afterglow extinguishing promptly upon cessation of the 254 nm UV lamp. CsCdCl 3 : x %Br, conversely, hold a bright blue-green color when exposed to 254 nm UV light. Subsequent to excitation cessation, CsCdCl 3 : x %Br exhibit color-variable LPL from blue-green to orange-red, effectively covering the entire visible spectrum. Notably, unlike conventional time-dependent luminescence, herein the time-valve in the color change can be regulated based on Br − ion concentration. To elucidate this phenomenon, steady-state luminescent decay curves were monitored at emission centers of 482 and 595 nm. As shown in Fig. 2 g, the afterglow intensity at 595 nm rapidly diminishes in the first 500 s, followed by a gradual decline extending up to 2000 s to discern from the background. The decay lifetime of 482 nm in the initial 60 s window is extended with increasing the Br − ion concentration to 10% (Fig. 2 h). As observed in Supplementary Movie 1, the afterglow persists for 1800 s to naked eyes. Analysis of time-resolved PL mapping in Fig. 2 b and Supplementary Fig. 11 indicate that the emission band at 595 nm remains consistently strong, while the band at 482 nm gradually intensifies with Br − ion concentration doping to 5%. The time-dependent afterglow spectrum exhibits that the emission bands at 595 and 482 nm initially merge into a broad acromion (Fig. 2 c, Supplementary Fig. 12), with the intensity at 595 and 482 nm linked to both time evolution and Br − ion doping concentrations. Hence, the color-variable LPL can be modulated by different decay lifetimes of emissions at 482 nm and 595 nm, as well as Br − ion concentrations in CsCdCl 3 : x %Br. Charge trap state analysis through TL measurements is an effective method for elucidating LPL. Firstly, CsCdCl 3 : x %Br show good thermal stability (Supplementary Fig. 6a). No TL signal is detected for the pristine CsCdCl 3 , implying the absence of LPL nature (Fig. 2 d). For CsCdCl 3 : x %Br, four different cases arise: ⅰ) x = 0.2 ~ 0.5, the TL single peak center appears at 370 K; ⅱ) x = 0.8, three peaks of 366, 392 and 465 K are observed; ⅲ) x = 1 ~ 5, the TL peaks lie in 380 and 445 K; ⅳ) x = 10 ~ 15, the TL peaks occur at 371 and 355 K. The trap energy level can be estimated by Urbach’s empirical formula E trap =T m /500 (T m is the temperature of TL peak) 56 . Accordingly, the aforementioned TL peaks are determined to be 0.74 (370 K), 0.73 (366 K), 0.78 (392 K), 0.93 (465 K), 0.76 (380 K), 0.89 (445 K), 0.74 (371 K), and 0.71 eV (355 K), respectively. These CsCdCl 3 : x %Br samples all possess shallow traps ranging from 0.67 to 0.76 eV, preferable for creating an ideal depth for LPL 57 . In addition, the trap depths in the range of 0.8–1.6 eV are categorized as deep traps, typically resulting in low LPL at room temperature due to the activation energy barrier 58 . However, as the temperature increases, the charge carriers in the deep traps overcome the activation energy barrier and migrate to the emission center, leading to an anti-thermal quenching property. An alternative avenue to achieve benefits involves selecting appropriate metal cations as activators in metal halides. Consequently, we opt for the Sn 2+ ion as the doped emissary for CsCdCl 3 to elucidate the luminous properties. As illustrated in Fig. 3 a and Supplementary Fig. 13b,13c, under the excitation of 254 nm UV light, a predominant emission peak at 595 nm is significantly enhanced in both prompt and delayed spectra with increasing Sn 2+ ion dopant concentration from 1–10%. However, further doping results in a slightly reduced peak intensity. CsCdCl 3 :10%Sn displays the highest PLQY up to 65.71% (Fig. 3 f, Supplementary Fig. 31). Subsequently, the PLQY experiences a marginal decline with a further increase of Sn 2+ ion concentration, attributed to intensified Sn 2+ -Sn 2+ dipole interactions causing nonradiative energy transition. The prompt and delayed PLE spectra exhibit a primary peak centered at 254 nm (Supplementary Fig. 13a, 13c), with an apparent shoulder peak at 282 nm becoming more pronounced as Sn 2+ ion concentration increases, consistent well with the absorption spectra (Supplementary Fig. 7b). As depicted in Fig. 3 a and Supplementary Fig. 13e, h, an obvious emission peak at 565 nm is enhanced upon increasing the Sn 2+ ions under the excitation wavelength of 282 nm. To further investigate this uncommon phenomenon, a series of excitation-wavelength dependent PL spectra and 2D excitation maps were performed for these CsCdCl 3 : x % Sn. As shown in Fig. 3 i and Supplementary Fig. 14, 18, as the excitation wavelength red-shifts from 250 to 285 nm, the emission band center at 595 nm undergoes a significant blue shift to 565 nm with reduced intensity in both prompt and delayed spectra. Continuous shifting of the excitation to 310 nm results in a faint peak at 480 nm, which is negligible in the 2D excitation map (Fig. 3 i, bottom, Supplementary Figs. 14 to 18, right). Notably, such a large contrast in the blue-shifted emission based on continuous red-shifted excitation at room temperature has not been reported in halide perovskites, even rarely among various current luminous materials (Supplementary Table 4). To elucidate this intriguing phenomenon, we conducted temperature-dependent PL spectra for representative CsCdCl 3 :3%Sn and CsCdCl 3 :10%Sn. As shown in Supplementary Fig. 19, 20, under 254 nm irradiation at low temperatures, the initial observation is the emergence of prompt PL band ⅲ, faintly mirrored in the delayed spectrum, alongside the prompt PLE peak at 254 nm (Supplementary Fig. 21). These findings suggest that the band ⅲ originates from unaltered [CdCl 6 ] 4− in D 3d symmetry. As the temperature rises to 177 K, a broad prompt PL band ⅱ becomes prominent, replacing the weakened band ⅲ, a change similarly in the delayed spectra, indicating their common origin in triplet excitons (Supplementary Figs. 19b, 20b). Considering Sn 2+ ions with a 5 s 2 electron configuration and 1 P 1 / 3 P 0,1,2 energy levels 59 . transitions such as 1 S 0 → 3 P 0 and 1 S 0 → 3 P 2 are deemed forbidden, while allowed transitions include 1 S 0 → 3 P 1 and 1 S 0 → 1 P 1 due to spin-orbit coupling 60 , 61 . The broad emission band ii is primarily attributed to the 3 P 1 → 1 S 0 transition of Sn 2+ ions situated in D 3d [SnCl 6 ] 4− symmetry, partially involving the breaking of the forbidden transition 3 P 2 → 1 S 0 at low temperatures 62 . Upon further temperature elevation, the emission band ⅰ gradually intensifies, with its FWHM increasing due to photon-phonon coupling in both prompt and delayed spectra (Supplementary Figs. 19, 20). Given the large Stokes shift is similar to the pristine CsCdCl 3 , band ⅰ can also be identified as STEs originating from Cd 2+ ions in conjunction with the distortion of [SnCdCl 9 ] 5− moieties in C 3v symmetry. To further substantiate this hypothesis, we adjusted the excitation wavelength to 282 nm. As illustrated in Supplementary Figs. 22, 23, the PL band ⅲ diminishes, while band ⅱ remains robust at low temperature, affirming their origin from [CdCl 6 ] 4− and [SnCl 6 ] 4− in D 3d symmetry, respectively. With increasing temperature, a newly emerging band ⅳ with an emission center at 565 nm gains strength progressively. This observation is influenced by two main factors: a) Lower excitation energy effectively populates the exciton to the lower-energy 3 P 1 state of the Sn 2+ ion in distorted [SnCdCl 9 ] 5− , where the thermodynamically favored 3 P 1 exciton serves as a trapped state, enhancing anti-thermal quenching ability. 60 – 61 , 63 b) The wide FWHM and large Stokes shift crucially support its STEs 64 . Further, a series of excitation-dependent PL experiments were conducted on CsCdCl 3 :3%Sn and CsCdCl 3 :10%Sn at 97 K. As shown in Fig. 3 h, Supplementary Figs. S24a, 25a, varying the excitation wavelength from 250 to 300 nm results in a red-shift of the prompt emission center from 440 to 565 nm, corresponding well with the above-mentioned band ⅲ, band ⅱ and band ⅳ. In the delayed spectra (Supplementary Figs. 24b, 25b), the emission band at 595 nm (band ⅰ) decreases, and the broad emission band centered at 525 nm (band ⅱ) intensifies, confirming that optical properties are influenced by the geometric symmetry and energy states of the metal centers 63 – 65 . The corresponding luminescence mechanism is depicted in Fig. 5 f. The distinctive feature as Janus-type luminescence – forward excitation-dependence at low temperature and the reverse excitation-dependence at room temperature – has not been reported previously (Supplementary Table 4), holding promise for potential applications in information safety and temperature recognition. After 46 days of storage at room temperature, all samples exhibit no significant spectral changes (Supplementary Figs. 28, 29), underscoring the excellent optical stability of CsCdCl 3 : x % Sn. Remarkably, all CsCdCl 3 : x %Sn samples emit orange-red LPL after the cessation of 254 nm UV light (Fig. 4 e and Supplementary Movie 1). The steady-state luminescent decay of the emission bands at 595 nm and 565 nm were investigated. Following the termination of 254 nm irradiation, the intensity of the CsCdCl 3 :3%Sn rapidly decreases in an initial 500 s and persists for up to 2000 s (Fig. 3 b). For Fig. 3 c, the intensity of the CsCdCl 3 :10%Sn at 565 nm also decays quickly in the first 400 s, and gradually slows down until reaching 1000 seconds. The characteristics of LPL at 595 nm and 565 nm are demonstrated through time-resolved PL mapping (Fig. 3 d, 3 e, Supplementary Fig. 26) and the time-dependent afterglow emission spectrum (Supplementary Fig. 27). Moreover, CsCdCl 3 : x %Sn exhibit good thermal stability (Figure S6 b). Focusing on the TL spectra (Fig. 3 g), CsCdCl 3 : x %Sn exhibit distinct peak centers and trap energy levels (estimated by E trap = T m /500) at different x values: x = 1 (355K→0.71eV), 3 (355K→0.71 eV, 395K→0.79 eV), 5 (363K→0.73 eV, 434K→0.87 eV), 10 (363K→0.73 eV, 374K→0.75 eV and 452K→0.90 eV), and 15 (342K→0.68 eV, 436K→0.87 eV), respectively. Given this, it is no surprise that trap states play a crucial role in saving excitons from the excited state, evoking the LPL of these CsCdCl 3 : x %Sn by releasing excitons from shallow traps and thermally breaking the energy barrier in deep traps to the ground state. Density Functional Theory (DFT) To gain deeper insights into the electronic structure and luminescence mechanisms of Br-doped and Sn-doped CsCdCl 3 , we conducted band structure and total density of states (DOS) calculations. The pristine CsCdCl 3 exhibits a direct bandgap, whereas the Br-doped and Sn-doped models exhibit indirect bandgaps (Fig. S33 to S34), thereby mitigating hole-electron recombination and extending exciton lifetimes 66 – 67 . In Fig. 5 a and Fig. S36 to S40, the projected DOS (PDOS) of D 3d -Br i -C 3v (i = 1,2,3) and C 3v -Br j -C 3v (j = 4,5,6) models reveal that the valence band (VB) is mainly composed of Cl 3 p and Br 4 p orbitals, while the conduction band (CB) consists of Cd 5 s /5 p , Br 4 p , and Cl 3 p orbitals. In contrast, Cs orbitals play a negligible role in the band structures of these models. The charge density maps illustrate that the valance band maximum (VBM) is localized at Br − and Cl − ions in [CdCl 6 − n Br n ] 4− moiety of both D 3d and C 3v symmetry, while the conduction band maximum (CBM) is predominantly formed from Cd 2+ (Fig. 5 c, Supplementary Figs. 36b to 40b). The small discrepancy in bandgaps between the D 3d -Br i -C 3v (i = 1,2,3) and C 3v -Br j -C 3v (j = 4,5,6) models, approximately 12.2 meV, has negligible impact on the PL of [CdCl 6 − n Br n ] 4− in both D 3d and C 3v symmetries (Supplementary Fig. 33g). This reaffirms that the broad emission band at 482 nm (band 2) in Br-doped CsCdCl 3 originates from the combined emission center of [CdCl 6 − n Br n ] 4− in both D 3d and C 3v symmetries (Fig. 2 a, 5 e, Supplementary Fig. 9). For Sn-doped CsCdCl 3 (Fig. 5 B, Fig. S41 to S43), PDOS shows that VBs consist of Cl 3 p and Sn 5 s orbitals, while the CBs comprise Cl 3 p , Sn 5 p and Cd 5 s /5 p orbitals in D 3d -Sn i (i = 1,4) and C 3v -Sn j (j = 2,3) models. The bandgap of D 3d -Sn i (i = 1,4) models is larger than C 3v -Sn j (j = 2,3) models, around 30.4–95.7 meV (Supplementary Fig. 34g), impacting the PL characteristics of [SnCl 6 ] 4− in both D 3d and C 3v symmetries due to exceeding the thermal energy of 26 meV 68 . This observation aligns with the experimental trend of Sn-doped materials exhibiting a reduced bandgap (Supplementary Fig. 7d). Additionally, these results underscore that the luminescence center of Sn 2+ ions in C 3v [SnCdCl 9 ] 5− symmetry requires less matching excitation energy, resulting in the reverse excitation-dependent behavior observed in experiment. From Fig. 5 d and Supplementary Figs. 41b to 43b, the charge density maps highlight Sn 2+ ion