Self-trapped Exciton Emission Research Articles

Scintillation characteristics of antimony based organic–inorganic hybrid compounds with a zero-dimensional structure

Antimony based organic–inorganic hybrid compounds (Ph4P)2SbCl5 (Ph4P: tetraphenylphosphonium) and (DTA)2SbCl5 (DTA: dodecyltrimethylammonium) with a zero-dimensional structure were fabricated, and the optical and scintillation characteristics were evaluated. A broadband photoluminescence possibly due to self-trapped exciton (STE) emission appeared at 692 nm for (Ph4P)2SbCl5 and 630 nm for (DTA)2SbCl5 under 370 nm excitation light. The quantum yields were 98 % for (Ph4P)2SbCl5 and 97 % for (DTA)2SbCl5. Under X-ray, the broad emission peak was also detected at 670 nm for (Ph4P)2SbCl5 and at 615 nm for (DTA)2SbCl5. Furthermore, scintillation decay time constants were 4.9 μs for (Ph4P)2SbCl5 and 5.0 μs for (DTA)2SbCl5. Moreover, the scintillation light yield of (Ph4P)2SbCl5 was estimated to be about 12,000 photons/MeV, whereas the light of (DTA)2SbCl5 could not be determined. In addition, afterglow levels were 56 ppm for (Ph4P)2SbCl5 and 130 ppm for (DTA)2SbCl5.

Effect of substituting on the transition dipole moment of the double perovskite Cs2AgInCl6

The all-inorganic double perovskite Cs2AgInCl6 with three dimensional structure has attracted much attention due to its direct bandgap property and particular luminescence mechanism, which is self-trapped exciton emission. However, it is a pity that Cs2AgInCl6 exhibits low photoluminescence quantum yield, which affects its application for light-emitting devices. In this paper, the band structure and transition dipole moment of Cs2AgIn(1−x)Sb x Cl6 (x = 0, 0.25, 0.5, 0.75) are calculated using first principle calculation. The calculated results shows that the pure material Cs2AgInCl6 not only has a large band gap but also has the dipole forbidden transition, which means that the electrons cannot be excited from the valence band maximum to the conduction band minimum. However, the substituted Cs2AgIn0.75Sb0.25Cl6 have a good property for the band gap about 3.066 eV and break forbidden transition at point X. The reason for its change is due to the overlap of electron and hole for charge density. Our work provides theoretical guidance for the design of more efficient light-emitting devices.

Scintillation and Optical Characterization of CsCu2I3 Single Crystals from 10 to 400 K.

Currently only Eu2+-based scintillators have approached the light yield needed to improve the 2% energy resolution at 662 keV of LaBr3:Ce3+,Sr2+. Their major limitation, however, is the significant self-absorption due to Eu2+. CsCu2I3 is an interesting new small band gap scintillator. It is nonhygroscopic and nontoxic, melts congruently, and has an extremely low afterglow, a density of 5.01 g/cm3, and an effective atomic number of 50.6. It shows self-trapped exciton emission at room temperature. The large Stokes shift of this emission ensures that this material is not sensitive to self-absorption, tackling one of the major problems of Eu2+-based scintillators. An avalanche photo diode, whose optimal detection efficiency matches the 570 nm mean emission wavelength of CsCu2I3, was used to measure pulse height spectra. From the latter, a light yield of 36 000 photons/MeV and energy resolution of 4.82% were obtained. The scintillation proportionality of CsCu2I3 was found to be on par with that of SrI2:Eu2+. Based on temperature-dependent emission and decay measurements, it was demonstrated that CsCu2I3 emission is already about 50% quenched at room temperature. Using temperature-dependent pulse height measurements, it is shown that the light yield can be increased up to 60 000 photons/MeV by cooling to 200 K, experimentally demonstrating the scintillation potential of CsCu2I3. Below this temperature, the light yield starts to decrease, which can be linked to the unusually large increase in the band gap energy of CsCu2I3.

