Radiative Recombination Of Self-trapped Excitons Research Articles

Pressure-induced abnormal blue-shift emission enhancement and phase transition of perovskite DMAPbI3

Designing low-dimensional hybrid organic–inorganic perovskites (HOIPs) with enhanced broadband emission under ambient conditions remains a pressing challenge. Here, interesting results of emission blueshift and enhancement were successfully achieved by pressure modulation of the (NH2(CH3)2PbI3 ((NH2(CH3)2 = DMA) structure. The observed rapid blueshifted emission is closely related to the distortion of PbI6 octahedron induced by phase transition from the P63/mc phase to the P1 phase at 0.8 GPa, which has been confirmed by in situ high-pressure PL, UV–vis absorption, synchrotron XRD and Raman spectroscopy. The pressure-induced PL enhancement of DMAPbI3 can be ascribed to the mechanism that the distorted PbI6 octahedrons promote the radiative recombination of self-trapped excitons by increasing the activation barrier energy for detrapping. The PL intensity enhancement was retained at 4 times the initial value after the pressure was released. These findings deepen the understanding of the structure-property relationships of one-dimensional perovskite and reveal the roles of pressure in regulating the optical properties of perovskites.

Dual-modal optical temperature sensing based on Sb3+/Mn2+ co-doped Cs2NaYCl6 double perovskites

Optical temperature sensing based on luminescence intensity ratio shows significant potential in achieving accurate temperature detection. In this work, Sb3+/Mn2+ co-doped Cs2NaYCl6 double perovskites were synthesised via a hydrothermal method. Introducing Sb3+ ions to the host significantly enhances the radiative recombination of self-trapped excitons (STEs), resulting in a broad blue emission. The co-doping of Mn2+ ions to the composition leads to a tunable dual-emission in the spectra, originating from the energy transfer between the STEs and Mn2+ ions. The dependence of the dual-emission on temperature is employed for optical temperature sensing. The maximum relative sensitivity, optimal thermal resolution, and optimal thermal repeatability are determined as 1.40 % K−1, 0.002 K and 99.3% at 250 K, respectively. The results indicate that the synthesised Cs2NaYCl6: Sb3+/Mn2+ double perovskites are promising candidates for high-sensitivity optical thermometers.

Blue light emissive zero-dimensional hybrid cadmium bromide as fluorescence sensor toward benzaldehyde

Organic-inorganic hybrid low-dimensional metal halides have been widely studied as a new class of luminescence materials due to abundant structural diversity and intriguing photophysical property. Herein, we explored two new Cd-based 0D halides of [BHEPZ]CdBr4 (BHEPZ = 1,4-Bis(2-hydroxyethyl) piperazine) and [EPIPZ]CdBr4 (EPIPZ = 1-ethylpiperazine) through facile wet-chemistry method. These 0D halides exhibit blue light emissions derived from radiative recombination of self-trapped excitons (STEs) based on detailed spectroscopy investigations. More interestingly, [BHEPZ]CdBr4 exhibits rapid luminescence off switching toward benzaldehyde but fails in any other organic solvents. In-depth investigations demonstrate that the detection limit can fall to 2.65 ppm indicating perfect real-time fluorescent probe to detect benzaldehyde with high sensitivity and selectivity. This work enriches the cadmium halide materials and provide a new perspective for potential applications of 0D hybrid metal halides.

CO2 Pressure‐Induced Self‐Trapped Excitons in SrTiO3

With strong electron–phonon coupling, self‐trapped excitons (STEs) are typically formed in perovskite materials, and radiative recombination of STEs can produce broadband emission with large Stokes shifts. STEs are essential to further improve the optoelectronic properties of materials. Surprisingly, 2D system is the edge case, with low even no self‐trapping barriers, leading to effortless formation of STEs. In this work, 2D strontium titanate (SrTiO3) with defects is prepared using supercritical carbon dioxide (SC CO2) and its carrier transport and transition are studied. The appearance of wide photoinduced positive absorption signals in the femtosecond transient absorption spectra is direct evidence for the formation of STEs. The presence of STEs is further supported by the increased Stokes shift and full width at half maximum in the steady‐state photoluminescence spectra.