with unique 5 s -related energy levels significantly influencing the VBM and contributing to multimode luminescence. Interestingly, when Sn 2+ ion doping at C 3v [SnCdCl 9 ] 5− symmetry (Supplementary Figs. 41b to 42b), the charge density of CBM is primarily located at the Cd 2+ ion of C 3v symmetry, further supporting the hypothesis that band ⅰ stems from C 3v symmetry (Fig. 3 a, 5 f, Supplementary Figs. 19, 20). High-level anti-counterfeiting using multifunctional LPL Programming advanced anti-counterfeiting technology is of considerable practical importance, by leveraging the LPL characteristics of all-inorganic halide perovskites to demonstrate their distinctive spatial-time-resolved, and time-logical color-variable afterglow properties. As depicted in Supplementary Fig. 44, no perceptible alterations are observed under ambient lighting conditions. However, upon exposure to 254 nm UV irradiation (Fig. 6 a), the combination of chaotic orange-red and cyan colors could potentially convey misleading messages such as “I ❤ BNU 8888” (BNU: Beijing Normal University) and two other false messages when individually viewed in the orange-red or cyan channel. After ceasing the UV lamp for 1s (Fig. 6 b), the subsequent error information is interpreted as "I ❤ BNU 2083", accompanied by two additional error messages, resembling a three-dimensional (3D) encryption featuring spatial-time-dual-resolved patterns. The cyan “❤”transfers to milk white, and some local areas exhibit color changes in 3 s (Fig. 6 c). Despite the message still reading as “I ❤ BNU 2083”, it has evolved into the 4D anti-counterfeiting category due to its variable color factor. Ultimately, a cohesive orange-yellow color palette effectively conveys the intended message of “I ❤ BNU 2023” (Fig. 6 d and Supplementary Movie 2). The overall process can be regarded as a 5D anti-counterfeiting technology, which is anticipated to surpass conventional afterglow materials due to its additional time-gated color change facilitated by Br-doping engineering. Furthermore, proof-of-concept experiments were conducted by filling a series of as-synthesized perovskites into the QR code groove. As depicted in Fig. 6 e, the security model operates under a mechanism wherein specific attributes are assigned to the QR code of each region: emission loss (marked in red), QR code with afterglow duration every 0.5 s (marked in blue), and modification of the afterglow color (marked in green). These attributes correspond to the binary shifts of one bit (+ 1) in the respective regions. Upon excitation by the 254 nm UV lamp, the QR code displays chaotic orange-red and cyan hues, representing the binary exchange algorithm “000”. At a delay time of 0.5 s, region C undergoes the first transition from cyanogen to cyanogen yellow, introducing binary ciphers for “011”, “110” and “101”. One second later, the emission from region A is nearly extinguished, while region C transforms to orange-yellow, resulting in adjustments of the binary ciphers to “11010”, “10110” and “10101”. After 18 s, the new binary ciphers take form, generating security codes “1161, 1764, 1508, 1481, 1175 and 1179” through binary and decimal conversion (Fig. 6 h). The final lock code is determined as “1508”. It is noteworthy that the above binary ciphers are applicable only when i = j = n at the respective time nodes. If the binary digits of all time nodes could be exchanged (Fig. 6 f), it would result in an information Big-Bang, achieving the maximal information loading capacity (Fig. 6 h). Therefore, these perovskites are anticipated to be highly effective for advanced high-security anti-counterfeiting due to leveraging the advantages of time-sensitive color and spatial-time four-resolved functionality. Discussion In summary, we have successfully demonstrated an ultralong (> 2,000 s) persistent luminescence by incorporating Br − or Sn 2+ ions into the hexagonal phase CsCdCl 3 , achieving the highest recorded PLQY (84.47%) among current halide perovskites. The simultaneous significant improvement in afterglow lifetime and efficiency can be attributed to the reconstruction of the luminescence center induced by doping, leading to a disruption of the local symmetry in the host framework. Unlike conventional long-afterglow materials, CsCdCl 3 : x %Br exhibits a precisely regulatable color change time valve, determined by varying Br − ion doping concentrations, enabling both time- and temperature-dependent LPL. The unique 5 s 2 electron configuration of Sn 2+ ions, coupled with distinct geometric symmetries that construct multiple luminescence centers, results in forward and reverse excitation-dependent PL behavior of CsCdCl 3 : x %Sn at low and room temperatures, respectively. Therefore, this work not only addresses the existing gap in the field concerning wide-range full-color long-afterglow and Janus-type Ex-De materials, but also introduces a significant paradigm for multifunctional LPL, with applications in high-security anti-counterfeiting and 5D information coding and storage. Methods Materials. Cesium chloride (CsCl, 99.99%, Innochem), Cadmium chloride (CdCl 2 , 99.99%, Aladdin), Cadmium Bromide (CdBr 2 , 99.99%, Adamas), Cesium Bromide (CsBr, 99.99%, Adamas), Tin(II) chloride (SnCl 2 , anhydrous, 99.99%, Aladdin), Hydrobromic acid (HBr, AR, 40 wt.% solution in water, Macklin), H 3 PO 2 (50 wt.% solution in water, Sigma Aldrich). Hydrochloric acid (HCl, 12 M) was purchased from Xilong Scientific Co. Ltd. Preparation of Br-doped CsCdCl 3 single crystals. For pure CsCdCl 3 single crystals (SCs), 4 mmol of CsCl, 4 mmol CdCl 2 were dissolved in 20 mL 12 M hydrochloric acid. The solution was heated at 180°C for 12 hours in a stainless steel Parr autoclave, and then was slowly cooled to room temperature (RT) at a speed of 5°C/h. The crystals at the bottom were rinsed with isopropanol before drying on a filter paper. For CsCdCl 3 : x %Br crystals, 4×(1- x ) mmol of CsCl, 4×(1- x ) mmol CdCl 2 , 4× x mmol of CsBr and 4× x mmol of CdBr 2 were dissolved in a total 20 mL mix solution of hydrochloric acid and hydrobromic acid with molar ratio of (1- x )/ x . the other procedures are the same as above. All crystals were preserved in a caped vial for further characterization. Preparation of Sn-doped CsCdCl 3 single crystals. According to the above method, replacing raw materials with 4 mmol of CsCl, 4×(1- x ) mmol CdCl 2 and 4× x mmol SnCl 2 to dissolve in 20 mL 12 M hydrochloric acid with 50 wt.% H 3 PO 2 (~ 132 µL, 1 mmol). Finally, CsCdCl 3 : x %Sn crystals ware harvested. Characterizations. Single-crystal X-ray diffraction data of these samples were investigated by Rigaku Oxford Diffraction Supernova X-ray source diffractometer equipped with monochromatized Mo-Kα radiation ( λ = 0.71073 Å) at 100 K. Scanning electron microscope (SEM) were characterized by Hitachi SU8010 instrument, and the corresponding element content was collected by energy disperse spectrometer (EDS, Oxford X-Max Aztec). X-ray Photoelectron Spectroscopy (XPS) data were collected using EscaLab 250Xi instrument. Solid UV − vis absorption spectra were collected on a Shimadzu UV-3600 spectrophotometer at room temperature with the wavelength range of 240 − 500 nm, and BaSO 4 powder was used as a standard (100% reflectance). TGA tests were collected on a Perkin-Elmer Diamond SII thermal analyzer under the atmosphere of nitrogen with a heating rate of 10 K min − 1 . All the relevant photoluminescence (PL) tests and time-resolved lifetime were conducted on an Edinburgh FLS980 fluorescence spectrometer. The PLQY values were acquired using a Hamamatsu Quantaurus-QY Spectrometer (Model C11347-11) equipped with a xenon lamp, integrated sphere sample chamber and CCD detector. The TL spectra were determined by Risϕ TL/OSL Da-20 (DTU Nutech, Denmark) instrument with samples were pre-irradiated under 254 nm UV lamp for 1 min at RT. Theoretical calculations. The calculations were performed with the density functional theory (DFT) by Quantum ESPRESSO (qe-7.2) 69 . The generalized gradient approximation of the Perdew–Burke–Ernzerhof (PBE) parameterization with projector-augmented wave method are performed for the exchange and correlation functional. Wavefunctions expanded in plane waves were cut off to 480 eV kinetic energy. The Brillouin zone was sampled using a 15×15×6 Monkhorst–Pack k-mesh, which was examined have good convergence. For the elements Cs, Cd, Sn, Br and Cl, ultra-soft pseudopotentials are used. The energy convergence criterion is set as 1.0×10 − 5 eV for structural relaxations. As for Br − - and Sb 2+ -doped CsCdCl 3 , we first adopt the models that a Br − ion or Sn 2+ ion substitutes one Cl − or Cd 2+ ion site, respectively. Declarations Acknowledgments Funding: This work was supported by the Beijing Municipal Natural Science Foundation (Grant No. JQ20003), and the National Natural Science Foundation of China (Grant Nos. 22288201 and 22275021). Author contributions: Conceptualization: D. Y. and T. C.; Methodology: D. Y. and T. C.; Investigation: T. C.; Supervision: D. Y.; Writing—original draft: T. C.; Writing—review & editing: D. Y. Competing interests: The authors declare that they have no competing interests. Data availability: All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Materials. 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Additional Declarations There is NO Competing Interest. Supplementary Files DateS1CheckCIFreportofpureCsCdCl3perovskites.pdf Date S1 3.SupportinginformationforNatureCommun.docx Supplementary Information MovieS1LPLofBrandSndopingCsCdCl3perovskites.mp4 Movie S1 MovieS2Theprogressof5Danticounterfeiting.mp4 Movies S2 Cite Share Download PDF Status: Published Journal Publication published 20 Jun, 2024 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3791302","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":266132094,"identity":"feb82486-6da7-495e-ae3c-8b793a3565b8","order_by":0,"name":"Dongpeng Yan","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA7ElEQVRIiWNgGAWjYJACCYYKBgY2dgY2KD+BGC1ngFqYwVoMiNTC2AYkidZicPzswduF87bJ8wG1POap+cPAz55jwPBzBx4tZ/KSrWduu23YxszAbsxzzIBBsueNAWPvGTxaDuSYSfNuu80I1MImzdtgwGBwI8eAGexUXFrOvwFqmXPbHq7FnqCWGyBbGm4nImyRIKBF8sYbY+sZx24ntzEzthvOOWbMI3HmWcHBXjxa+M7nGN4uqLltO7+9+diDNzVycvztyRsf/MSjReEAKEbAgLEBRPKAiAO4NTAwyDfAtYyCUTAKRsEowAEA0e1IDX2XZSoAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0001-8261-154X","institution":"Beijing Normal University","correspondingAuthor":true,"prefix":"","firstName":"Dongpeng","middleName":"","lastName":"Yan","suffix":""},{"id":266132095,"identity":"293770f8-a36f-4c31-8e07-970a7c6fd474","order_by":1,"name":"Tianhong Chen","email":"","orcid":"","institution":"Beijing Normal University","correspondingAuthor":false,"prefix":"","firstName":"Tianhong","middleName":"","lastName":"Chen","suffix":""}],"badges":[],"createdAt":"2023-12-22 10:02:19","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3791302/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3791302/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-024-49654-7","type":"published","date":"2024-06-20T04:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":49412657,"identity":"cf49518a-bc87-4208-aa19-5c4671f920cc","added_by":"auto","created_at":"2024-01-10 10:48:23","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":612392,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eDesign concept and material characterization.\u003c/strong\u003e (\u003cstrong\u003ea\u003c/strong\u003e) Schematic representation of the rational design of Cl\u003csup\u003e− \u003c/sup\u003eor Cd\u003csup\u003e2+\u003c/sup\u003e sites in the CsCdCl\u003csub\u003e3\u003c/sub\u003e crystal structure, occupied by (Ⅰ) Br\u003csup\u003e−\u003c/sup\u003e or (Ⅱ) Sn\u003csup\u003e2+ \u003c/sup\u003eions to disrupt local symmetry in the host framework and promote LPL, color and PLQY properties. Rietveld refinements of the typical XRD patterns of (\u003cstrong\u003eb\u003c/strong\u003e) CsCdCl\u003csub\u003e3\u003c/sub\u003e:0.8%Br and (\u003cstrong\u003ec\u003c/strong\u003e) CsCdCl\u003csub\u003e3\u003c/sub\u003e:10%Sn. SEM image of (\u003cstrong\u003ed\u003c/strong\u003e) CsCdCl\u003csub\u003e3\u003c/sub\u003e:0.8%Br and (\u003cstrong\u003ee\u003c/strong\u003e) CsCdCl\u003csub\u003e3\u003c/sub\u003e:10%Sn, along with their corresponding elemental mapping images of Cs, Cd, Cl, Br and Sn. (\u003cstrong\u003ef\u003c/strong\u003e) Wet-chemistry method for the synthesis of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br and CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn all-inorganic perovskites.\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-3791302/v1/c4cf476f94f44ad8f54e56b2.png"},{"id":49412864,"identity":"36aea997-1e6e-4a61-b8c6-3ae75688e747","added_by":"auto","created_at":"2024-01-10 10:56:23","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":663049,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePhotophysical properties of CsCdCl\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e:\u003c/strong\u003e\u003cem\u003e\u003cstrong\u003ex\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e%Br.