Self-trapped Exciton Emission Research Articles

Theory and experiments of pressure-tunable broadband light emission from self-trapped excitons in metal halide crystals

Hydrostatic pressure has been commonly applied to tune broadband light emissions from self-trapped excitons (STE) in perovskites for producing white light and study of basic electron-phonon interactions. However, a general theory is still lacking to understand pressure-driven evolution of STE emissions. In this work we first identify a theoretical model that predicts the effect of hydrostatic pressure on STE emission spectrum, we then report the observation of extremely broadband photoluminescence emission and its wide pressure spectral tuning in 2D indirect bandgap CsPb2Br5 crystals. An excellent agreement is found between the theory and experiment on the peculiar experimental observation of STE emission with a nearly constant spectral bandwidth but linearly increasing energy with pressure below 2 GPa. Further analysis by the theory and experiment under higher pressure reveals that two types of STE are involved and respond differently to external pressure. We subsequently survey published STE emissions and discovered that most of them show a spectral blue-shift under pressure, as predicted by the theory. The identification of an appropriate theoretical model and its application to STE emission through the coordinate configuration diagram paves the way for engineering the STE emission and basic understanding of electron-phonon interaction.

Circularly Polarized Luminescence from Zero-Dimensional Hybrid Lead-Tin Bromide with Near-Unity Photoluminescence Quantum Yield.

Zero-dimensional (0D) hybrid metal halides with perfect host-guest structures are promising candidates to construct circularly polarized luminescence (CPL)-active materials. However, it still remains challenging to obtain 0D chiral metal halides with simultaneously strong CPL and high photoluminescence quantum yield. Here, a new enantiomeric pair of 0D hybrid lead-tin bromides, (RR/SS-C6 N2 H16 )2 Pb0.968 Sn0.032 Br6 ⋅ 2H2 O (R/S-PbSnBr ⋅ H2 O), is reported. The R/S-PbSnBr ⋅ H2 O compounds not only show intriguing self-trapped exciton emissions with near-unity quantum yield, but also present intense CPL with a dissymmetry factor glum of ±3.0×10-3 . Such CPL activities originate from the asymmetric [SnBr6 ]4- luminophores in R/S-PbSnBr ⋅ H2 O, due to the induced structural chirality by the organic ligands via N-H⋅⋅⋅Br hydrogen bonds. Furthermore, CPL emissions with tunable colors from R/S-PbSnBr ⋅ H2 O and dehydrated compounds are reversibly observed, which extends their chiroptical applications.

Blue Light-Excitable Broadband Yellow Emission in a Zero-Dimensional Hybrid Bismuth Halide with Type-II Band Alignment

Zero-dimensional (0D) organic-inorganic hybrid metal halides have captured broad interest in the lighting and display fields because of their unique electronic structures and splendid broadband emission properties. However, the blue light-excitable broadband yellow emissions have been rarely reported in 0D hybrid metal halides. Here, we design a new 0D bismuth hybrid, (4cmpyH)2BiCl5 (1, 4cmpy = 4-(chloromethyl)pyridine), featuring isolated edge-sharing bioctahedral [Bi2Cl10]4- dimers surrounded by rigid, conjugated, and luminescent organic [4cmpyH]+ cations. This material is able to show intrinsic broadband yellow emissions under blue light (468 nm) excitation with a long lifetime of 22.33 μs and a photoluminescence (PL) quantum yield of 5.56%. Solid-state UV-vis spectroscopy studies prove that introducing organic π-conjugated groups into hybrid systems leads to absorption in the visible light region, in favor of photoexcitation by visible light. By comparing the PL data of 1 and the organic template at room temperature and measuring variable-temperature PL spectra of 1, the blue light-excited broadband emission of 1 can be attributed to the synergistic emissions of intramolecular π → π* and n → π* transitions in the organic cations and triple self-trapped exciton (STE) states centralized at the highly distorted Bi-Cl lattices. Moreover, density functional theory calculations reveal a type-II band alignment in 1 with an indirect band gap of 2.64 eV, which is together determined by organic cations and inorganic bioctahedral units. To the best of our knowledge, our work represents the first report on the blue light-excitable STE emission in 0D Bi-based metal halides, which will largely promote the rapid development of novel high-performance yellow light-emitting materials.