Accommodative Organoammonium Cations in A‐Sites of Sb─In Halide Perovskite Derivatives for Tailoring BroadBand Photoluminescence with X‐Ray Scintillation and White‐Light Emission

AbstractBroadband emissive perovskites are next‐generation materials for solid‐state lighting and radiative detection. However, white‐emitting perovskites are generally synthesized by regulating B/X sites, while not enough attention is paid to the A‐site, which is thought to hardly affect the band‐edge structures and optoelectronic properties. Here, a series of Sb3+‐doped In‐based 0D halide perovskite derivatives are described with various organoammonium cations in A‐sites. Warm‐white light emitting across the visible spectrum (450–850 nm), large Stokes shifts, and high photoluminescence quantum yields are easily tunable by molecularly tailoring A‐site cations. These features enable a light yield up to 60976 Photons/MeV as X‐ray scintillator, and a detection limit of 90 nGyair/s that is ≈60 times lower than the medical requirement. It is proved that A‐site plays a critical role in determining the degree of distortion of polyhedra, which influences the broadband photoluminescence and self‐trapped exciton (STE) dominates the emission process. Moreover, for the first time, via the incorporation of 2,6‐dimethylpiperazine, a mixed A‐site regulating strategy produces a standard white‐light emission, which originates from the blue‐light and yellow‐light related to various STE emission centers. It is foreseen that this strategy highlights the expanded role of A‐site and the importance of rethinking A‐sites in perovskites.

Broadband Emission Origin in Metal Halide Perovskites: Are Self-Trapped Excitons or Ions?

It has always been a goal to realize high efficiency and broadband emission in single-component materials. The appearance of metal halide perovskites makes it possible. Their soft lattice characteristics and significant electron-phonon coupling synergistically generate self-trapped excitons (STEs), contributing to a broadband emission with a large Stokes shift. Meanwhile, their structural/compositional diversity provides suitable active sites and coordination environments for doping of ns2 ions, allowing 3 Pn ( n =0,1,2) →1 S0 transitions toward broadband emission. The ns2 ions emission is phenomenologically similar to that of STE emission, hindering in-depth understanding of their emission origin, and leading to failure to meet the design requirements for practical applications. In this scenario, herein, the fundamentals and development of such two emission mechanisms are summarized to establish a clear and comprehensive understanding of the broadband emission phenomenon, which may pave the way to an ideal customization of broadband-emission metal halide perovskites.

Pressure-Regulated Excitonic Transitions in Emergent Metal Halides.

ConspectusEmergent metal halides are generating significant interest as novel optical materials, and their diverse applications have brought them to the spotlight of chemistry and material science. The optical properties of semiconducting metal halides are fundamentally dominated by excitonic transitions, which refer to the complex processes of excitonic formation, self-trapping, as well as subsequent transitions of intersystem crossing (ISC) and internal conversion (IC). In this regard, high pressure has recently opened a new research dimension to regulate excitonic transitions in metal halides via continuous structural modulations, to understand the intriguing excitonic emissions from a new perspective. In this Account, we aim to rationalize the fundamental strategy for modulating and optimizing the optical properties of metal halides based on delicate exciton regulation via high-pressure method. First, the band gaps of metal halides that are directly related to the efficiency of excitonic formation, are accurately modulated through contraction, distortion, and destruction of metal-halogen polyhedra under compression. Then, considerable enhancement of self-trapped exciton emission is demonstrated by inducing proper polyhedral distortions via high-pressure method. Furthermore, the emission energy of metal halides could also be controllably and widely tuned through pressure-modulated excitonic transitions. Upon compression on different metal halides, excitonic IC is promoted with sufficient polyhedral distortions, and different sets of ISC could also be achieved. In the end, we emphasize the significance of high-pressure investigations in uncovering the complex excitonic transitions in emergent metal halides and predicting novel metal halides with desired optical properties at ambient conditions. It is expected that these discussions could inspire researchers in different fields to perform interdisciplinary high-pressure studies on novel functional materials.

Manipulating Lone-Pair-Driven Luminescence in 0D Tin Halides by Pressure-Tuned Stereochemical Activity from Static to Dynamic.