Composition engineering of lead-free double perovskites towards efficient warm white light emission for health and well-being

Lead-free halide double perovskites (DPs) [A2B(I)B(III)X6] (A: monovalent cation, B(I): monovalent cation, B(II): trivalent cation, X: halide anion) has drawn tremendous attention because of their environmental-friendliness and high stability compared to traditional lead-based perovskites ABX3 (A: monovalent cation; B: Pb2+; X: halide anion). The optoelectronic properties of DPs are, however, compromised. This work provides a methodology for improving the photophysical properties of DPs and achieving high-efficiency warm white light emission. First principles density functional theory (DFT) was used in material design and the ligand-free synthesis of halide DP Cs2Ag1−xKxIn0.875Bi0.125Cl6 (x ≤ 0.60) via a facile recrystallization process was demonstrated. The compositional tuning of K+ to Ag+ resulted in an improvement in photophysical properties. Independent of K+ content, all the samples exhibit strong absorption at a wavelength of λmax ∼ 375 nm with a direct bandgap which is consistent with our DFT calculation results. Broadband photoluminescence (PL) emission profiles covering the spectra from blue to deep red (405–820 nm at λmax ∼ 629 nm) were observed. Besides, with an optimized K+ alloying content of 0.20, the optical performance of these halide DPs was impressively regulated, demonstrating improved photoluminescence quantum yield (PLQY) of host Cs2AgInCl6 crystals from ∼ 2.70 % (x = 0) to ∼15.96 % (x = 0.20), due to increased radiative recombination of self-trapped excitons. the highest report for such structures. It also shows high stability over 180 days. Furthermore, the use of blue-emitting CsPbBr3 and DP Cs2Ag0.80K0.20In0.875Bi0.125Cl6 as color conversion layers in white light-emitting diodes (LEDs) demonstrates that high-quality white light emission with the CIE color coordinate of (0.387, 0.385) and a correlated color temperature (CCT) of 3878 K, color rendering index (CRI) of 85, and luminous efficacy of radiation (LER) of 214 lm/W. Hence, the research work provides insight into realizing environmentally friendly and high-efficiency white light emission with high color quality by using earth-abundant elements and the low-cost synthesis method.

Growth of β-Ga2O3 Single-Crystal Microbelts by the Optical Vapor Supersaturated Precipitation Method

Monoclinic β-Ga2O3 microbelts were successfully fabricated using a one-step optical vapor supersaturated precipitation method, which exhibited advantages including a free-standing substrate, prefect surface, and low cost. The as-grown microbelts possessed a well-defined geometry and perfect crystallinity. The dimensions of individual β-Ga2O3 microbelts were a width of ~50 μm, length of ~5 mm, and thickness of ~3 μm. The SEM, XRD, HRTEM, XPS, and Raman spectra demonstrated the high single-crystalline structure of β-Ga2O3 microbelts. Twelve frequency modes were activated in Raman spectra. The optical band gap of the β-Ga2O3 microbelt was calculated to be ~4.45 eV. Upon 266 nm excitation, 2 strong UV emissions occurred in photoluminescence spectra through the radiative recombination of self-trapped excitons, and the blue emission band was attributed to the presence of donor-acceptor-pair transition. The individual β-Ga2O3 microbelt was employed as metal-semiconductor-metal deep-ultraviolet photodetector, which exhibits the photoresponse under 254 nm. This work provides a simple and economical route to fabricate high-quality β-Ga2O3 single-crystal microbelts, which should be a potential synthetic strategy for ultra-wide bandgap semiconductor materials.