Large-area flexible scintillator screen based on copper-based halides for sensitive and stable X-ray imaging

X-ray scintillators, which convert high-energy radiation into visible light signals, have been rapidly developed for their widespread use in medical, security, and commercial diagnostic technologies. However, the development of large-area flexible scintillator screens with excellent stability and scintillation performance for non-planar objects is relatively lagging behind. Here, we fabricated large-area flexible scintillator screens with excellent stability and scintillation properties by loading nanoscale Cs3Cu2I5 particles into an elastic polydimethylsiloxane (PDMS) matrix. Copper halide Cs3Cu2I5, with self-trapped exciton emission, exhibits intense blue emission with a large Stokes shift, which can effectively reduce the light self-absorption effect. The experimental results reveal that the PDMS matrix can effectively passivate the surface defects of Cs3Cu2I5 particles, improve the exciton binding energy and ensure effective exciton recombination, thereby achieving more efficient optical coupling efficiency. In addition, the Cs3Cu2I5@PDMS flexible film exhibits excellent thermal stability, photostability, and water stability, and the radiative luminescence intensity does not decay after a continuous irradiation for 100 min under high-dose X-rays. Large-area flexible scintillator screen with uniform luminescence achieves a high spatial resolution of 8.6 lp/mm and a high light yield of 46000 photons/MeV, and exhibits excellent linear response to X-ray dose rate and low detection limit of 96.54 nGyair/s. Moreover, the large-area flexible scintillator screen exhibits high-quality X-ray imaging for both planar and non-planar objects. Our results demonstrate that the stable and sensitive Cs3Cu2I5@PDMS scintillator screen may have promising application prospects in flexible X-ray imaging fields.

Eu3+, Tb3+ doping induced tunable luminescence of Cs2AgInCl6 double perovskite nanocrystals and its mechanism

Incorporation of lanthanide ions (Ln3+) can remarkably enhance the structural stability and optical properties of lead-free perovskite NCs. Herein, we have established the relationship between the intrinsic emission of Cs2AgInCl6 host and the Ln3+ by Eu3+, Tb3+ doping in Cs2AgInCl6 NCs, realizing tunable luminescence of NCs in the visible region. Experimental studies and density functional theory (DFT) calculations analysis show that Eu3+ and Tb3+ occupy the sites of In3+ in Cs2AgInCl6, the defect formation energy for Cs2AgInCl6:Ln3+ is larger than the pristine Cs2AgInCl6, resulting in a more stable cubic double perovskite structure. The optical band gap increases with the increase in Ln3+ doping percentage. Turning excitation from 250 nm to 300 nm, the broad self-trapped excitons (STEs) emission is more remarkable, and the narrow Ln3+ emission is less notable. The emitted color can be adjusted from white to red and to green light by altering the doping concentration of Eu3+ or Tb3+ and excitation wavelength. This work promotes the design and optoelectronic application of desired lead-free perovskites.

Growth of SnX2 (X = Br, I) Single Crystals with Self-Trapped Exciton Emission.

Broadband emission with a large Stokes shift is important to obtain an excellent color rendering index of the solid-state lighting device. Among low-dimensional material and perovskite-like phosphors with broadband self-trapped emission, Sn-based phosphors have attracted much attention due to their high photoluminescence quantum yield (PLQY). However, the disadvantage is that the synthesis of Sn-based phosphors needs to be performed in a glovebox. Upon photoexcitation, the broadband emission of self-trapped excitons results from exciton-phonon coupling induced by the transient distortion of the lattice. Low-dimensional material structures often promote self-trapped emission because of more vibrational degrees of freedom and easier polarization under photoexcitation. Here, zero-dimensional (0D) SnX2 (X = Br, I) single crystals are synthesized by the solvent evaporation method in the air. SnX2 emits blue light, broadband yellow light, and deep red light, among which SnBr2 has the best luminescence performance. The photoluminescence quantum yield (PLQY) of SnBr2 reaches 85% and the Stokes shift reaches 265 nm. The PL intensity of SnX2 is linearly related to excitation power, which preliminarily indicates that the origin of SnX2 luminescence is attributed to self-trapped emission (STE). The white light-emitting diodes (WLEDs) were fabricated using yellow-emitting SnBr2 and blue-emitting BaMgAl10O17:Eu2+, which has a low correlated color temperature (3160 K) and a relatively common color rendering index (79).