\u003c/strong\u003e (\u003cstrong\u003ea\u003c/strong\u003e) Normalized PL spectra of CsCdCl\u003csub\u003e3\u003c/sub\u003e:0.8%Br based on prompt and delayed (t\u003csub\u003ed\u003c/sub\u003e = 1 ms) patterns under 254 nm excitation, along with the corresponding normalized PLE spectra. (\u003cstrong\u003eb\u003c/strong\u003e) Pseudo color map of time-resolved PL spectra of afterglow for CsCdCl\u003csub\u003e3\u003c/sub\u003e:0.8%Br under 254 nm flash lamp. (\u003cstrong\u003ec\u003c/strong\u003e) Three-dimensional time-resolved PL spectra of CsCdCl\u003csub\u003e3\u003c/sub\u003e:0.8%Br under 254 nm excitation. (\u003cstrong\u003ed\u003c/strong\u003e) TL spectra of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br were obtained after pre-irradiation with a 254 nm UV lamp for 1 min. Temperature-dependent PL mapping of CsCdCl\u003csub\u003e3\u003c/sub\u003e:0.8%Br based on (\u003cstrong\u003ee\u003c/strong\u003e) prompt and (\u003cstrong\u003ef\u003c/strong\u003e) delayed (t\u003csub\u003ed\u003c/sub\u003e = 1 ms) patterns under 254 nm excitation. Afterglow decay curve of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br with the detected emission wavelength at (\u003cstrong\u003eg\u003c/strong\u003e) 595 nm and (\u003cstrong\u003eh\u003c/strong\u003e) 482 nm. (\u003cstrong\u003ei\u003c/strong\u003e) The PLQY values of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br.\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-3791302/v1/91ccb9276f5a35a12c8a8d6d.png"},{"id":49412658,"identity":"49f6fdb8-b125-4d98-a88f-5c7a20a836d2","added_by":"auto","created_at":"2024-01-10 10:48:23","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":540727,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eLuminescent performances of CsCdCl\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e:\u003c/strong\u003e\u003cem\u003e\u003cstrong\u003ex\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e%Sn.\u003c/strong\u003e (\u003cstrong\u003ea\u003c/strong\u003e) Normalized PL spectra of CsCdCl\u003csub\u003e3\u003c/sub\u003e:10%Sn based on prompt and delayed (t\u003csub\u003ed\u003c/sub\u003e = 1 ms) patterns under 254 nm or 283 nm excitation, along with the corresponding normalized PLE spectra. Afterglow decay curve of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn with the detected emission wavelength (\u003cstrong\u003eb\u003c/strong\u003e) 595 nm and (\u003cstrong\u003ec\u003c/strong\u003e) 565 nm. Pseudo color map of time-resolved PL spectra of afterglow for CsCdCl\u003csub\u003e3\u003c/sub\u003e:10%Sn under (\u003cstrong\u003ed\u003c/strong\u003e) 254 nm and (\u003cstrong\u003ee\u003c/strong\u003e) 282 nm flash lamp. (\u003cstrong\u003ef\u003c/strong\u003e) The PLQY of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn. (\u003cstrong\u003eg\u003c/strong\u003e) TL spectra of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn. Excitation-prompt mapping of CsCdCl\u003csub\u003e3\u003c/sub\u003e:10%Sn under (\u003cstrong\u003eh\u003c/strong\u003e) 97 K and (\u003cstrong\u003ei\u003c/strong\u003e) 297 K.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-3791302/v1/143d38d606f1c0a932010fd7.png"},{"id":49412660,"identity":"28461189-ea4e-434a-a033-08d64241e658","added_by":"auto","created_at":"2024-01-10 10:48:23","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":941017,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eLuminescent and afterglow behaviors of CsCdCl\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e:\u003c/strong\u003e\u003cem\u003e\u003cstrong\u003ex\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e%Br and CsCdCl\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e:\u003c/strong\u003e\u003cem\u003e\u003cstrong\u003ex\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e%Sn. \u003c/strong\u003e(\u003cstrong\u003ea\u003c/strong\u003e) Afterglow photographs for CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br, A (x=0), C (\u003cem\u003ex\u003c/em\u003e=0.2%), D (\u003cem\u003ex\u003c/em\u003e=0.5%), E (\u003cem\u003ex\u003c/em\u003e=0.8), F (\u003cem\u003ex\u003c/em\u003e=1), G (\u003cem\u003ex\u003c/em\u003e=3), H (\u003cem\u003ex\u003c/em\u003e=5), J (\u003cem\u003ex\u003c/em\u003e=10) and K (\u003cem\u003ex\u003c/em\u003e=15). CIE coordinate diagram of CsCdCl\u003csub\u003e3\u003c/sub\u003e:0.8%Br in temperature-responsive (\u003cstrong\u003eb\u003c/strong\u003e) prompt and (\u003cstrong\u003ec\u003c/strong\u003e) delayed mode. (\u003cstrong\u003ed\u003c/strong\u003e) Temperature dependent PL emission color of CsCdCl\u003csub\u003e3\u003c/sub\u003e:0.8%Br were controlled by switching on/off the 254 nm UV lamp. (\u003cstrong\u003ed\u003c/strong\u003e) Afterglow photographs for CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn, L (\u003cem\u003ex\u003c/em\u003e=1), M (\u003cem\u003ex\u003c/em\u003e=3), O (\u003cem\u003ex\u003c/em\u003e=5), S (\u003cem\u003ex\u003c/em\u003e=10) and T (\u003cem\u003ex\u003c/em\u003e=15).\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-3791302/v1/2d6a54fd6a2a31e7ca41e126.png"},{"id":49412662,"identity":"a63edec7-ce4c-43d0-bd31-07d89cb792e2","added_by":"auto","created_at":"2024-01-10 10:48:23","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":527423,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eDFT calculations and luminescent mechanism of Br- and Sn-doped perovskites. \u003c/strong\u003ePDOS of (\u003cstrong\u003ea\u003c/strong\u003e) D\u003csub\u003e3d\u003c/sub\u003e-Br\u003csub\u003e1\u003c/sub\u003e-C\u003csub\u003e3v\u003c/sub\u003e and (\u003cstrong\u003eb\u003c/strong\u003e) D\u003csub\u003e3d\u003c/sub\u003e-Sn\u003csub\u003e1\u003c/sub\u003e model.\u0026nbsp; Visualization of the Gamma point with VBM and CBM-associated charge density maps in (\u003cstrong\u003ec\u003c/strong\u003e) D\u003csub\u003e3d\u003c/sub\u003e-Br\u003csub\u003e1\u003c/sub\u003e-C\u003csub\u003e3v\u003c/sub\u003e and (\u003cstrong\u003ed\u003c/strong\u003e) D\u003csub\u003e3d\u003c/sub\u003e-Sn\u003csub\u003e1\u003c/sub\u003e model, as well as H point for 5\u003cem\u003es\u003c/em\u003e-contributed charge density map. PL mechanism diagram of (\u003cstrong\u003ee\u003c/strong\u003e) Br\u003csup\u003e−\u003c/sup\u003e-doped and (\u003cstrong\u003ef\u003c/strong\u003e) Sn\u003csup\u003e2+\u003c/sup\u003e-doped CsCdCl\u003csub\u003e3\u003c/sub\u003e perovskites.\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-3791302/v1/c112ecf8b3d678bce3edc702.png"},{"id":49412661,"identity":"1068d9b9-17be-46eb-8922-5afc4708861c","added_by":"auto","created_at":"2024-01-10 10:48:23","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":816144,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eTime-valve controlled color for multilevel security.\u003c/strong\u003e (\u003cstrong\u003ea\u003c/strong\u003e) Photographs of labels prepared by CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br and CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn sample powders under 254 nm irradiation, along with corresponding afterglow emission after ceasing excitation at (\u003cstrong\u003eb\u003c/strong\u003e) 1 s, (\u003cstrong\u003ec\u003c/strong\u003e) 3 s and (\u003cstrong\u003ed\u003c/strong\u003e) 120 s. (\u003cstrong\u003ee\u003c/strong\u003e) QR code image of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br and CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn under 254 nm UV lamp, followed by afterglow imaging at different time intervals. (\u003cstrong\u003ef\u003c/strong\u003e) Schematic illustration of the QR code of the encryption and decryption process. (\u003cstrong\u003eg\u003c/strong\u003e) QR code map including CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br and CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn, with A (0%Br), C(0.2%Br), D (0.5%Br), E (0.8%Br), F (1%Br), G (3%Br), H (5%Br), J (10%Br), H (15%Br), L (1%Sn), M (3%Sn), O (5%Sn), S (10%Sn) and T (15%Sn). (\u003cstrong\u003eh\u003c/strong\u003e) Conversion between binary and decimal for QR code with afterglow imaging after 18 s.\u003c/p\u003e","description":"","filename":"image6.png","url":"https://assets-eu.researchsquare.com/files/rs-3791302/v1/5fd9b0429a8d71bd402a76fc.png"},{"id":58789975,"identity":"d27445ff-7b80-48a3-ad65-a02bd00f6b81","added_by":"auto","created_at":"2024-06-21 07:06:59","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5316583,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3791302/v1/d43a21ec-a592-463d-96e4-6b1f92b3bcfe.pdf"},{"id":49412664,"identity":"7bfd0d11-cd1d-4d4e-b3c6-9a44bc89e52f","added_by":"auto","created_at":"2024-01-10 10:48:23","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":81028,"visible":true,"origin":"","legend":"Date S1","description":"","filename":"DateS1CheckCIFreportofpureCsCdCl3perovskites.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3791302/v1/f6b6b9bb3276faa289d757de.pdf"},{"id":49412667,"identity":"410f713f-c10e-4e17-bc24-bfd6757aa1c4","added_by":"auto","created_at":"2024-01-10 10:48:26","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":21573005,"visible":true,"origin":"","legend":"\u003cp\u003eSupplementary Information\u003c/p\u003e","description":"","filename":"3.SupportinginformationforNatureCommun.docx","url":"https://assets-eu.researchsquare.com/files/rs-3791302/v1/78674f399943404cae6d68b1.docx"},{"id":49412666,"identity":"be9f33e6-8390-467c-b9e0-e48d0719dfba","added_by":"auto","created_at":"2024-01-10 10:48:26","extension":"mp4","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":47248815,"visible":true,"origin":"","legend":"\u003cp\u003eMovie S1\u003c/p\u003e","description":"","filename":"MovieS1LPLofBrandSndopingCsCdCl3perovskites.mp4","url":"https://assets-eu.researchsquare.com/files/rs-3791302/v1/8f922baa094bcd953e2eb8db.mp4"},{"id":49412665,"identity":"a752aa74-301e-407c-8679-069435662bfb","added_by":"auto","created_at":"2024-01-10 10:48:24","extension":"mp4","order_by":4,"title":"","display":"","copyAsset":false,"role":"supplement","size":48923214,"visible":true,"origin":"","legend":"\u003cp\u003eMovies S2\u003c/p\u003e","description":"","filename":"MovieS2Theprogressof5Danticounterfeiting.mp4","url":"https://assets-eu.researchsquare.com/files/rs-3791302/v1/5f190cd276abd67736d6c18f.mp4"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Full-color and time-valve controllable long-persistent luminescence from all-inorganic halide perovskites","fulltext":[{"header":"Introduction","content":"\u003cp\u003eLong-persistent luminescence (LPL) is an intriguing optical phenomenon characterized by sustained luminescence for durations ranging from seconds to several days after the cessation of excitation. Its earliest documented observation date back to the 17th century\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e. However, significant advancements in this research field only materialized in the 20th century, notably with the discovery of LPL in copper-doped zinc sulfide, leading to its application in glow-in-the-dark materials\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e. A groundbreaking moment occurred in the mid-1990s when Matsuzawa \u003cem\u003eet al\u003c/em\u003e. introduced the green inorganic LPL material SrAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e:Eu\u003csup\u003e2+\u003c/sup\u003e,Dy\u003csup\u003e3+\u003c/sup\u003e, utilizing oxygen-vacancy traps\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. Since then, a diverse array of afterglow phosphors, involving oxides, sulfides, and nitrides doped with various lanthanides or transition metals has been developed \u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e,\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e. These materials find widespread applications in lighting\u003csup\u003e\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e,\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e, displays\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e, bioimaging\u003csup\u003e\u003cspan additionalcitationids=\"CR10\" citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003e, photocatalysis\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e, information storage and security encryption\u003csup\u003e\u003cspan additionalcitationids=\"CR14\" citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e. However, during this rapid expansion \u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e, scientists recognized that the high-temperature synthesis process (1000\u0026thinsp;~\u0026thinsp;1500 \u003csup\u003eo\u003c/sup\u003eC) not only fails to meet the requirements of energy conservation and environmental protection requirements, but also poses a significant safety risk for manufacturers.