Three homologous 1D lead halide perovskites with broadband white-light emissions

Three new one-dimensional (1D) face-shared octahedral perovskites with unified APbBr3 composition, namely, [DTHPE]Pb2Br6 (1), [TMPDA]PbBr3 (2) and [MPD]PbBr3 (3) have been synthesized by using different types of organic cations. These 1D perovskites exhibit tunable broadband luminescence from orange to blue light emissions. Experimental and computational studies unveil that these broadband emissions are derived from the radiative recombination of self-trapped excitons due to strong electron–phonon coupling.

A Zero-Dimensional Hybrid Cadmium Perovskite with Highly Efficient Orange-Red Light Emission.

Low-dimensional organic-inorganic hybrid metal halide materials have been extensively studied due to their excellent optoelectronic performances. Herein, by using the facile wet-chemistry method, we designed one new hybrid cadmium bromide of (H3AEP)2CdBr6·2Br based on discrete octahedral [CdBr6]4- units. Remarkably, the bulk crystal of (H3AEP)2CdBr6·2Br exhibits strong broadband orange-red light emission from the radiative recombination of self-trapped excitons (STEs) with a high photoluminescence quantum yield (PLQY) of 9%. Benefiting from the highly efficient luminescent performance, this 0D cadmium perovskite can be utilized as an excellent down-conversion red phosphor to assemble a white light-emitting diode, and a high color rendering index (CRI) of 93 is realized. As far as we know, this is the first orange-red light-emitting hybrid cadmium perovskite which promotes the full-color display in this system.

Co-Doping of Cerium and Bismuth into Lead-Free Double Perovskite Cs2AgInCl6 Nanocrystals Results in Improved Photoluminescence Efficiency.

Lead-free double cation metal halide perovskites have recently attracted considerable attention, with continuing research efforts focusing on the improvement of their stability and photoluminescence quantum yield (PL QY). In this study, Ce3+ has been co-doped together with Bi3+ into lead-free double perovskite Cs2AgInCl6 nanocrystals (NCs) in order to improve their crystallinity and PL QY. Both uncoordinated chloride ions and silver vacancies could be eliminated using this co-doping strategy, and the resulting Ce3+,Bi3+-co-doped Cs2AgInCl6 NCs showed adjustable PL emission peaks in the range of 589 to 577 nm by varying the doping amount of Ce3+ with a fixed feeding ratio of bismuth precursor set at 1%. Cs2AgInCl6 NCs doped with 1% Bi alone reached a PL QY of 10% for the PL peak centered at 591 nm, while those co-doped with 1% Bi and 2% Ce together achieved the highest PL QY of 26% for the PL peak centered at 580 nm. The use of Ce3+ as a dopant promoted the localization of self-trapped excitons to prevent PL quenching, although the ion's 5d excited state may potentially provide an energetically favorable indirect route for the radiative relaxation process. This also resulted in a blue shift of the PL maximum and increased the exciton binding energy, thus promoting the radiative recombination of self-trapped excitons.

Three-Dimensional Cuprous Iodide Framework with Intrinsic Broadband Red-to-Near-Infrared Light Emission.

Herein, a new organic-inorganic hybrid cuprous iodide of [(Me)2-DABCO]Cu6I8 was prepared and structurally characterized with a novel three-dimensional (3D) [Cu6I8]2- framework. Significantly, this 3D cuprous iodide displays infrequent broadband red-to-near-infrared light emission (600-1000 nm) stemming from the radiative recombination of self-trapped excitons.

Pressure-Induced Emission toward Harvesting Cold White Light from Warm White Light.

