Self-trapped Exciton Emission Research Articles

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.

Toward first-principles approaches for mechanistic study of self-trapped exciton luminescence

In recent years, broadband photo-luminescence phenomena arising from self-trapped exciton (STE) in metal halides, including perovskites and various low-dimensional derivatives and variants, have attracted increasing attention for their potential diverse optoelectronic applications like lighting, display, radiation detection, and sensing. Despite great success in experimental discovery of many efficient STE emitters, the current understanding of the STE emission mechanism in metal halides is still immature, and often controversial, which calls for help urgently from predictive first-principles theoretical calculation. Although density-functional theory (DFT) based calculations are routinely used to provide electronic band structure of materials and have contributed greatly to qualitative analysis of luminescence mechanism, more in-depth and quantitative information is highly needed to provide guidelines for rational design of new luminescent materials with desirable features. However, due to the complicated nature of STE emission, involving in particular electron–phonon coupling in both ground and excited states, the usage of DFT is no longer a routine job as for ground state properties. While more sophisticated methods formulated in the framework of many-body perturbation theory like GW-Bethe–Salpeter equation are available and provide theoretically rigorous and accurate description of electronic transitions in extended systems, their application to real STE systems is still severely limited due to highly demanding computational cost. In practice, approximated DFT methods are employed, which have their own strengths and limitations. In this review, we focus on the theoretical approaches that have been heavily used in interpreting STE luminescence mechanism, with a particular emphasis on theoretical methods for exciton self-trapping structural optimization. It is hoped that this review, by summarizing the current status and limitations of theoretical research in the STE emission, will motivate more methodological development efforts in this important field, and push forward the frontiers of excited state electronic structure theory of materials in general.

White light emitting diodes based on lanthanide ions doped Cs2NaInCl6 double perovskites

Lead-free halide double perovskites are widely used for phosphors converted light emitting diode (pc-LED) devices. However, it remains a challenge to modulate their spectra to meet different application requirements. Herein, Cs2NaInCl6:Sb3+ double perovskite crystals with excellent blue emission of self-trapped excitons (STEs) were prepared and a lanthanide ions (Ln3+) doping strategy was employed to enable multicolor emissions in this system. The emission colors can be continuously adjusted in a wide range by altering the Ln3+ ions doping levels. Especially, white light emissions with tunable correlated color temperature were obtained in Tb3+, Ho3+ ions codoped samples. Outstanding photoluminescence quantum yields of the samples are ascribed to the sensitization effect of Sb3+ ions and the efficient energy-transfer from STEs to Ln3+ ions. LED devices were further fabricated to demonstrate the great application potentials of the prepared phosphors. These findings provide deep insights for the designing of multicolor double perovskite phosphors.

Excellent Switchable Properties, Broad-Band Emission, Ferroelectricity, and High Tc in a Two-Dimensional Hybrid Perovskite: (4,4-DCA)2PbBr4 Exploited by H/F Substitution.

Switchable materials have gained significant attention due to their potential applications in data storage, sensors, and switching devices. Two-dimensional (2D) hybrid perovskites have demonstrated promising prospects for designing switchable materials, where the dynamic motion of the organic components coupled with the distortion of the inorganic framework provides the driving force for triggering multifunctional switchable properties. Herein, through the H/F substitution strategy, we report a polar 2D hybrid lead-based perovskite, (4,4-DCA)2PbBr4 (4,4-DCA = 4,4-difluorocyclohexylammonium) (1), which exhibits dual-stable behavior in a dielectric and second harmonic generation (SHG) response during the reversible phase transition process near the high Curie temperature Tc ∼ 409 K. The phase transition temperature is significantly increased by 41 K compared to the corresponding non-fluorinated (CHA)2PbBr4 (CHA = cyclohexylammonium). Remarkably, the material shows rare broad-band yellow emission under UV excitation, attributed to the induction of self-trapped exciton emission by the distortion of the [PbBr6]4- octahedra, as confirmed by the first-principles analysis. 1 also exhibited ferroelectricity with a saturation polarization value and a small coercive field. This study provides a new insight into the modification of multifunctional switchable materials through the H/F substitution strategy.