\u003c/p\u003e \u003cp\u003eIn response to these challenges, new distinctive design concepts have recently emerged, involving molecule-based LPL through chemical synthesis and/or molecular self-assembly. In 2017, Adachi \u003cem\u003eet al.\u003c/em\u003e utilized two simple organic molecules to achieve LPL by recombining long-lived charge-separated states, marking the advent of organic LPL (OLPL)\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e. In 2022, Tang \u003cem\u003eet al.\u003c/em\u003e disrupted the pattern of multi-component synergies by employing a single-component molecular LPL system capable of detectable afterglow for more than 12 min under ambient conditions\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e. Our group has contributed to this field by developing LPL systems based on organic-inorganic halides\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e,\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e, which have emerged as promising and cost-effective semiconductor materials for sensor, optical waveguide, and information storage\u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e. However, these hybrid perovskites have only exhibited short afterglow times, attributed to mechanisms such as room temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF)\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. In 2021, Zhang \u003cem\u003eet al.\u003c/em\u003e reported a double halide perovskite system, Cs\u003csub\u003e2\u003c/sub\u003eNa\u003csub\u003ex\u003c/sub\u003eAg\u003csub\u003e1\u0026thinsp;\u0026minus;\u0026thinsp;x\u003c/sub\u003eInCl\u003csub\u003e6\u003c/sub\u003e:y%Mn\u003csup\u003e23\u003c/sup\u003e. incorporating energy transfer (ET) processes and self-trapped excitons (STEs) mechanisms to obtain LPL. Despite significant efforts in the aforementioned progress, achieving high luminescent efficiency in halide perovskite engineering or OLPL systems remains a formidable task\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e. Notably, the majorities of LPL materials tend to exhibit monochromatic (solitary color) afterglow, lacking proficiency in multifarious stimulated-response skills.\u003c/p\u003e \u003cp\u003eThe recent extensive exploration of stimuli-responsive luminescent materials\u003csup\u003e\u003cspan additionalcitationids=\"CR26\" citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e underscores their excitation-wavelength-dependence (Ex-De)\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e, as well as their intelligent response to mechanical force\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e, pH\u003csup\u003e\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e, electric field\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e, and temperature\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e in various application scenarios. In addition to advancing the development of various molecules and manipulating their lifetimes and emission efficiency, it is crucial to establish a versatile platform for LPL materials to ensure their practical utility. Simultaneously, the burgeoning field of materials exhibiting time-dependent, color-varying afterglow holds promising prospects in optoelectronic devices and high-end anti-counterfeiting products\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e. In this context, two primary strategies exist for creating such exquisite materials. One involves incorporating fluorescent dyes as acceptors (guests) into a rigid polymer matrix donor (host), facilitating F\u0026ouml;rster resonance energy transfer (FRET) in the host-guest system\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e,\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e. Commonly, their color-varying afterglow is shifted from long to short wavelengths, while the occurrence of afterglow changing towards longer wavelengths is a rare and huge task. The other entails constructing multiple luminescence centers through the regulation of the triplet and singlet energy levels\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e,\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e. Nevertheless, these advanced schemes have several drawbacks, including potential cross-chromaticity with multiple similar fluorescent dyes, short lifetimes at the millisecond to second level, challenges in tailoring a single component, and difficulty in controlling the discoloration time point during the afterglow process. Notably, the controllable time valve at the color change point is a significant gap in this field. To overcome these challenges through halide perovskite engineering, several requirements must be met: a) achieving ultralong persistent luminescence, b) demonstrating multimode luminescence, c) exhibiting a wide range of afterglow color variability, d) allowing for easy determination by the naked eye, and e) enabling an adjustable time valve for afterglow discoloration based on specific variables.\u003c/p\u003e \u003cp\u003eIn the pursuit of performance breakthroughs for typical ABX\u003csub\u003e3\u003c/sub\u003e all-inorganic perovskites, the focus primarily revolves around the regulation of B or X sites\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e. We propose that introducing doped ions into the all-inorganic skeleton can disrupt the original symmetry, forming new trap states and luminescence centers. Here, we present a dually positive design strategy to achieve color-tunable LPL by introducing Br\u003csup\u003e\u0026minus;\u003c/sup\u003e or Sn\u003csup\u003e2+\u003c/sup\u003e ions into the hexagonal phase CsCdCl\u003csub\u003e3\u003c/sub\u003e through a modified wet-chemistry method. This involves a) ensuring the Br\u003csup\u003e\u0026minus;\u003c/sup\u003e or Sn\u003csup\u003e2+\u003c/sup\u003e ion radius is comparable to that of Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e ions, b) leveraging the 4\u003cem\u003ep\u003c/em\u003e orbital effects of Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ions on the band gap and the 5\u003cem\u003es\u003c/em\u003e\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e electronic configuration of Sn\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e⁺ ions to distort the lattice, and c) using doping to break the local symmetry in the main framework, thereby establishing different trapping centers to compensate for forbidden energy transitions. Our findings indicate that disrupting geometric symmetry may generate multimode luminescence in Br\u003csup\u003e\u0026minus;\u003c/sup\u003e or Sn\u003csup\u003e2+\u003c/sup\u003e-doped perovskites at both face-shared (C\u003csub\u003e3v\u003c/sub\u003e symmetry) and corner-shared (D\u003csub\u003e3d\u003c/sub\u003e symmetry) [CdCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e octahedrons. Thermoluminescence (TL) curves demonstrate the coexistence of shallow and deep trapping centers in both Br\u003csup\u003e\u0026minus;\u003c/sup\u003e or Sn\u003csup\u003e2+\u003c/sup\u003e-doped perovskites, contributing to their anti-thermal quenching ability up to 377 K. Ultimately, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br and CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn exhibit long afterglow durations (2,000 s), with optimized photoluminescence quantum yields (PLQY) of 84.47% and 65.71%, respectively, representing cutting-edge levels among current LPL perovskites and inorganic-organic hybrids. Significantly, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br demonstrate remarkable color-varying long-afterglow properties, with color alteration at different time points precisely regulated by varying concentrations of Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ions. Moreover, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br display wide-range (97K-377K) temperature-dependent PL properties, enabling full-color adjustability. Specifically, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn exhibit a unique optical behavior analogous to Janus-type emission\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e, including forward and reverse excitation-dependent LPL at low or room temperature, respectively. These multifunctional LPL perovskites hold substantial potential for high-level anti-counterfeiting and information security in extreme scenarios.\u003c/p\u003e"},{"header":"Results","content":"\u003cp\u003e\u003cstrong\u003eSynthesis and structure.\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eA straightforward synthesis method is essential for achieving LPL. In the elevated temperature solid state method (1000\u0026thinsp;~\u0026thinsp;1500℃) for afterglow phosphors\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e, the high-temperature melting process towards OLPL materials heavily depends on the melting/boiling point similarity of each component to prevent bond breakage and reorientation\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e. Conventional solution chemistry methods have been employed for short-lived afterglow of organic-inorganic halides and crystalline/polymeric organic materials\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e22\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e23\u003c/span\u003e,\u003cspan class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/sup\u003e. In this work, single crystals of CsCdCl\u003csub\u003e3\u003c/sub\u003e can be grown using a modified hydrothermal reaction (details in Methods, Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ef), and its crystal lattice adapts a space group P6\u003csub\u003e3\u003c/sub\u003e/mmc (CCDC No. 2313854). The 3D asymmetric unit, as shown in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ea and Supplementary Fig.\u0026nbsp;1, is constructed with [CdCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e octahedrons. Two of these share a triangular face to form [Cd\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e9\u003c/sub\u003e]\u003csup\u003e5\u0026minus;\u003c/sup\u003e in C\u003csub\u003e3v\u003c/sub\u003e symmetry, which then connected with six additional [CdCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e octahedra to achieve corner-shared D\u003csub\u003e3d\u003c/sub\u003e symmetry. This unique packing arrangement offers numerous coordination sites for diverse halides and divalent metal cations, allowing for the\u0026nbsp;arbitrarily anchoring of Br\u003csup\u003e\u0026minus;\u003c/sup\u003e or Sn\u003csup\u003e2+\u003c/sup\u003e ions at the Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e or Cd\u003csup\u003e2+\u003c/sup\u003e ion sites, potentially leading to distinct optical properties. Upon alternation by Br\u003csup\u003e\u0026minus;\u003c/sup\u003e or Sn\u003csup\u003e2+\u003c/sup\u003e ions, the powdered X-ray diffraction (PXRD) patterns of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br and CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn closely agree with the pattern in the PDF#18\u0026ndash;0337, confirming the single-phase purity of the synthesized Br\u003csup\u003e\u0026minus;\u003c/sup\u003e or Sn\u003csup\u003e2+\u003c/sup\u003e-doped CsCdCl\u003csub\u003e3\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e, b to c and Supplementary Figs.\u0026nbsp;2 and 3). This leads to the expansion of the host lattice, manifested by the shifting of Bragg positions at [104] and [110] to lower angles (Supplementary Figs.\u0026nbsp;2 and 3). The ion radius values of Br\u003csup\u003e\u0026minus;\u003c/sup\u003e (r\u0026thinsp;=\u0026thinsp;1.96 \u0026Aring;) and Sn\u003csup\u003e2+\u003c/sup\u003e (r\u0026thinsp;=\u0026thinsp;1.02 \u0026Aring;, CN\u0026thinsp;=\u0026thinsp;6) are larger than those of Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e (r\u0026thinsp;=\u0026thinsp;1.81 \u0026Aring;) and Cd\u003csup\u003e2+\u003c/sup\u003e (r\u0026thinsp;=\u0026thinsp;0.95 \u0026Aring;, CN\u0026thinsp;=\u0026thinsp;6), respectively, contributing to the observed lattice expansion. X-ray photoelectron spectroscopy (XPS) profiles describe Br\u003csup\u003e\u0026minus;\u003c/sup\u003e- and Sn\u003csup\u003e2+\u003c/sup\u003e-doped samples, with the characteristic peaks of Br\u003csup\u003e\u0026minus;\u003c/sup\u003e 3\u003cem\u003ed\u003c/em\u003e and Sn ion 3\u003cem\u003ed\u003c/em\u003e\u003csub\u003e3/2\u003c/sub\u003e and 3\u003cem\u003ed\u003c/em\u003e\u003csub\u003e5/2\u003c/sub\u003e becoming more pronounced with increasing guest-doped concentration (Supplementary Figs.\u0026nbsp;4 and 5). Particularly, the peaks centered at 3\u003cem\u003ed\u003c/em\u003e\u003csub\u003e3/2\u003c/sub\u003e = 496.02 eV and 3\u003cem\u003ed\u003c/em\u003e\u003csub\u003e5/2\u003c/sub\u003e = 487.02 eV correspond to Sn\u003csup\u003e2\u0026thinsp;+\u0026thinsp;43,44\u003c/sup\u003e, suggesting that a tiny amount of Sn\u003csup\u003e2+\u003c/sup\u003e doping can preserve its stability (Supplementary Fig.