The pressure-induced emission (PIE) behavior of halide perovskites has attracted widespread attention and has potential application in pressure sensing. However, high-pressure reversibility largely inhibits practical applications. Here, we describe the emission enhancement and non-doping control of the color temperature in two-dimensional perovskite (C6 H5 CH2 CH2 NH3 )2 PbCl4 ((PEA)2 PbCl4 ) nanocrystals (NCs) through high-pressure processing. A remarkable 5 times PIE was achieved at a mild pressure of 0.4 GPa, which was highly associated with the enhanced radiative recombination of self-trapped excitons. Of particular importance is the retention of the 1.6 times emission of dense (PEA)2 PbCl4 NCs upon the complete release of pressure, accompanied by a color change from "warm" (4403 K) to "cold" white light with 14295 K. The irreversible pressure-induced structural amorphization, which facilitates the remaining local distortion of inorganic Pb-Cl octahedra with respect to the steric hindrance of organic PEA+ cations, should be greatly responsible for the quenched high-efficiency photoluminescence.

Pressure-Induced Emission (PIE) of One-Dimensional Organic Tin Bromide Perovskites.

Low-dimensional halide perovskites easily suffer from the structural distortion related to significant quantum confinement effects. Organic tin bromide perovskite C4N2H14SnBr4 is a unique one-dimensional (1D) structure in which the edge sharing octahedral tin bromide chains [SnBr42-]∞ are embraced by the organic cations C4N2H142+ to form the bulk assembly of core-shell quantum wires. Some unusual phenomena under high pressure are accordingly expected. Here, an intriguing pressure-induced emission (PIE) in C4N2H14SnBr4 was successfully achieved by means of a diamond anvil cell. The observed PIE is greatly associated with the large distortion of [SnBr6]4- octahedral motifs resulting from a structural phase transition, which can be corroborated by in situ high-pressure photoluminescence, absorption, and angle-dispersive X-ray diffraction spectra. The distorted [SnBr6]4- octahedra would accordingly facilitate the radiative recombination of self-trapped excitons (STEs) by lifting the activation energy of detrapping of self-trapped states. First-principles calculations indicate that the enhanced transition dipole moment and the increased binding energy of STEs are highly responsible for the remarkable PIE. This work will improve the potential applications in the fields of pressure sensors, trademark security, and information storage.

Absorption and emission features of Ho3+ ion in Nb2O5 mixed Lithium zirconium silicate glasses

Li2O–ZrO2–SiO2: Ho3+ glasses mixed with Nb2O5 were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The optical absorption spectra of all glasses recorded at room temperature in the wavelength region 300-2000 nm exhibited several absorption bands all from the ground state 5I8 to 5G5, 5G6, 5F1, 5F3, (5F4+5S2), 5F5, 5I5, 5I6, 5I7. The luminescence spectra of all the glasses recorded at room temperature in the visible and NIR regions exhibited the following prominent emission bands 5F3 → 5I8, 5S2 → 5I8, 5G4 → 5I6, 5K8 → 5I7, 5F5 → 5I8 ,5G5 → 5I6, 5F4 →5I7, 5G5 → 5I5, 5F2 → 5I6, 5F3 → 5I6, 5I5 → 5I8 (Visible region) and ,5I7 → 5I8 (NIR region). The luminescence spectra of Nb2O5 mixed Li2O–ZrO2–SiO2 glasses (free of Ho3+ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Nb5+ ions in the glass network. The Judd–Ofelt theory was successfully applied to characterize Ho3+ spectra of all the glasses. From this theory, various radiative properties like transition probability A, branching ratio βr, the radiative lifetime τr, for 5S2 emission levels in the spectra of these glasses has been evaluated. The radiative life time for 5S2 level of Ho3+ ions has also been measured and quantum efficiencies were estimated.

Broadband Emission with a Massive Stokes Shift from Sulfonium Pb–Br Hybrids

Similar to organoammonium cations that template the well-studied layered perovskites, organosulfonium cations template the layered Pb–Br hybrid (tms)4Pb3Br10 (1; tms = (CH3)3S+). Upon ultraviolet excitation, this colorless, organic-inorganic hybrid exhibits broad red/near-infrared photoluminescence (PL) with a massive Stokes shift of ca. 1.7 eV. A suite of PL measurements suggests that the broad emission is an intrinsic property of the material. We ascribe this emission to radiative recombination of self-trapped excitons in the inorganic sublattice, which features both face- and corner-sharing Pb–Br octahedra. We further demonstrate that complex sulfonium-based cations can expand this family of lead-halide hybrids while maintaining the broad, Stokes-shifted PL. The use of more exotic main-group cations affords an exciting opportunity for synthetic chemists to expand the phase-space of semiconducting hybrids with unusual properties for potential applications in optoelectronics.