A ratiometric optical thermometer with dual-color emission based on Eu2+-doped CsCu2I3 microcrystals

With the increasing demand for non-contact fluorescence intensity ratio-based optical thermometry, novel phosphor materials with high-efficiency, dual-emitting centers, and differentiable temperature sensitivity are highly desired. In this work, rare earth Eu2+ ions were incorporated into CsCu2I3 microcrystals by solid-state reaction. Under a single UV excitation, the as-synthesized samples exhibit two emissions: 452 nm blue emission from the 5d→4f transition of Eu2+ and 582 nm yellow emission from self-trapped exciton emission of CsCu2I3. The photoluminescence quantum yield reaches to 50%. The dual-band emission of Eu2+-doped CsCu2I3 shows different temperature responses in the range of 260–360 K. Based on fluorescence intensity ratio technology, the maximum absolute sensitivity and relative sensitivity are 0.091 K–1 (at 360 K) and 2.60%/K (at 260 K), respectively. These results suggest that Eu2+-doped CsCu2I3 could be a good candidate for highly sensitive optical thermometer.

A‐site coordinating cation engineering in zero‐dimensional antimony halide perovskites for strong self‐trapped exciton emission

AbstractLow‐dimensional hybrid halide perovskites represent a promising class of materials in optoelectronic applications because of strong broad self‐trapped exciton (STE) emissions. However, there exists a limitation in designing the ideal A‐site cation that makes the material satisfy the structure tolerance and exhibit STE emission raised by the appropriate electron–phonon coupling effect. To overcome this dilemma, we developed an inorganic metal‐organic dimethyl sulfoxide (DMSO) coordinating strategy to synthesize a series of zero‐dimensional (0D) Sb‐based halide perovskites including Na3SbBr6·DMSO6 (1), AlSbBr6·DMSO6 (2), AlSbCl6·DMSO6 (3), GaSbCl6·DMSO6 (4), Mn2Sb2Br10·DMSO13 (5) and MgSbBr5·DMSO7 (6), in which the distinctive coordinating A‐site cation [Am‐DMSO6]n+ efficiently separate the [SbXz] polyhedrons. Advantageously, these materials all exhibit broadband‐emissions with full widths at half maxima (FWHM) of 95–184 nm, and the highest photoluminescent quantum yield (PLQY) of 3 reaches 92%. Notably, compounds 2–4 are able to remain stable after storage of more than 120 d. First‐principles calculations indicate that the origin of the efficient STE emission can be attributed to the localized distortion in [SbXz] polyhedron upon optical excitation. Experimental and calculational results demonstrate that the proposed coordinating strategy provides a way to efficiently expand the variety of novel high‐performance STE emitters and continuously regulate their emission behaviors.

Designing multi-mode optical thermometers via Sb3+/Er3+ co-doped Cs2NaInCl6 lead-free double perovskite microcrystals

Contactless optical thermometers are widely studied in scientific research and technology because of their apparent advantages. The combination of multi-mode thermometric techniques can realize self-referenced temperature sensing, making temperature monitoring signals more accurate. Herein, a series of Cs2NaInCl6: Sb3+, Er3+ microcrystals (MCs) were prepared via the ligand-assisted reprecipitation method. Under 320 nm excitation, the energy transfer from the self-trapped excitons (STEs) to Er3+ is established, which leads to the blue emission of STEs and intrinsic emissions of Er3+. Additionally, the MCs can also produce up-conversion green emissions under the excitation of NIR laser. Based on this, a multi-mode thermometer is developed, including the luminescence intensity ratio of two thermally coupled levels of Er3+ (2H11/2/4S3/2), the luminescence intensity ratio of a non-thermally coupled system of STEs and Er3+(4S3/2), and fluorescence lifetime of Er3+(4S3/2). Moreover, the MCs exhibit thermochromic properties, the luminescent color changes from blue to green as the temperature increases. To monitor the temperature more objectively by color variation, a novel sensing mode is constructed via the relationship between chromatic coordinates and temperature. The favorable thermometry performances for four-mode temperature sensing reveal that Cs2NaInCl6: Sb3+/Er3+ MCs are good candidates for thermometric materials for the novel multi-mode design.