\u0026nbsp;5b, 5d).\u003c/p\u003e\n\u003cp\u003eScanning electron microscope (SEM) images show a typical spindle shape of Br\u003csup\u003e\u0026minus;\u003c/sup\u003e or Sn\u003csup\u003e2+\u003c/sup\u003e-doped CsCdCl\u003csub\u003e3\u003c/sub\u003e crystals, with uniform distribution of elemental constituents (Cs, Cd, Cl, Br or Sn) in element mapping images, confirming the successful dopant engineering of Br\u003csup\u003e\u0026minus;\u003c/sup\u003e or Sn\u003csup\u003e2+\u003c/sup\u003e ions (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ed, \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ee). The standard Rietveld refinement technique reveals a poor linear relationship between the nominal concentrations of Br or Sn and the distance of the (110) planes, somewhat deviating from the Vegard's law. To investigate this deviation, energy dispersive spectroscopy (EDS) was employed to determine the actual concentrations of Br\u003csup\u003e\u0026minus;\u003c/sup\u003e or Sn\u003csup\u003e2+\u003c/sup\u003e ions in crystals (Supplementary Figs.\u0026nbsp;2b and 3b, Supplementary Table S2 and S3). Interestingly, the actual concentrations exhibit perfect linearity with respect to the \u003cem\u003ed\u003c/em\u003e\u003csub\u003e110\u003c/sub\u003e plane and strictly adhere to Vegard's law\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e. These results suggest that the concentrations of Br-doping slightly exceed the nominal value, while the opposite holds true for Sn-doping, which can be attributed to differences in solubility and solvent boiling points.\u003c/p\u003e\n\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\n\u003ch2\u003ePhotophysical Properties\u003c/h2\u003e\n\u003cp\u003eThe optical characteristics of CsCdCl\u003csub\u003e3\u003c/sub\u003e single crystals were initially investigated. As depicted in Supplementary Fig.\u0026nbsp;8a to 8c, the optimal excitation wavelength for the photoluminescence excitation (PLE) center of pure CsCdCl\u003csub\u003e3\u003c/sub\u003e is 254 nm, inducing a broad emission peak at 595 nm with a full width at half-maximum (FWHM) of 88 nm in both prompt and delayed spectra (collected after 1 ms of excitation). CsCdCl\u003csub\u003e3\u003c/sub\u003e displays robust excitonic absorption, aligning well with the PLE spectrum (Supplementary Figs.\u0026nbsp;7a, 8c). Given the substantial Stokes shift (341 nm) and wide FWHM, the observed orange emission is attributed to the self-trapping excitons (STEs) emission, consistent with the prior report\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e. Nevertheless, the low emission intensity (PLQY\u0026sim;25.47%) significantly restricts its applicability (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ei, Supplementary Fig.\u0026nbsp;30a).\u003c/p\u003e\n\u003cp\u003eOne strategy to modulate PL properties is introducing different halide cations with tunable band gaps, as observed in lead-based perovskites to achieve nanosecond luminescent lifetimes\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e. Doping a series of Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ions produces noticeable changes in the corresponding optical spectra. As shown in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea and Supplementary Fig.\u0026nbsp;8a, under 254 nm excitation, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br (\u003cem\u003ex\u003c/em\u003e\u0026thinsp;=\u0026thinsp;0.2\u0026ndash;15) crystals exhibit a blue-shifted\u0026nbsp;and progressively stronger broad emission peak at 482 nm compared to the pristine CsCdCl\u003csub\u003e3\u003c/sub\u003e crystals. The delayed spectra reveal that intensities peaking at 482 and 595 nm are both enhanced with increasing Br\u003csup\u003e\u0026minus;\u003c/sup\u003e doping concentration (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea, Supplementary Fig.\u0026nbsp;8b), resulting in a merging into a single large peak spanning from 350 to 800 nm, akin to the behavior observed in the prompt spectra. CsCdCl\u003csub\u003e3\u003c/sub\u003e possesses both C\u003csub\u003e3v\u003c/sub\u003e and D\u003csub\u003e3d\u003c/sub\u003e symmetries\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e, with the a\u003csub\u003e1\u003c/sub\u003e\u0026rarr;e transition allowed in C\u003csub\u003e3v\u003c/sub\u003e symmetry and the a\u003csub\u003e1g\u003c/sub\u003e\u0026rarr;e\u003csub\u003eg\u003c/sub\u003e transition in D\u003csub\u003e3d\u003c/sub\u003e symmetry undergoing an S-T-splitting route\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e. The radiative transition in both symmetries originates from the triplet exciton, with the energy gap of D\u003csub\u003e3d\u003c/sub\u003e tending to be larger than that of C\u003csub\u003e3v\u003c/sub\u003e\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e. Previous studies have indicated that D\u003csub\u003e3d\u003c/sub\u003e symmetry's PL is in the UV region at low temperatures due to constrained molecular vibrations accelerating the S-T splitting process\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e49\u003c/span\u003e,\u003cspan class=\"CitationRef\"\u003e50\u003c/span\u003e\u003c/sup\u003e. However, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br (\u003cem\u003ex\u003c/em\u003e\u0026thinsp;=\u0026thinsp;0.2\u0026ndash;15) crystals show robust emission centered at 482 nm without the need for low temperatures. To comprehend this behavior, we analyze the structure-luminescence relationship: replacing Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e ions with Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ions distorts the [CdCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e octahedron into [CdCl\u003csub\u003e6\u0026thinsp;\u0026minus;\u0026thinsp;n\u003c/sub\u003eBr\u003csub\u003en\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e due to distinct Cd\u0026ndash;Cl (2.66 \u0026Aring;) and Cd\u0026ndash;Br (2.71 \u0026Aring;) bond lengths\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e51\u003c/span\u003e\u003c/sup\u003e. The emission peak at 482 nm, with a large Stokes shift (228 nm) and wide FWHM, is attributed to STEs, consistent with previous reports\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e52\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e. All the PLE spectra of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br show gradually red-shifting and broadening peaks beyond 300 nm, aligning well with the absorption spectrum (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea, Supplementary Figs.\u0026nbsp;7a, 8c to 8d). This further suggests that transitions involving [e\u0026thinsp;+\u0026thinsp;a\u003csub\u003e1\u003c/sub\u003e] \u0026rarr;a\u003csub\u003e1\u003c/sub\u003e and [e\u0026thinsp;+\u0026thinsp;a\u003csub\u003e1\u003c/sub\u003e] \u0026rarr;e, a\u003csub\u003e1\u003c/sub\u003e in C\u003csub\u003e3v\u003c/sub\u003e, as well as [e\u003csub\u003eu\u003c/sub\u003e + a\u003csub\u003e2u\u003c/sub\u003e] \u0026rarr;a\u003csub\u003e1g\u003c/sub\u003e in D\u003csub\u003e3d\u003c/sub\u003e are all activated. Therefore, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br samples exhibit a significantly enhanced PLQY up to 84.47% without relying on rare-earth metals (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ei, Supplementary Fig.\u0026nbsp;30), signifying a resource-saving approach for high-efficiency luminescence.\u003c/p\u003e\n\u003cp\u003eTo understand the PL mechanism, temperature-dependent PL spectra for the representative of CsCdCl\u003csub\u003e3\u003c/sub\u003e:0.8%Br and CsCdCl\u003csub\u003e3\u003c/sub\u003e:10%Br were conducted. As illustrated in Supplementary Fig.\u0026nbsp;9a, the PL peak (band 3) emerges at low temperatures, followed by band 2 as temperature increases to room level, and then band 3 becomes more prominent at higher temperatures. Obviously, because of the low doping concentration of Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ions, both D\u003csub\u003e3d\u003c/sub\u003e and C\u003csub\u003e3v\u003c/sub\u003e exist in [CdCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e and [CdCl\u003csub\u003e6\u0026thinsp;\u0026minus;\u0026thinsp;n\u003c/sub\u003eBr\u003csub\u003en\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e forms, with band 3 assigned to pure [CdCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e in D\u003csub\u003e3d\u003c/sub\u003e symmetry at low temperature\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e, and band 2 with broad emission corresponding to the Br-doped of [CdCl\u003csub\u003e6\u0026thinsp;\u0026minus;\u0026thinsp;n\u003c/sub\u003eBr\u003csub\u003en\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e in both D\u003csub\u003e3d\u003c/sub\u003e and C\u003csub\u003e3v\u003c/sub\u003e symmetry, while band 1 represents the undoped [CdCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e unit in C\u003csub\u003e3v\u003c/sub\u003e symmetry\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e52\u003c/span\u003e,\u003cspan class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e. For the delayed spectra (Supplementary Fig.\u0026nbsp;9b), bands 3 and 2 have maintained long-lived photoemission owing to the triplet exciton arising from D\u003csub\u003e3d\u003c/sub\u003e and C\u003csub\u003e3v\u003c/sub\u003e symmetry to cause phosphorescence. The increased FWHM by photon-phonon coupling in a specific temperature range of 217 to 277 K (Supplementary Fig.\u0026nbsp;9a, 9b), along with the large Stokes-shift, provides direct evidence that band 2 emission is associated with STEs\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e51\u003c/span\u003e,\u003cspan class=\"CitationRef\"\u003e54\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e55\u003c/span\u003e\u003c/sup\u003e. Upon 10% Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ion doping, the prompt spectra show that band 3 blends into band 2 at low temperatures due to the transformation of [CdCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e into [CdCl\u003csub\u003e6\u0026thinsp;\u0026minus;\u0026thinsp;n\u003c/sub\u003eBr\u003csub\u003en\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e in D\u003csub\u003e3d\u003c/sub\u003e (Supplementary Fig.\u0026nbsp;9c), again confirming the band 3 originates from D\u003csub\u003e3d\u003c/sub\u003e symmetry. The corresponding luminescence mechanism is depicted in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ee. It is noteworthy that band 1 in both samples becomes stronger with increasing temperature up to 377 K (Supplementary Fig.\u0026nbsp;9), illustrating its anti-thermal quenching ability, which will be further discussed below. Intriguingly, both the prompt and delayed spectra of CsCdCl\u003csub\u003e3\u003c/sub\u003e:0.8%Br and 10%Br exhibit excellent temperature-dependent luminescent properties (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ee and \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ef, Supplementary Fig.\u0026nbsp;10). Of that, CsCdCl\u003csub\u003e3\u003c/sub\u003e:0.8%Br displays remarkable color variation, ranging from blue to cyan, then across yellow-green and finally to orange-red, observable with naked eyes (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ed), in good agreement with CIE coordination (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eb, \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ec). Such a wide range of full-color tunable luminescence and the anti-thermal quenching properties are still rare, particularly in state-of-the-art LPL materials (Supplementary Table\u0026nbsp;4).\u003c/p\u003e\n\u003cp\u003eRemarkably, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br samples exhibit substantial LPL with distinctive time-dependent afterglow alterations. As illustrated in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ea, the pristine CsCdCl\u003csub\u003e3\u003c/sub\u003e host manifests an orange-red afterglow extinguishing promptly upon cessation of the 254 nm UV lamp. CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br, conversely, hold a bright blue-green color when exposed to 254 nm UV light. Subsequent to excitation cessation, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br exhibit color-variable LPL from blue-green to orange-red, effectively covering the entire visible spectrum. Notably, unlike conventional time-dependent luminescence, herein the time-valve in the color change can be regulated based on Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ion concentration. To elucidate this phenomenon, steady-state luminescent decay curves were monitored at emission centers of 482 and 595 nm. As shown in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eg, the afterglow intensity at 595 nm rapidly diminishes in the first 500 s, followed by a gradual decline extending up to 2000 s to discern from the background. The decay lifetime of 482 nm in the initial 60 s window is extended with increasing the Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ion concentration to 10% (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eh). As observed in Supplementary Movie 1, the afterglow persists for 1800 s to naked eyes. Analysis of time-resolved PL mapping in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eb and Supplementary Fig.