Large-area vapor-deposited Cs3Cu2I5 perovskite thin films for highly effective third-order nonlinear optics

Zero-dimensional (0D) lead-free perovskites hold promise for efficient optoelectronic and photonic devices, but there are still critical challenges in fabricating large-area, high-quality thin films for practical applications. Herein, we report a simple vapor route to prepare 0D lead-free Cs3Cu2I5 perovskite thin films of high optical quality over large areas. Importantly, the deposition approach can be applied to diverse substrates, including mica, fused silica, MgO, and indium tin-oxide (ITO) coated glass. The deposited Cs3Cu2I5 thin films are phase pure and highly uniform. These Cs3Cu2I5 thin films exhibit strong blue emission upon UV light illumination, a broad band centered at 445 nm assigned to the self-trapped exciton emission. Furthermore, third-order nonlinear optical properties of the as-prepared thin films were determined by means of the Z-scan method. These thin films showed the third-order nonlinear absorption coefficient β as ∼ 1.07 × 10−7 m/W, which is five orders of magnitude larger than three-dimensional counterpart, CsPbI3. Thus, we demonstrate that large-area, high-quality Cs3Cu2I5 thin films can be vapor-deposited and have great potentials in optical switching and optical limiting applications.

Electron-Phonon Coupling Mediated Self-Trapped-Exciton Emission and Internal Quantum Confinement in Highly Luminescent Zero-Dimensional (Guanidinium)6Mn3X12 (X = Cl and Br).

We report a large Stokes shift and broad emission band in a Mn-based organic-inorganic hybrid halide, (Guanidinium)6Mn3Br12 [GuMBr], consisting of trimeric units of distorted MnBr6 octahedra representing a zero-dimensional compound with a liquid like crystalline lattice. Analysis of the photoluminescence (PL) line width and Raman spectra reveals the effects of electron-phonon coupling, suggestive of the formation of Frenkel-like bound excitons. These bound excitons, regarded as the self-trapped excitons (STEs), account for the large Stokes shift and broad emission band. The excited-state dynamics was studied using femtosecond transient absorption spectroscopy, which confirms the STE emission. Further, this compound is highly emissive with a PL quantum yield of ∼50%. With chloride ion incorporation, we observe enhancement of the emissive properties and attribute it to the effects of intrinsic quantum confinement. Localized electronic states in flat bands lining the gap and their strong coupling with phonons are confirmed with first-principles calculations.

Direct Electron Transfer Enables Highly Efficient Dual Emission Modes of Mn2+-Doped Cs2Na1-xAgxBiCl6 Double Perovskites.

Double perovskites with bright emission, low toxicity, and excellent stability have drawn considerable attention. Herein, we report the hydrothermal synthesis of Mn2+-doped Cs2Na1-xAgxBiCl6 double perovskites that exhibit dual emission modes. Introducing Ag+ ions to Cs2NaBiCl6 samples enables a bright self-trapped exciton (STE) emission in orange-red color, whereas Mn2+ dopants induce a yellow-orange emission. Importantly, Mn2+ doping into Cs2Na1-xAgxBiCl6 double perovskites with an indirect bandgap enables a high photoluminescence quantum yield of 49.52 ± 2%. Density functional theory calculations reveal that bringing Ag+ ions into Cs2NaBiCl6 can localize wave function to the [AgCl6]5- octahedron and convert dark transitions to bright STE transitions. Moreover, the 3d orbitals of Mn2+ dopants hybridize with Bi-6p and Cl-3p orbitals at the conduction band minimum, resulting in direct electron transfer from the host to Mn2+ and a significant increase in photoluminescence efficiency. These results shed light on the optical physical process of Mn2+-doped systems, providing useful information for further improvement of the photoluminescence efficiency of double perovskites.