The excellent luminescence properties and structural dynamics driven by the stereoactivity of the lone pair in a variety of low-dimensional ns2 metal halides have attracted growing investigations for optoelectronic applications. However, the structural and photophysical aspects of the excited state associated with the lone pair expression are currently open questions. Herein, zero-dimensional Sn-based halides with static stereoactive 5 s2 lone pairs are selected as a model system to understand the correlations between the distinctive lone pair expression and the excited-state structural relaxation and charge carrier dynamics by continuous lattice manipulation. Lattice compression drives 5 s2 lone pair active switching and self-trapped exciton (STE) redistribution by suppressing excited-state structural deformation of the isolated SnBr4 2- units. Our results demonstrate that the static expression of the 5 s2 lone pair results in a red broadband triplet STE emission with a large Stokes shift, while its dynamic expression creates a sky-blue narrowband emission dominated by the radiative recombination of singlet STEs. Our findings and the photophysical mechanism proposed highlight the stereochemical effects of lone pair expression in controlling light emission properties and offer constructive guidelines for tuning the optoelectronic properties in diverse ns2 metal halides.

Manipulating Lone‐Pair‐Driven Luminescence in 0D Tin Halides by Pressure‐Tuned Stereochemical Activity from Static to Dynamic

AbstractThe excellent luminescence properties and structural dynamics driven by the stereoactivity of the lone pair in a variety of low‐dimensional ns2 metal halides have attracted growing investigations for optoelectronic applications. However, the structural and photophysical aspects of the excited state associated with the lone pair expression are currently open questions. Herein, zero‐dimensional Sn‐based halides with static stereoactive 5 s2 lone pairs are selected as a model system to understand the correlations between the distinctive lone pair expression and the excited‐state structural relaxation and charge carrier dynamics by continuous lattice manipulation. Lattice compression drives 5 s2 lone pair active switching and self‐trapped exciton (STE) redistribution by suppressing excited‐state structural deformation of the isolated SnBr42− units. Our results demonstrate that the static expression of the 5 s2 lone pair results in a red broadband triplet STE emission with a large Stokes shift, while its dynamic expression creates a sky‐blue narrowband emission dominated by the radiative recombination of singlet STEs. Our findings and the photophysical mechanism proposed highlight the stereochemical effects of lone pair expression in controlling light emission properties and offer constructive guidelines for tuning the optoelectronic properties in diverse ns2 metal halides.

Mn2+ and Sb3+ Codoped Cs2ZnCl4 Metal Halide with Excitation-Wavelength-Dependent Emission for Fluorescence Anticounterfeiting.

In recent years, there has been a growing demand for luminescence anticounterfeiting materials that possess the properties of environmentally friendly, single-component, and multimode fluorescence. Among the materials explored, the low dimensional metal halides have gained wide attention because of unique characteristics including low toxicity, simple synthesis, good stability, and so on. Here, we synthesized Mn2+ and Sb3+ codoped Cs2ZnCl4 single crystals by a facile hydrothermal method. Under 365 nm excitation, the codoped compound exhibits dual-band emissions at 530 and 730 nm. However, under 316 nm excitation, the compound only shows one emission band from 500 to 850 nm peaking at 730 nm, while under 460 nm excitation, the emission from 500 to 650 nm with an emission peak at 530 nm can be observed. Based on the study of the photoluminescence mechanism, the green and red emissions originate from the Mn2+ located in the tetrahedron and self-trapped exciton emission of [SbCl4]- clusters, respectively. Due to the zero-dimensional structure of the Cs2ZnCl4 host, there is minimal energy transfer between these dopants. Consequently, the luminous ratios of the two emissions can be independently regulated. Except by tuning the dopant concentrations, the Cs2ZnCl4:Mn2+, Sb3+ demonstrates excitation-wavelength-dependent properties, which could emit more than two colors with the change of excitation wavelength. As a result, multimode anticounterfeiting based on Cs2ZnCl4:Mn2+, Sb3+ crystals has been designed, which aligns with the requirements of environmentally friendly, single-component, and multimode fluorescence properties.

Multimode Luminescence Tailoring and Improvement of Cs2 NaHoCl6 Cryolite Crystals via Sb3+ /Yb3+ Alloying for Versatile Photoelectric Applications.