\u0026nbsp;11 indicate that the emission band at 595 nm remains consistently strong, while the band at 482 nm gradually intensifies with Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ion concentration doping to 5%. The time-dependent afterglow spectrum exhibits that the emission bands at 595 and 482 nm initially merge into a broad acromion (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ec, Supplementary Fig.\u0026nbsp;12), with the intensity at 595 and 482 nm linked to both time evolution and Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ion doping concentrations. Hence, the color-variable LPL can be modulated by different decay lifetimes of emissions at 482 nm and 595 nm, as well as Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ion concentrations in CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br.\u003c/p\u003e\n\u003cp\u003eCharge trap state analysis through TL measurements is an effective method for elucidating LPL. Firstly, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br show good thermal stability (Supplementary Fig.\u0026nbsp;6a). No TL signal is detected for the pristine CsCdCl\u003csub\u003e3\u003c/sub\u003e, implying the absence of LPL nature (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ed). For CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br, four different cases arise: ⅰ) \u003cem\u003ex\u003c/em\u003e\u0026thinsp;=\u0026thinsp;0.2\u0026thinsp;~\u0026thinsp;0.5, the TL single peak center appears at 370 K; ⅱ) \u003cem\u003ex\u003c/em\u003e\u0026thinsp;=\u0026thinsp;0.8, three peaks of 366, 392 and 465 K are observed; ⅲ) \u003cem\u003ex\u003c/em\u003e\u0026thinsp;=\u0026thinsp;1\u0026thinsp;~\u0026thinsp;5, the TL peaks lie in 380 and 445 K; ⅳ) \u003cem\u003ex\u003c/em\u003e\u0026thinsp;=\u0026thinsp;10\u0026thinsp;~\u0026thinsp;15, the TL peaks occur at 371 and 355 K. The trap energy level can be estimated by Urbach\u0026rsquo;s empirical formula E\u003csub\u003etrap\u003c/sub\u003e =T\u003csub\u003em\u003c/sub\u003e/500 (T\u003csub\u003em\u003c/sub\u003e is the temperature of TL peak)\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e56\u003c/span\u003e\u003c/sup\u003e. Accordingly, the aforementioned TL peaks are determined to be 0.74 (370 K), 0.73 (366 K), 0.78 (392 K), 0.93 (465 K), 0.76 (380 K), 0.89 (445 K), 0.74 (371 K), and 0.71 eV (355 K), respectively. These CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br samples all possess shallow traps ranging from 0.67 to 0.76 eV, preferable for creating an ideal depth for LPL\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e57\u003c/span\u003e\u003c/sup\u003e. In addition, the trap depths in the range of 0.8\u0026ndash;1.6 eV are categorized as deep traps, typically resulting in low LPL at room temperature due to the activation energy barrier\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e58\u003c/span\u003e\u003c/sup\u003e. However, as the temperature increases, the charge carriers in the deep traps overcome the activation energy barrier and migrate to the emission center, leading to an anti-thermal quenching property.\u003c/p\u003e\n\u003cp\u003eAn alternative avenue to achieve benefits involves selecting appropriate metal cations as activators in metal halides. Consequently, we opt for the Sn\u003csup\u003e2+\u003c/sup\u003e ion as the doped emissary for CsCdCl\u003csub\u003e3\u003c/sub\u003e to elucidate the luminous properties. As illustrated in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea and Supplementary Fig.\u0026nbsp;13b,13c, under the excitation of 254 nm UV light, a predominant emission peak at 595 nm is significantly enhanced in both prompt and delayed spectra with increasing Sn\u003csup\u003e2+\u003c/sup\u003e ion dopant concentration from 1\u0026ndash;10%. However, further doping results in a slightly reduced peak intensity. CsCdCl\u003csub\u003e3\u003c/sub\u003e:10%Sn displays the highest PLQY up to 65.71% (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ef, Supplementary Fig.\u0026nbsp;31). Subsequently, the PLQY experiences a marginal decline with a further increase of Sn\u003csup\u003e2+\u003c/sup\u003e ion concentration, attributed to intensified Sn\u003csup\u003e2+\u003c/sup\u003e-Sn\u003csup\u003e2+\u003c/sup\u003e dipole interactions causing nonradiative energy transition. The prompt and delayed PLE spectra exhibit a primary peak centered at 254 nm (Supplementary Fig.\u0026nbsp;13a, 13c), with an apparent shoulder peak at 282 nm becoming more pronounced as Sn\u003csup\u003e2+\u003c/sup\u003e ion concentration increases, consistent well with the absorption spectra (Supplementary Fig.\u0026nbsp;7b).\u003c/p\u003e\n\u003cp\u003eAs depicted in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea and Supplementary Fig.\u0026nbsp;13e, h, an obvious emission peak at 565 nm is enhanced upon increasing the Sn\u003csup\u003e2+\u003c/sup\u003e ions under the excitation wavelength of 282 nm. To further investigate this uncommon phenomenon, a series of excitation-wavelength dependent PL spectra and 2D excitation maps were performed for these CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e% Sn. As shown in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ei and Supplementary Fig.\u0026nbsp;14, 18, as the excitation wavelength red-shifts from 250 to 285 nm, the emission band center at 595 nm undergoes a significant blue shift to 565 nm with reduced intensity in both prompt and delayed spectra. Continuous shifting of the excitation to 310 nm results in a faint peak at 480 nm, which is negligible in the 2D excitation map (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ei, bottom, Supplementary Figs.\u0026nbsp;14 to 18, right). Notably, such a large contrast in the blue-shifted emission based on continuous red-shifted excitation at room temperature has not been reported in halide perovskites, even rarely among various current luminous materials (Supplementary Table\u0026nbsp;4).\u003c/p\u003e\n\u003cp\u003eTo elucidate this intriguing phenomenon, we conducted temperature-dependent PL spectra for representative CsCdCl\u003csub\u003e3\u003c/sub\u003e:3%Sn and CsCdCl\u003csub\u003e3\u003c/sub\u003e:10%Sn. As shown in Supplementary Fig.\u0026nbsp;19, 20, under 254 nm irradiation at low temperatures, the initial observation is the emergence of prompt PL band ⅲ, faintly mirrored in the delayed spectrum, alongside the prompt PLE peak at 254 nm (Supplementary Fig.\u0026nbsp;21). These findings suggest that the band ⅲ originates from unaltered [CdCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e in D\u003csub\u003e3d\u003c/sub\u003e symmetry. As the temperature rises to 177 K, a broad prompt PL band ⅱ becomes prominent, replacing the weakened band ⅲ, a change similarly in the delayed spectra, indicating their common origin in triplet excitons (Supplementary Figs.\u0026nbsp;19b, 20b). Considering Sn\u003csup\u003e2+\u003c/sup\u003e ions with a 5\u003cem\u003es\u003c/em\u003e\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e electron configuration and \u003csup\u003e1\u003c/sup\u003eP\u003csub\u003e1\u003c/sub\u003e/\u003csup\u003e3\u003c/sup\u003eP\u003csub\u003e0,1,2\u003c/sub\u003e energy levels\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e59\u003c/span\u003e\u003c/sup\u003e. transitions such as \u003csup\u003e\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eS\u003csub\u003e0\u003c/sub\u003e \u0026rarr;\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003eP\u003csub\u003e0\u003c/sub\u003e and \u003csup\u003e\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eS\u003csub\u003e0\u003c/sub\u003e \u0026rarr;\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003eP\u003csub\u003e2\u003c/sub\u003e are deemed forbidden, while allowed transitions include \u003csup\u003e\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eS\u003csub\u003e0\u003c/sub\u003e\u0026rarr;\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003eP\u003csub\u003e1\u003c/sub\u003e and \u003csup\u003e\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eS\u003csub\u003e0\u003c/sub\u003e\u0026rarr;\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eP\u003csub\u003e1\u003c/sub\u003e due to spin-orbit coupling\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e60\u003c/span\u003e,\u003cspan class=\"CitationRef\"\u003e61\u003c/span\u003e\u003c/sup\u003e. The broad emission band ii is primarily attributed to the \u003csup\u003e\u003cspan class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003eP\u003csub\u003e1\u003c/sub\u003e \u0026rarr;\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eS\u003csub\u003e0\u003c/sub\u003e transition of Sn\u003csup\u003e2+\u003c/sup\u003e ions situated in D\u003csub\u003e3d\u003c/sub\u003e [SnCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e symmetry, partially involving the breaking of the forbidden transition \u003csup\u003e\u003cspan class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003eP\u003csub\u003e2\u003c/sub\u003e\u0026rarr;\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eS\u003csub\u003e0\u003c/sub\u003e at low temperatures\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e62\u003c/span\u003e\u003c/sup\u003e. Upon further temperature elevation, the emission band ⅰ gradually intensifies, with its FWHM increasing due to photon-phonon coupling in both prompt and delayed spectra (Supplementary Figs.\u0026nbsp;19, 20). Given the large Stokes shift is similar to the pristine CsCdCl\u003csub\u003e3\u003c/sub\u003e, band ⅰ can also be identified as STEs originating from Cd\u003csup\u003e2+\u003c/sup\u003e ions in conjunction with the distortion of [SnCdCl\u003csub\u003e9\u003c/sub\u003e]\u003csup\u003e5\u0026minus;\u003c/sup\u003e moieties in C\u003csub\u003e3v\u003c/sub\u003e symmetry.\u003c/p\u003e\n\u003cp\u003eTo further substantiate this hypothesis, we adjusted the excitation wavelength to 282 nm. As illustrated in Supplementary Figs.\u0026nbsp;22, 23, the PL band ⅲ diminishes, while band ⅱ remains robust at low temperature, affirming their origin from [CdCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e and [SnCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e in D\u003csub\u003e3d\u003c/sub\u003e symmetry, respectively. With increasing temperature, a newly emerging band ⅳ with an emission center at 565 nm gains strength progressively. This observation is influenced by two main factors: a) Lower excitation energy effectively populates the exciton to the lower-energy \u003csup\u003e\u003cspan class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003eP\u003csub\u003e1\u003c/sub\u003e state of the Sn\u003csup\u003e2+\u003c/sup\u003e ion in distorted [SnCdCl\u003csub\u003e9\u003c/sub\u003e]\u003csup\u003e5\u0026minus;\u003c/sup\u003e, where the thermodynamically favored \u003csup\u003e\u003cspan class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003eP\u003csub\u003e1\u003c/sub\u003e exciton serves as a trapped state, enhancing anti-thermal quenching ability. \u003csup\u003e\u003cspan class=\"CitationRef\"\u003e60\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e61\u003c/span\u003e,\u003cspan class=\"CitationRef\"\u003e63\u003c/span\u003e\u003c/sup\u003e b) The wide FWHM and large Stokes shift crucially support its STEs\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e64\u003c/span\u003e\u003c/sup\u003e. Further, a series of excitation-dependent PL experiments were conducted on CsCdCl\u003csub\u003e3\u003c/sub\u003e:3%Sn and CsCdCl\u003csub\u003e3\u003c/sub\u003e:10%Sn at 97 K. As shown in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eh, Supplementary Figs. S24a, 25a, varying the excitation wavelength from 250 to 300 nm results in a red-shift of the prompt emission center from 440 to 565 nm, corresponding well with the above-mentioned band ⅲ, band ⅱ and band ⅳ. In the delayed spectra (Supplementary Figs.\u0026nbsp;24b, 25b), the emission band at 595 nm (band ⅰ) decreases, and the broad emission band centered at 525 nm (band ⅱ) intensifies, confirming that optical properties are influenced by the geometric symmetry and energy states of the metal centers\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e63\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e65\u003c/span\u003e\u003c/sup\u003e. The corresponding luminescence mechanism is depicted in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ef. The distinctive feature as Janus-type luminescence \u0026ndash; forward excitation-dependence at low temperature and the reverse excitation-dependence at room temperature \u0026ndash; has not been reported previously (Supplementary Table\u0026nbsp;4), holding promise for potential applications in information safety and temperature recognition. After 46 days of storage at room temperature, all samples exhibit no significant spectral changes (Supplementary Figs.