Luminescence from Self‐Trapped Excitons and Energy Transfers in Vacancy‐Ordered Hexagonal Halide Perovskite Cs2HfF6 Doped with Rare Earths for Radiation Detection (Advanced Optical Materials 19/2022)

Cs2HfX6 halides show a vacancy-ordered cubic double perovskite structure when X = Cl, Br, and I. As to the first member of the halide family, Zhiping Luo and co-workers (article number 2201374) identify Cs2HfF6 as a new type of vacancy-ordered hexagonal perovskite. It is composed of single layers of building blocks. Tunable emission is obtained based on self-trapped exciton emissions from the host and energy transfers in the rare-earth-doped material. From energy-dependent cathodoluminescence and time-resolved X-ray radioluminescence, the co-doped material is found to be more sensitive to radiation energy than the singly-doped or pristine host.

Zero-dimensional rubidium zinc halide blue-emitting quantum dots for X-ray imaging

Low-dimensional-networked metal halide (MH) materials are emerged as a new class of semiconductors owing to their unique structure and outstanding photoelectric properties. Compared with the extensively studied three-dimensional (3D) MHs, the zero-dimensional (0D) MHs are of great interest to be widely studied. Here we report the successful colloidal synthesis of all-inorganic lead-free 0D MHs, including undoped and Cu-doped Rb2ZnCl4 quantum dots (QDs) with bright broad blue and cyan emissions, respectively. Combining the theoretical and experimental study, the band structures are well characterized and the originations of the blue and cyan emissions are attributed to the singlet and triplet self-trapped exciton (STE) emissions, respectively. Finally, owing to the bright radioluminescence (RL), the Cu-doped Rb2ZnCl4 QDs is prepared into a thin film to demonstrate the feasibility for X-ray imaging application. This work not only provides a cyan-emitting all-inorganic 0D MH QDs, but also exploits it as a scintillator for X-ray imaging.

Efficient and tunable photoluminescence for terbium-doped rare-earth-based Cs2NaYCl6 double perovskite.

Lead-free double perovskite materials with efficient and stable self-trapped exciton (STE) emissions show enormous potential for next-generation solid-state lighting. However, the low-emission efficiency and difficulty of spectral regulation are two major obstacles to their application. Here, all-inorganic rare-earth-based double perovskite Cs2NaYCl6 single crystals with strong blue emissions were reported as effective hosts to accommodate lanthanide ion doping. By controlling the introduction of Tb3 + ions and efficient energy transfer from the STEs to the dopants, the emission color of Cs2NaYCl6 single crystals was flexibly modulated from blue to green. The quantum yields were also significantly improved from 10% to 78.81% by optimizing the Tb3 + ion concentration. Further, stable light-emitting diode prototypes based on Cs2NaYCl6 color conversion materials were fabricated to demonstrate the practical applications of rare-earth-based double perovskite.

High Quantum Efficiency of Stable Sb‐Based Perovskite‐Like Halides toward White Light Emission and Flexible X‐Ray Imaging

AbstractAlthough low‐dimensional hybrid metal halides have emerged as promising light emitters due to their broadband emission originated from self‐trapped exciton (STE), the synthesis of lead‐free halides with high photoluminescence quantum yield remains a challenge. Herein, a series of new luminescent single crystals of antimony‐based metal halides [Na(DMSO)2]3SbBr6−xClx (x = 0, 2, 3, 4, 6) is synthesized. By optimizing the ratio of Br and Cl, [Na(DMSO)2]3SbBr3Cl3 exhibits an ultra‐broadband yellow light emission peaking at 606 nm with a full width at half‐maximum of 160 nm and a high photoluminescence quantum yield of 90.6%. Both experimental characterizations and theoretical calculations indicate that STE emission is responsible for the ultra‐broadband yellow light emission. Furthermore, blue LED chip‐pumped white light‐emitting diodes by using the yellow‐emitting [Na(DMSO)2]3SbBr3Cl3 are demonstrated, showing a correlated color temperature of 3948 K and a color rendering index of 85. Finally, a large‐size and flexible [Na(DMSO)2]3SbBr3Cl3 scintillator used for X‐ray imaging is prepared by a template assembled method, exhibiting a high spatial resolution of 15.5 lp mm−1 and a low detection limit of 285.8 nGyair s−1. This work highlights the potential of Sb‐based halides in solid‐state illumination and X‐ray imaging.

Boosting the Self-Trapped Exciton Emission in Cs2NaYCl6 Double Perovskite Single Crystals and Nanocrystals.