Lead-free halide double perovskites are currently gaining significant attention owing to their exceptional environmental friendliness, structural adjustability as well as self-trapped exciton emission. However, stable and efficient double perovskite with multimode luminescence and tunable spectra are still urgently needed for multifunctional photoelectric application. Herein, holmium based cryolite materials (Cs2 NaHoCl6 ) with anti-thermal quenching and multimode photoluminescence were successfully synthesized. By the further alloying of Sb3+ (s-p transitions) and Yb3+ (f-f transitions) ions, its luminescence properties can be well modulated, originating from tailoring band gap structure and enriching electron transition channels. Upon Sb3+ substitution in Cs2 NaHoCl6 , additional absorption peaking at 334 nm results in the tremendous increase of photoluminescence quantum yield (PLQY). Meanwhile, not only the typical NIR emission around 980 nm of Ho3+ is enhanced, but also the red and NIR emissions show a diverse range of anti-thermal quenching photoluminescence behaviors. Furthermore, through designing Yb3+ doping, the up-conversion photoluminescence can be triggered by changing excitation laser power density (yellow-to-orange) and Yb3+ doping concentration (red-to-green). Through a combined experimental-theoretical approach, the related luminescence mechanism is revealed. In general, by alloying Sb3+ /Yb3+ in Cs2 NaHoCl6 , abundant energy level ladders are constructed and more luminescence modes are derived, demonstrating great potential in multifunctional photoelectric applications.

Bluish-white Light-emitting 2D Sheets of Lead-free Perovskite Cesium Titanium Bromide (CsTiBr3) by a Two-stage Deposition Technique.

Bluish-white light-emitting materials are commonly used in LED lighting because they produce natural-looking light. Here we report the photoluminescent emission (PL) of novel, two-dimensional lead-free CsTiBr3 perovskite prepared via a two-stage deposition process. The formation of two-dimensional nanosheets of CsTiBr3 perovskite is confirmed by XRD, EDAX, and FESEM analysis. The height of the cesium bromide thin film substrate from the titanium bromide vapor source plays an important role in the formation of two-dimensional CsTiBr3. The CsTiBr3 perovskite nanosheets exhibit unique exciton- luminescence at 440nm and self-trapped exciton emission at 595nm which are the characteristics of two-dimensional halide structure, along with the band-to-band emission at 400nm at an excitation wavelength of 340nm. The resulting bluish-white light PL emission makes two-dimensional CsTiBr3 perovskite an alternative material to the traditional lead-based perovskite in LEDs, display technology, solid-state lighting, and various optoelectronic devices, addressing environmental concerns.

Doping suppresses lattice distortion of vacant quadruple perovskites to activate self-trapped excitons emission

Doping suppresses lattice distortion of vacant quadruple perovskites to activate self-trapped excitons emission

Impurity, host and defect-related luminescence of CsLaSiS4 thiosilicate crystals doped with Ce3+ ions

Ce+3 doped CsLaSiS4 single crystals were synthesized using high-temperature flux synthesis. XRD analysis showed that the products are isostructural to CsLaSiS4 and crystallize in orthorhombic space group Pnma. Absorption spectra were studied at room temperature, and photoluminescence properties were examined in the temperature range of 5–310 K. The energy of interband transitions Eg = 3.75 eV was determined at room temperature in the Tauc model. At room temperature, only a non-elementary d → f emission band of Ce+3 ions was observed in the 520 nm region. The luminescence kinetics upon excitation by a pulsed cathode beam or X-ray synchrotron radiation exhibited a dominant nanosecond component. Decay time, as well as build-up time, decreased with increasing concentration of Ce+3 ions. Concentration quenching of Ce+3 emission was not observed up to 11.9 mol% of Ce+3 ions. At a low temperature of 5 K, new wide emission bands at 422 and 688 nm appeared in the photoluminescence spectrum. It is shown that the 422 nm band in the photoluminescence spectrum corresponds to host emission, specifically the luminescence of self-trapped excitons (STE). The 688 nm emission band corresponds to defect-related luminescence. STE emission is quenched according to the Mott law at temperatures above 26 K with an activation energy of 20 meV. An efficient energy transfer channel from the STE to the Ce+3 ion via the radiative resonance mechanism is observed. The emission of Ce+3 ions and defect-related luminescence can be excited by the intracenter way, due to electron-hole recombination, or by the creation of defect bound excitons. Based on the obtained spectroscopic data, a band scheme illustrating the processes of relaxation of electronic excitations at T = 5 K in Ce+3 doped CsLaSiS4 crystals is proposed.