\u0026nbsp;28, 29), underscoring the excellent optical stability of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e% Sn.\u003c/p\u003e\n\u003cp\u003eRemarkably, all CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn samples emit orange-red LPL after the cessation of 254 nm UV light (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ee and Supplementary Movie 1). The steady-state luminescent decay of the emission bands at 595 nm and 565 nm were investigated. Following the termination of 254 nm irradiation, the intensity of the CsCdCl\u003csub\u003e3\u003c/sub\u003e:3%Sn rapidly decreases in an initial 500 s and persists for up to 2000 s (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eb). For Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ec, the intensity of the CsCdCl\u003csub\u003e3\u003c/sub\u003e:10%Sn at 565 nm also decays quickly in the first 400 s, and gradually slows down until reaching 1000 seconds. The characteristics of LPL at 595 nm and 565 nm are demonstrated through time-resolved PL mapping (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ed, \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ee, Supplementary Fig.\u0026nbsp;26) and the time-dependent afterglow emission spectrum (Supplementary Fig.\u0026nbsp;27). Moreover, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn exhibit good thermal stability (Figure S6 b). Focusing on the TL spectra (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eg), CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn exhibit distinct peak centers and trap energy levels (estimated by E\u003csub\u003etrap\u003c/sub\u003e = T\u003csub\u003em\u003c/sub\u003e/500) at different \u003cem\u003ex\u003c/em\u003e values: \u003cem\u003ex\u003c/em\u003e\u0026thinsp;=\u0026thinsp;1 (355K\u0026rarr;0.71eV), 3 (355K\u0026rarr;0.71 eV, 395K\u0026rarr;0.79 eV), 5 (363K\u0026rarr;0.73 eV, 434K\u0026rarr;0.87 eV), 10 (363K\u0026rarr;0.73 eV, 374K\u0026rarr;0.75 eV and 452K\u0026rarr;0.90 eV), and 15 (342K\u0026rarr;0.68 eV, 436K\u0026rarr;0.87 eV), respectively. Given this, it is no surprise that trap states play a crucial role in saving excitons from the excited state, evoking the LPL of these CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn by releasing excitons from shallow traps and thermally breaking the energy barrier in deep traps to the ground state.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\n\u003ch2\u003eDensity Functional Theory (DFT)\u003c/h2\u003e\n\u003cp\u003eTo gain deeper insights into the electronic structure and luminescence mechanisms of Br-doped and Sn-doped CsCdCl\u003csub\u003e3\u003c/sub\u003e, we conducted band structure and total density of states (DOS) calculations. The pristine CsCdCl\u003csub\u003e3\u003c/sub\u003e exhibits a direct bandgap, whereas the Br-doped and Sn-doped models exhibit indirect bandgaps (Fig. S33 to S34), thereby mitigating hole-electron recombination and extending exciton lifetimes\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e66\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e67\u003c/span\u003e\u003c/sup\u003e. In Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ea and Fig. S36 to S40, the projected DOS (PDOS) of D\u003csub\u003e3d\u003c/sub\u003e-Br\u003csub\u003ei\u003c/sub\u003e-C\u003csub\u003e3v\u003c/sub\u003e (i\u0026thinsp;=\u0026thinsp;1,2,3) and C\u003csub\u003e3v\u003c/sub\u003e-Br\u003csub\u003ej\u003c/sub\u003e-C\u003csub\u003e3v\u003c/sub\u003e (j\u0026thinsp;=\u0026thinsp;4,5,6) models reveal that the valence band (VB) is mainly composed of Cl 3\u003cem\u003ep\u003c/em\u003e and Br 4\u003cem\u003ep\u003c/em\u003e orbitals, while the conduction band (CB) consists of Cd 5\u003cem\u003es\u003c/em\u003e/5\u003cem\u003ep\u003c/em\u003e, Br 4\u003cem\u003ep\u003c/em\u003e, and Cl 3\u003cem\u003ep\u003c/em\u003e orbitals. In contrast, Cs orbitals play a negligible role in the band structures of these models. The charge density maps illustrate that the valance band maximum (VBM) is localized at Br\u003csup\u003e\u0026minus;\u003c/sup\u003e and Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e ions in [CdCl\u003csub\u003e6\u0026thinsp;\u0026minus;\u0026thinsp;n\u003c/sub\u003eBr\u003csub\u003en\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e moiety of both D\u003csub\u003e3d\u003c/sub\u003e and C\u003csub\u003e3v\u003c/sub\u003e symmetry, while the conduction band maximum (CBM) is predominantly formed from Cd\u003csup\u003e2+\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ec, Supplementary Figs.\u0026nbsp;36b to 40b). The small discrepancy in bandgaps between the D\u003csub\u003e3d\u003c/sub\u003e-Br\u003csub\u003ei\u003c/sub\u003e-C\u003csub\u003e3v\u003c/sub\u003e (i\u0026thinsp;=\u0026thinsp;1,2,3) and C\u003csub\u003e3v\u003c/sub\u003e-Br\u003csub\u003ej\u003c/sub\u003e-C\u003csub\u003e3v\u003c/sub\u003e (j\u0026thinsp;=\u0026thinsp;4,5,6) models, approximately 12.2 meV, has negligible impact on the PL of [CdCl\u003csub\u003e6\u0026thinsp;\u0026minus;\u0026thinsp;n\u003c/sub\u003eBr\u003csub\u003en\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e in both D\u003csub\u003e3d\u003c/sub\u003e and C\u003csub\u003e3v\u003c/sub\u003e symmetries (Supplementary Fig.\u0026nbsp;33g). This reaffirms that the broad emission band at 482 nm (band 2) in Br-doped CsCdCl\u003csub\u003e3\u003c/sub\u003e originates from the combined emission center of [CdCl\u003csub\u003e6\u0026thinsp;\u0026minus;\u0026thinsp;n\u003c/sub\u003eBr\u003csub\u003en\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e in both D\u003csub\u003e3d\u003c/sub\u003e and C\u003csub\u003e3v\u003c/sub\u003e symmetries (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea, \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ee, Supplementary Fig.\u0026nbsp;9).\u003c/p\u003e\n\u003cp\u003eFor Sn-doped CsCdCl\u003csub\u003e3\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003eB, Fig. S41 to S43), PDOS shows that VBs consist of Cl 3\u003cem\u003ep\u003c/em\u003e and Sn 5\u003cem\u003es\u003c/em\u003e orbitals, while the CBs comprise Cl 3\u003cem\u003ep\u003c/em\u003e, Sn 5\u003cem\u003ep\u003c/em\u003e and Cd 5\u003cem\u003es\u003c/em\u003e/5\u003cem\u003ep\u003c/em\u003e orbitals in D\u003csub\u003e3d\u003c/sub\u003e-Sn\u003csub\u003ei\u003c/sub\u003e (i\u0026thinsp;=\u0026thinsp;1,4) and C\u003csub\u003e3v\u003c/sub\u003e-Sn\u003csub\u003ej\u003c/sub\u003e (j\u0026thinsp;=\u0026thinsp;2,3) models. The bandgap of D\u003csub\u003e3d\u003c/sub\u003e-Sn\u003csub\u003ei\u003c/sub\u003e (i\u0026thinsp;=\u0026thinsp;1,4) models is larger than C\u003csub\u003e3v\u003c/sub\u003e-Sn\u003csub\u003ej\u003c/sub\u003e (j\u0026thinsp;=\u0026thinsp;2,3) models, around 30.4\u0026ndash;95.7 meV (Supplementary Fig.\u0026nbsp;34g), impacting the PL characteristics of [SnCl\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e in both D\u003csub\u003e3d\u003c/sub\u003e and C\u003csub\u003e3v\u003c/sub\u003e symmetries due to exceeding the thermal energy of 26 meV\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e68\u003c/span\u003e\u003c/sup\u003e. This observation aligns with the experimental trend of Sn-doped materials exhibiting a reduced bandgap (Supplementary Fig.\u0026nbsp;7d). Additionally, these results underscore that the luminescence center of Sn\u003csup\u003e2+\u003c/sup\u003e ions in C\u003csub\u003e3v\u003c/sub\u003e [SnCdCl\u003csub\u003e9\u003c/sub\u003e]\u003csup\u003e5\u0026minus;\u003c/sup\u003e symmetry requires less matching excitation energy, resulting in the reverse excitation-dependent behavior observed in experiment. From Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ed and Supplementary Figs.\u0026nbsp;41b to 43b, the charge density maps highlight Sn\u003csup\u003e2+\u003c/sup\u003e ion with unique 5\u003cem\u003es\u003c/em\u003e-related energy levels significantly influencing the VBM and contributing to multimode luminescence. Interestingly, when Sn\u003csup\u003e2+\u003c/sup\u003e ion doping at C\u003csub\u003e3v\u003c/sub\u003e [SnCdCl\u003csub\u003e9\u003c/sub\u003e]\u003csup\u003e5\u0026minus;\u003c/sup\u003e symmetry (Supplementary Figs.\u0026nbsp;41b to 42b), the charge density of CBM is primarily located at the Cd\u003csup\u003e2+\u003c/sup\u003e ion of C\u003csub\u003e3v\u003c/sub\u003e symmetry, further supporting the hypothesis that band ⅰ stems from C\u003csub\u003e3v\u003c/sub\u003e symmetry (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea, \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ef, Supplementary Figs.\u0026nbsp;19, 20).\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\n\u003ch2\u003eHigh-level anti-counterfeiting using multifunctional LPL\u003c/h2\u003e\n\u003cp\u003eProgramming advanced anti-counterfeiting technology is of considerable practical importance, by leveraging the LPL characteristics of all-inorganic halide perovskites to demonstrate their distinctive spatial-time-resolved, and time-logical color-variable afterglow properties. As depicted in Supplementary Fig.\u0026nbsp;44, no perceptible alterations are observed under ambient lighting conditions. However, upon exposure to 254 nm UV irradiation (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ea), the combination of chaotic orange-red and cyan colors could potentially convey misleading messages such as \u0026ldquo;I ❤ BNU 8888\u0026rdquo; (BNU: Beijing Normal University) and two other false messages when individually viewed in the orange-red or cyan channel. After ceasing the UV lamp for 1s (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003eb), the subsequent error information is interpreted as \"I ❤ BNU 2083\", accompanied by two additional error messages, resembling a three-dimensional (3D) encryption featuring spatial-time-dual-resolved patterns. The cyan \u0026ldquo;❤\u0026rdquo;transfers to milk white, and some local areas exhibit color changes in 3 s (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ec). Despite the message still reading as \u0026ldquo;I ❤ BNU 2083\u0026rdquo;, it has evolved into the 4D anti-counterfeiting category due to its variable color factor. Ultimately, a cohesive orange-yellow color palette effectively conveys the intended message of \u0026ldquo;I ❤ BNU 2023\u0026rdquo; (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ed and Supplementary Movie 2). The overall process can be regarded as a 5D anti-counterfeiting technology, which is anticipated to surpass conventional afterglow materials due to its additional time-gated color change facilitated by Br-doping engineering.\u003c/p\u003e\n\u003cp\u003eFurthermore, proof-of-concept experiments were conducted by filling a series of as-synthesized perovskites into the QR code groove. As depicted in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ee, the security model operates under a mechanism wherein specific attributes are assigned to the QR code of each region: emission loss (marked in red), QR code with afterglow duration every 0.5 s (marked in blue), and modification of the afterglow color (marked in green). These attributes correspond to the binary shifts of one bit (+\u0026thinsp;1) in the respective regions. Upon excitation by the 254 nm UV lamp, the QR code displays chaotic orange-red and cyan hues, representing the binary exchange algorithm \u0026ldquo;000\u0026rdquo;. At a delay time of 0.5 s, region C undergoes the first transition from cyanogen to cyanogen yellow, introducing binary ciphers for \u0026ldquo;011\u0026rdquo;, \u0026ldquo;110\u0026rdquo; and \u0026ldquo;101\u0026rdquo;. One second later, the emission from region A is nearly extinguished, while region C transforms to orange-yellow, resulting in adjustments of the binary ciphers to \u0026ldquo;11010\u0026rdquo;, \u0026ldquo;10110\u0026rdquo; and \u0026ldquo;10101\u0026rdquo;. After 18 s, the new binary ciphers take form, generating security codes \u0026ldquo;1161, 1764, 1508, 1481, 1175 and 1179\u0026rdquo; through binary and decimal conversion (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003eh). The final lock code is determined as \u0026ldquo;1508\u0026rdquo;. It is noteworthy that the above binary ciphers are applicable only when i\u0026thinsp;=\u0026thinsp;j\u0026thinsp;=\u0026thinsp;n at the respective time nodes. If the binary digits of all time nodes could be exchanged (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ef), it would result in an information Big-Bang, achieving the maximal information loading capacity (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003eh). Therefore, these perovskites are anticipated to be highly effective for advanced high-security anti-counterfeiting due to leveraging the advantages of time-sensitive color and spatial-time four-resolved functionality.