Halide double perovskites have aroused substantial research interest because of their unique optical properties and intriguing flexibility for various compositional adjustments. Herein, we report the synthesis and photophysics of rare-earth element yttrium (Y)-based double perovskite single crystals (SCs) and nanocrystals (NCs). The pristine Cs2NaYCl6 bulk SCs exhibit a weak sky-blue emission with a low photoluminescence quantum yield (PLQY) of 7.68% based on the self-trapped exciton (STE), while no PL emission was observed for NCs. Excitingly, the STE emission of SCs and NCs is greatly enhanced via Sb3+ doping. The optimized Cs2NaYCl6:Sb3+ SCs and NCs exhibit high PLQYs up to 82.5% and 51.8%, respectively. Theoretical calculations and charge-carrier dynamic studies demonstrate that the giant emission enhancement after Sb3+ doping is related with the enhancement of the sensitization of the emissive STE states, the passivating of the nonradiative carrier trapping processes, and the regulation of carrier-phonon coupling.

Organic Cation-Directed Modulation of Emissions in Zero-Dimensional Hybrid Tin Bromides.

Zero-dimensional hybrid metal halides (0D HMHs) are attractive due to their intriguing self-trapped exciton (STE) emission properties. However, the effect of organic cations on the emission of 0D HMHs is relatively underexplored. Herein, we report two types of 0D hybrid tin bromides, (BMe)2SnBr6 (BMe = C8N2H18) and (MeH)2SnBr6 (MeH = C7N2H16), which share similar structural features with different hydrogen bonding (HB) interactions between [SnBr6]4- anions and organic cations. The (BMe)2SnBr6 with weak HB interactions exhibits only STE emission, while the (MeH)2SnBr6 exhibits both STE and charge transfer exciton emissions owing to the strong HB interactions, resulting in an excitation-dependent emission at cryogenic conditions. Detailed structural analyses and Hirshfeld surface calculations confirm that the enhanced HB interactions are essential to obtain the multiple emissions in (MeH)2SnBr6.

Chiral 2D Cu(I) Halide Frameworks

Hybrid multifunctional materials have great potential in a wide variety of applications due to their flexible combination of organic and inorganic components. Introducing chiral organic modules into the metal halide frameworks can effectively generate multifunctional materials, achieving new functionalities with noncentrosymmetric structures. Here, by incorporating (R)- or (S)-piperidine-3-carboxylic acid (R/S-PCA) as the templating cation, we report the synthesis and characterization of three pairs of new 2D chiral hybrid Cu(I) halides, namely, (R/S-PCA)CuBr2, (R/S-PCA)CuBr2·0.5H2O, and (R/S-PCA)CuI2. These chiral Cu(I) halides crystallize in the noncentrosymmetric space group C2 and belong to a new structural type similar to layered silicates. The optical absorption edges of these chiral materials can be tuned by changing the halide or upon the absorption of water and range from 2.70 to 3.66 eV. A dynamic conversion between (R/S-PCA)CuBr2 and (R/S-PCA)CuBr2·0.5H2O occurs through exposure to moisture or vacuum drying along with changes in the reversible bandgap and photoluminescence. Chiroptical properties such as circular dichroism, circular polarized light emission, and second harmonic generation are investigated. Density functional theory calculations (DFT) show the indirect and direct bandgap natures of these Cu(I) halides and reveal the mechanism for the broadband self-trapped exciton emission at the excited state. The fascinating structural type, chiroptical properties, and reversible hydrochromic behavior of these Cu(I)-based halides make them viable candidates for next-generation multifunctional optoelectronic materials.

Efficient and self-healing copper halide Cs3Cu2Cl5 film assisted by microwave treatment for high-resolution X-ray imaging

Lead-free Cs3Cu2Cl5 metal halide exhibits high photoluminescence quantum yield (PLQY), large Stokes shifts and small self-absorption due to self-trapped excitons (STE) emission, which undoubtedly is a potential scintillator material. However, Cs3Cu2Cl5 nanocrystals (NCs) are susceptible to degradation by moisture at high humidity environment, which severely affects its long-term application in X-ray imaging. Herein, we prepared Cs3Cu2Cl5 scintillator films with a PLQY of 72.4% and a high spatial resolution of 20 lp mm−1. Moreover, we firstly propose a self-healing strategy with facile microwave treatment to recover the crystal structure of Cs3Cu2Cl5 film which damaged by moisture, while the photoluminescence (PL) and radioluminescence (RL) intensities of the damaged Cs3Cu2Cl5 film are repaired to more than 95% and the spatial resolution can be restored to 20 lp mm−1. Furtherly, the imaging quality of the self-healing scintillator film can be maintained stably by cyclic microwave treatment. It found that microwave treatment provides a simultaneous and molecular level heating environment for the Cs3Cu2Cl5 film, which drives the hydrolysates to re-crystallize along with the surface of the destroyed crystals. Therefore, microwave treatment opens a new avenue to recover Cs3Cu2Cl5 films degraded by moisture, and provides a solution for long-term application of scintillator films at low cost.