Satellite Red Emission from a Single Green-Emissive MnBr42- Tetrahedron in Soft Hybrid Single Crystals.

Photoinduced self-trapped exciton emission is common in soft matter metal halide semiconductors, whereas analogous phenomena in metal halide insulators with localized emitting centers and delayed satellite emission have rarely been identified. In this study, a new zero-dimensional Mn(II) hybrid of [3DPTPP]MnBr4 (3DPTPP = (3-(dimethylamino)propyl)(triphenyl)phosphonium) with only one crystallographic Mn2+ site but dual emission is reported. The delayed red emission (∼630 nm) is successfully assigned to a satellite of the green-emissive (∼530 nm) MnBr42- tetrahedron shifted by N-H vibration (∼2500 cm-1), directly evidenced by the Raman spectra and further supported by density functional theory calculation. The photoluminescence decay curves demonstrate their same origin, but the red emission exhibits a delayed process. The temperature- and pressure-dependent PL spectra, temperature-dependent distortion of the MnBr42- tetrahedron, and light polarization spectra confirmed the consistency and distinctness of the dual emission. This study will inspire further research on self-trapped optoelectronic processes in soft metal halides.

Electron–phonon coupling mediated self-trapped exciton emission in organic–inorganic hybrid manganese halides

Electron–phonon coupling mediated self-trapped exciton emission in organic–inorganic hybrid manganese halides

Green synthesis of Mn doped Cs3Cu2X5 (X=Cl, Br) powders with excellent photoluminescence and stability for anti-counterfeiting

Lead halide perovskite have drawn enormous attention recently for their excellent optoelectronic properties in many fields. However, the toxicity of Pb element and poor stability extremely hinder their practical applications. Herein, 0 D orthorhombic Cs3Cu2X5 powders (X = Cl, Br) are simply synthesized by a novel method, which using H2O as green solvent, CuX2 as the substitute of CuX. They exhibit broadband blue-green photoluminescence (PL) emissions of 468–530 nm with large Stokes shifts, which are attributed to their intrinsic self-trapped exciton (STE) emission characteristics. Moreover, Mn doped Cs3Cu2Cl5 powder present higher PLQY (78%) and longer average lifetime (108 μs), which also have an improved stability for moist air, UV light and high temperature. The obtained Cs3Cu2Br5 microrods show a low PLQY ∼20% and bad stability, but the faded photoluminescence can be recovered by further thermal treatment. Finally, a kind of green economic anti-counterfeiting ink is obtained, which would be activated by high temperature and deep-ultraviolet. The CIE coordinate of fabricated green emitting LED is (0.30, 0.53), which indicates they have a potential for future lighting application.

Boosting the Self-Trapped Exciton Emission in Cs4SnBr6 Zero-Dimensional Perovskite via Rapid Heat Treatment.

Zero-dimensional (0D) tin halide perovskites feature extraordinary properties, such as broadband emission, high photoluminescence quantum yield, and self-absorption-free characteristics. The innovation of synthesis approaches for high-quality 0D tin halide perovskites has facilitated the flourishing development of perovskite-based optoelectronic devices in recent years. However, discovering an effective strategy to further enhance their emission efficiency remains a considerable challenge. Herein, we report a unique strategy employing rapid heat treatment to attain efficient self-trapped exciton (STE) emission in Cs4SnBr6 zero-dimensional perovskite. Compared to the pristine Cs4SnBr6, rapid thermal treatment (RTT) at 200 °C for a duration of 120 s results in an augmented STE emission with the photoluminescence (PL) quantum yield rising from an initial 50.1% to a substantial 64.7%. Temperature-dependent PL spectra analysis, Raman spectra, and PL decay traces reveal that the PL improvement is attributed to the appropriate electron-phonon coupling as well as the increased binding energies of STEs induced by the RTT. Our findings open up a new avenue for efficient luminescent 0D tin-halide perovskites toward the development of efficient optoelectronic devices based on 0D perovskites.

Achieving Highly Efficient Warm-White Light Emission in All-Inorganic Copper-Silver Halides via Structural Regulation.