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"Discussion","content":"\u003cp\u003eIn summary, we have successfully demonstrated an ultralong (\u0026gt;\u0026thinsp;2,000 s) persistent luminescence by incorporating Br\u003csup\u003e\u0026minus;\u003c/sup\u003e or Sn\u003csup\u003e2+\u003c/sup\u003e ions into the hexagonal phase CsCdCl\u003csub\u003e3\u003c/sub\u003e, achieving the highest recorded PLQY (84.47%) among current halide perovskites. The simultaneous significant improvement in afterglow lifetime and efficiency can be attributed to the reconstruction of the luminescence center induced by doping, leading to a disruption of the local symmetry in the host framework. Unlike conventional long-afterglow materials, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br exhibits a precisely regulatable color change time valve, determined by varying Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ion doping concentrations, enabling both time- and temperature-dependent LPL. The unique 5\u003cem\u003es\u003c/em\u003e\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e electron configuration of Sn\u003csup\u003e2+\u003c/sup\u003e ions, coupled with distinct geometric symmetries that construct multiple luminescence centers, results in forward and reverse excitation-dependent PL behavior of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn at low and room temperatures, respectively. Therefore, this work not only addresses the existing gap in the field concerning wide-range full-color long-afterglow and Janus-type Ex-De materials, but also introduces a significant paradigm for multifunctional LPL, with applications in high-security anti-counterfeiting and 5D information coding and storage.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e \u003cb\u003eMaterials.\u003c/b\u003e Cesium chloride (CsCl, 99.99%, Innochem), Cadmium chloride (CdCl\u003csub\u003e2\u003c/sub\u003e, 99.99%, Aladdin), Cadmium Bromide (CdBr\u003csub\u003e2\u003c/sub\u003e, 99.99%, Adamas), Cesium Bromide (CsBr, 99.99%, Adamas), Tin(II) chloride (SnCl\u003csub\u003e2\u003c/sub\u003e, anhydrous, 99.99%, Aladdin), Hydrobromic acid (HBr, AR, 40 wt.% solution in water, Macklin), H\u003csub\u003e3\u003c/sub\u003ePO\u003csub\u003e2\u003c/sub\u003e (50 wt.% solution in water, Sigma Aldrich). Hydrochloric acid (HCl, 12 M) was purchased from Xilong Scientific Co. Ltd.\u003c/p\u003e \u003cp\u003e \u003cb\u003ePreparation of Br-doped CsCdCl\u003c/b\u003e \u003csub\u003e \u003cb\u003e3\u003c/b\u003e \u003c/sub\u003e \u003cb\u003esingle crystals.\u003c/b\u003e For pure CsCdCl\u003csub\u003e3\u003c/sub\u003e single crystals (SCs), 4 mmol of CsCl, 4 mmol CdCl\u003csub\u003e2\u003c/sub\u003e were dissolved in 20 mL 12 M hydrochloric acid. The solution was heated at 180\u0026deg;C for 12 hours in a stainless steel Parr autoclave, and then was slowly cooled to room temperature (RT) at a speed of 5\u0026deg;C/h. The crystals at the bottom were rinsed with isopropanol before drying on a filter paper. For CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br crystals, 4\u0026times;(1-\u003cem\u003ex\u003c/em\u003e) mmol of CsCl, 4\u0026times;(1-\u003cem\u003ex\u003c/em\u003e) mmol CdCl\u003csub\u003e2\u003c/sub\u003e, 4\u0026times;\u003cem\u003ex\u003c/em\u003e mmol of CsBr and 4\u0026times;\u003cem\u003ex\u003c/em\u003e mmol of CdBr\u003csub\u003e2\u003c/sub\u003e were dissolved in a total 20 mL mix solution of hydrochloric acid and hydrobromic acid with molar ratio of (1-\u003cem\u003ex\u003c/em\u003e)/\u003cem\u003ex\u003c/em\u003e. the other procedures are the same as above. All crystals were preserved in a caped vial for further characterization.\u003c/p\u003e \u003cp\u003e \u003cb\u003ePreparation of Sn-doped CsCdCl\u003c/b\u003e \u003csub\u003e \u003cb\u003e3\u003c/b\u003e \u003c/sub\u003e \u003cb\u003esingle crystals.\u003c/b\u003e According to the above method, replacing raw materials with 4 mmol of CsCl, 4\u0026times;(1-\u003cem\u003ex\u003c/em\u003e) mmol CdCl\u003csub\u003e2\u003c/sub\u003e and 4\u0026times;\u003cem\u003ex\u003c/em\u003e mmol SnCl\u003csub\u003e2\u003c/sub\u003e to dissolve in 20 mL 12 M hydrochloric acid with 50 wt.% H\u003csub\u003e3\u003c/sub\u003ePO\u003csub\u003e2\u003c/sub\u003e (~\u0026thinsp;132 \u0026micro;L, 1 mmol). Finally, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn crystals ware harvested.\u003c/p\u003e \u003cp\u003e \u003cb\u003eCharacterizations.\u003c/b\u003e Single-crystal X-ray diffraction data of these samples were investigated by Rigaku Oxford Diffraction Supernova X-ray source diffractometer equipped with monochromatized Mo-Kα radiation (\u003cem\u003eλ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;0.71073 \u0026Aring;) at 100 K. Scanning electron microscope (SEM) were characterized by Hitachi SU8010 instrument, and the corresponding element content was collected by energy disperse spectrometer (EDS, Oxford X-Max Aztec). X-ray Photoelectron Spectroscopy (XPS) data were collected using EscaLab 250Xi instrument. Solid UV\u0026thinsp;\u0026minus;\u0026thinsp;vis absorption spectra were collected on a Shimadzu UV-3600 spectrophotometer at room temperature with the wavelength range of 240\u0026thinsp;\u0026minus;\u0026thinsp;500 nm, and BaSO\u003csub\u003e4\u003c/sub\u003e powder was used as a standard (100% reflectance). TGA tests were collected on a Perkin-Elmer Diamond SII thermal analyzer under the atmosphere of nitrogen with a heating rate of 10 K min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. All the relevant photoluminescence (PL) tests and time-resolved lifetime were conducted on an Edinburgh FLS980 fluorescence spectrometer. The PLQY values were acquired using a Hamamatsu Quantaurus-QY Spectrometer (Model C11347-11) equipped with a xenon lamp, integrated sphere sample chamber and CCD detector. The TL spectra were determined by Risϕ TL/OSL Da-20 (DTU Nutech, Denmark) instrument with samples were pre-irradiated under 254 nm UV lamp for 1 min at RT.\u003c/p\u003e \u003cp\u003e \u003cb\u003eTheoretical calculations.\u003c/b\u003e The calculations were performed with the density functional theory (DFT) by Quantum ESPRESSO (qe-7.2)\u003csup\u003e\u003cspan citationid=\"CR69\" class=\"CitationRef\"\u003e69\u003c/span\u003e\u003c/sup\u003e. The generalized gradient approximation of the Perdew\u0026ndash;Burke\u0026ndash;Ernzerhof (PBE) parameterization with projector-augmented wave method are performed for the exchange and correlation functional. Wavefunctions expanded in plane waves were cut off to 480 eV kinetic energy. The Brillouin zone was sampled using a 15\u0026times;15\u0026times;6 Monkhorst\u0026ndash;Pack k-mesh, which was examined have good convergence. For the elements Cs, Cd, Sn, Br and Cl, ultra-soft pseudopotentials are used. The energy convergence criterion is set as 1.0\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e eV for structural relaxations. As for Br\u003csup\u003e\u0026minus;\u003c/sup\u003e- and Sb\u003csup\u003e2+\u003c/sup\u003e-doped CsCdCl\u003csub\u003e3\u003c/sub\u003e, we first adopt the models that a Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ion or Sn\u003csup\u003e2+\u003c/sup\u003e ion substitutes one Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e or Cd\u003csup\u003e2+\u003c/sup\u003e ion site, respectively.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding:\u0026nbsp;\u003c/strong\u003eThis work was supported by the Beijing Municipal Natural Science Foundation (Grant No. JQ20003), and the National Natural Science Foundation of China (Grant Nos. 22288201 and 22275021).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions:\u003c/strong\u003e Conceptualization: D. Y. and T. C.; Methodology: D. Y. and T. C.; Investigation: T. C.; Supervision: D. Y.; Writing\u0026mdash;original draft: T. C.; Writing\u0026mdash;review \u0026amp; editing: D. Y.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests:\u003c/strong\u003e The authors declare that they have no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability:\u003c/strong\u003e All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Materials. The accession number for the crystallographic data of CsCdCl\u003csub\u003e3\u003c/sub\u003e in this paper is Cambridge Crystallographic Data Center (CCDC):2313854.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eHarvey, E. N. A History of Luminescence from the Earliest Times until 1900 (\u003cem\u003eAmerican Philosophical Society\u003c/em\u003e: Philadelphia, PA, USA, 1957).\u003c/li\u003e\n\u003cli\u003eHoogenstraaten, W. Klasens, H. A. 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Phys.\u003c/em\u003e \u003cstrong\u003e152\u003c/strong\u003e,154105(2020).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-3791302/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3791302/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eLong persistent luminescence (LPL) has gained considerable attention for the applications in decoration, emergency signage, information encryption and biomedicine. However, recently developed LPL materials \u0026ndash; encompassing inorganics, organics and inorganic-organic hybrids \u0026ndash; often display monochromatic afterglow with limited functionality. Furthermore, triplet exciton-based phosphors are prone to thermal quenching, significantly restricting their high emission efficiency. Here, we present a straightforward wet-chemistry approach for fabricating multimode LPL materials by introducing both anion (Br\u003csup\u003e\u0026minus;\u003c/sup\u003e) and cation (Sn\u003csup\u003e2+\u003c/sup\u003e) doping into hexagonal CsCdCl\u003csub\u003e3\u003c/sub\u003e all-inorganic perovskites. This process involves establishing new trapping centers from [CdCl\u003csub\u003e6\u0026thinsp;\u0026minus;\u0026thinsp;n\u003c/sub\u003eBr\u003csub\u003en\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e and/or [Sn\u003csub\u003e2\u0026thinsp;\u0026minus;\u0026thinsp;n\u003c/sub\u003eCd\u003csub\u003en\u003c/sub\u003eCl\u003csub\u003e9\u003c/sub\u003e]\u003csup\u003e5\u0026minus;\u003c/sup\u003e linker units, disrupting the local symmetry in the host framework. These halide perovskites demonstrate obviously extended afterglow duration time (\u0026gt;\u0026thinsp;2,000 s), nearly full-color coverage, and high photoluminescence quantum yield (~\u0026thinsp;84.47%). Moreover, they exhibit remarkable anti-thermal quenching properties within the temperature range of 297 to 377 K. Notably, the color-changed time valve of CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br can be precisely controlled by manipulating the concentration of Br\u003csup\u003e\u0026minus;\u003c/sup\u003e ions, distinguishing them from conventional color-varying long-afterglow materials. Additionally, CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Br display time- and temperature-dependent luminescence, while CsCdCl\u003csub\u003e3\u003c/sub\u003e:\u003cem\u003ex\u003c/em\u003e%Sn exhibit forward and reverse excitation-dependent Janus-type luminescence. These characteristics endow the LPL materials with dynamic tunability, offering new opportunities in high-security anti-counterfeiting and 5D information coding. Therefore, this work not only introduces a local-symmetry breaking strategy for simultaneously enhancing afterglow lifetime and efficiency, but also provides new insights into the multimode LPL materials for applications in luminescence, photonics, and information storage.\u003c/p\u003e","manuscriptTitle":"Full-color and time-valve controllable long-persistent luminescence from all-inorganic halide perovskites","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-01-10 10:48:18","doi":"10.21203/rs.3.rs-3791302/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"c551e16f-d3f2-4c77-930e-cfd71a5d1285","owner":[],"postedDate":"January 10th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":28040723,"name":"Physical sciences/Materials science/Materials for optics"},{"id":28040724,"name":"Physical sciences/Chemistry/Materials chemistry/Optical materials"}],"tags":[],"updatedAt":"2024-06-21T07:06:52+00:00","versionOfRecord":{"articleIdentity":"rs-3791302","link":"https://doi.org/10.1038/s41467-024-49654-7","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2024-06-20 04:00:00","publishedOnDateReadable":"June 20th, 2024"},"versionCreatedAt":"2024-01-10 10:48:18","video":"","vorDoi":"10.1038/s41467-024-49654-7","vorDoiUrl":"https://doi.org/10.1038/s41467-024-49654-7","workflowStages":[]},"version":"v1","identity":"rs-3791302","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3791302","identity":"rs-3791302","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}