Competitive Dual-Emission-Induced Thermochromic Luminescence in Organic-Metal Halides.

Lead-free Halides, especially Mn-based ones, are preferred as hotspots in the exploration of photoluminescent materials. However, there are few reports on sensitive reversible thermochromism and switchable dual emission originating from self-trapped exciton emission in pure Mn-Based materials. Here, we report a new Mn-based hybrid material [TMPA]2MnI4 (TMPA = trimethylphenylammonium), which shows two emission peaks at 545 and 660 nm benefitting from the d-d orbital transition of Mn2+ and the generation of self-trapped excitons, respectively. Due to the different sensitivity to temperature, the stages of thermal activation and thermal quenching of the two emission types are also inconsistent, showing a certain competition relationship and dominating the emission colors in different temperature ranges, resulting in adjustable green-orange-green thermochromic luminescence from 100 to 403 K (both high and low temperatures correspond to green, and orange is displayed at near room temperature). Therefore, thermochromic luminescence can be easily achieved by controlling the temperature under the guidance of excited states. This work provides new insights into the synthesis and application of thermochromic materials. Therefore, it is certain that regulating temperature while being guided by excited states will achieve thermochromic luminescence. This research offers fresh perspectives on the development and potential of thermochromic materials.

Excitation-Dependent Luminescence of 0D ((CH3)4N)2ZrCl6 across the Full Visible Region.

Herein, we report a novel hybrid organic-inorganic Zr(IV) metal halide ((CH3)4N)2ZrCl6, which demonstrates fascinating excitation-dependent luminescence across the full visible region. The single crystal of ((CH3)4N)2ZrCl6 showed an unexpected high degree of symmetry and formed a unique 0D structure with isolated [ZrCl6]2- octahedrons. Amazingly, three different emission groups emerged under changeable excitation light. The first emission group peaked at 462 nm with a ns lifetime and a μs lifetime, which is assigned to free-exciton fluorescence and thermally activated delayed fluorescence (TADF). The second group of emissions featured elaborate multipeak light-emitting components, which is ascribed to the d-d transitions of Zr(IV). The third emission group centered at 660 nm was attributed to the typical self-trapped exciton (STE) emission. To our best knowledge, this work for the first time reports a 0D organic-inorganic metal halide with distinctive excitation-dependent full-visible-spectrum luminescence via four different emission mechanisms.

Site-selective luminescence of Eu3+ ions in silicate-tungstates with apatite and scheelite structures

The present work studies europium-ion spectroscopic features in solid solutions based on silicate-tungstates Ca2La6.8Eu1.2Si5.6W0.4O26.4 and Ca8Eu2Si3W3O26 microcrystalline powders with the crystal structure of silicate apatite and scheelite respectively. The spectroscopic features were studied by means of photoluminescence spectroscopy and X-ray excited luminescence at temperatures 4.6, 90 and 295 K. In Ca2La6.8Eu1.2Si5.6W0.4O26.4 only intensive luminescence was observed, which was characterized by a set of 5D0 → 7FJ dominant intraconfigurational transitions for Eu3+ ion. In Ca8Eu2Si3W3O26, both 5D0→ 7FJ intraconfigurational transitions for Eu3+ ion and wide 430 nm emission band corresponding to host self-trapped exciton (STE) emission are observed. This STE emission band is reabsorbed by the f – f absorption of Eu3+ ions by means of energy transfer from host to Eu3+. The asymmetry coefficient which characterizes the shape of the emission spectrum of Eu3+ ions strongly depends on the energy of exciting photons. The Eu3+ ion might occupy two nonequivalent crystallographic sites. Some features of this phenomenon were discussed.