Single-component metal halides with white light emission are highly attractive for solid-state lighting applications, but it is still challenging to develop all-inorganic lead-free metal halides with high white-light emission efficiency. Herein, by rationally introducing silver (Ag) into zero-dimensional (0D) Cs3 Cu2 Br5 as new structural building unit, a one-dimensional (1D) bimetallic halide Cs6 Cu3 AgBr10 is designed that emits strong warm-white light with an impressive photoluminescence quantum yield (PLQY) of 94.5% and excellent stability. This structural transformation lowers the conduction band minimum while maintaining the localized nature of the valence band maximum, which is crucial in expanding the excitation spectrum and obtaining efficient self-trapped excitons (STEs) emission simultaneously. Detailed spectroscopy studies reveal that the white-light originates from triplet STEs emission, which can be remarkably improved by weakening the strong electron-phonon coupling and thus suppressing phonon-induced non-radiative processes. Moreover, the interesting temperature-dependent emission behavior, together with self-absorption-free property, make Cs6 Cu3 AgBr10 as sensitive luminescent thermometer and high-performance X-ray scintillator, respectively. These findings demonstrate a general approach to achieving effective single-component white-light emitters based on lead-free, all-inorganic metal halides, thereby opening up a new avenue to explore their versatile applications such as lighting, temperature detection and X-ray imaging.

A High-Rigidity Organic-Inorganic Metal Halide Hybrid Enabling Reversible and Enhanced Self-Trapped Exciton Emission under High Pressure.

Zero-dimensional organic-inorganic metal halide hybrids provide ideal bulk-crystal platforms for exploring the pressure engineering of electron-phonon coupling (EPC) and self-trapped exciton (STE) emission at the molecular level. However, the low stiffness of inorganic clusters hinders the reversible tuning of these physical properties. Herein, we designed a Sb3+-doped metal halide with a high emission yield (89.4%) and high bulk modulus (35 GPa) that enables reversible and enhanced STE emission (20-fold) under pressure. The high lattice rigidity originates from the corner-shared cage-structured inorganic tetramers and ring-shaped organic ligands. Further, we reveal that the pressure-enhanced emission regime below 4.5 GPa is owing to the lattice hardening and preferably EPC strength reducing, while the pressure-insensitive emission regime within 4.5-8.5 GPa results from the enhanced intercluster Coulombic attraction force that resists intracluster compression. These results provide insights into the structure-property relation and molecular engineering of zero-dimensional metal halides toward wide-band and pressure-sensitive light sources.

Doping-induced Ti3+ state and oxygen vacancies in TiO2: A single-chip combinatorial investigation

TiO2 is widely recognized as a high performance photocatalyst for photocatalytic applications. Oxygen vacancies (VO) and titanium defects are known to make a significant contribution to the enhanced photocatalytic efficiency of TiO2, accordingly control of these two centers is pivotal to optimizing the surface photochemical activity. In this work, the formation of VO and Ti3+ ions induced by n-type doping of TiO2 with Nb is demonstrated using a combinatorial investigation approach. Chemical Beam Vapour Deposition (CBVD) is used to fabricate Nb concentration-graded (NbxTi1-x)O2 anatase films with 0.009 ≤ x ≤ 0.033 over a 5 mm length on a single chip. Cathodoluminescence (CL) microanalysis shows the luminescence intensity decreases with increasing Nb concentration; however, the presence of a self-trapped exciton (STE) emission, characteristic of anatase TiO2, indicates that the Nb incorporation does not affect the structural properties of TiO2. Notably, the introduction of Nb donors induces the formation of the signature luminescence bands of VO and Ti3+ at 2.05 and 2.60 eV at 80 K, respectively, and their intensities rise by up to 28% with increasing Nb content. The formation of VO and Ti3+ is attributed to the effect of excess electrons locally produced by Nb donor doping. The thermal activation energies for the STE and defect-related emissions are found to be identical at 32 ± 4 meV, suggesting that the recombination kinetics is mediated by Nb donors. Significantly, we demonstrate that the near-surface VO density can be further increased by two different post-growth treatment approaches: (i) remote hydrogen plasma and (ii) low-energy electron beam irradiation (LEEBI), without effecting the valence state of Ti. Our results open opportunities to optimize the photocatalytic properties of TiO2 by defect engineering.