Self-trapped exciton emission from carbon dots investigated by polarization anisotropy of photoluminescence and photoexcitation.

Carbon dots have attracted tremendous attention because of their intrinsic advantages that open up opportunities to replace traditional fluorescent materials in various application fields. However, until now, the emission mechanism from carbon dots has been controversial, substantially hindering the extensive exploitation of these materials. Here, we explore systematically the essential emission behavior of carbon dots by using polarization anisotropy spectroscopy, electric-field modulation spectroscopy, and time-resolved photoluminescence measurements. We probe the momentum evolution dynamics and evaluate the decay process of the photoexcited hot carriers, which manifest characteristics that are distinct from band edge emission. We provide clear evidence that carbon dot emission originates from radiative recombination of self-trapped excitons, where the mobilization of the carriers is largely impeded due to the existence of a strong local potential field and thus the relaxation of the hot carriers is strongly suppressed. Based on the self-trapped exciton model, all the optical properties of carbon dots inferred from both steady-state and time-resolved optical spectroscopy can be interpreted consistently. Our investigation provides an alternative insight into the emission mechanisms of carbon dots, which may improve our understanding of these novel materials.

Luminescence and scintillation properties of Cs3BiCl6 crystals

The optical and scintillation properties of Cs3BiCl6 single crystals were characterized, and absorption properties were investigated for thin films. The thin films showed two absorption bands at ∼220 nm and 330 nm; these bands can be attributed to the 1A1g → 1T1u and 1A1g → 3T1u transitions of Bi3+ ions, respectively. A luminescence band was observed at ∼390 nm in the photoluminescence spectra; this band can be attributed to the 3T1u → 1A1g transition of Bi3+ ions. In the X-ray-induced radioluminescence spectrum, in addition to the luminescence band at 390 nm, another band was observed at 600–700 nm; this band was tentatively attributed to the radiative recombination of self-trapped excitons. The decay-time constants of photoluminescence and scintillation decay were of the order of nanoseconds. The scintillation light yield was 800 photons/MeV. The results indicate that Cs3BiCl6 has a fast scintillation decay and a relatively poor light yield.

Photoluminescence of monoclinic Li3AlF6 crystals under vacuum ultraviolet and soft X-ray excitations

Using Bridgman technique we have grown monoclinic β-LiAF crystals suitable for optical studies, performed XRD-identification and Rietveld refinement of the crystal structure and carried out a photoluminescence study upon vacuum ultraviolet (VUV) and extreme ultraviolet (XUV)-excitations, using the low-temperature (T=7.2K) time-resolved VUV-spectroscopy technique. The intrinsic PL emission band at 340–350nm has been identified as due to radiative recombination of self-trapped excitons. The electronic structure parameters were determined: bandgap Eg≈12.5eV, energy threshold for creation of unrelaxed excitons 11.8eV<En<12.5eV. The PL emission bands at 320–325 and 450nm were attributed to luminescence caused by lattice defects. We have discovered an efficient excitation of PL emission bands in the energy range of interband transitions (Eex>13.5eV), as well as in the energy range of core transitions at 130eV. We have revealed UV–VUV PL emission bands at 170 and 208nm due to defects. A reasonable assumptions about the origin of the UV–VUV bands were discussed.

Optical properties of hierarchical-nanostructured TiO2 and its time-dependent photo-degradation of gaseous acetaldehyde

The TiO2 hierarchical nanostructures (HNs) composed of rutile TiO2 nanowires on anatase TiO2 nanofibers had higher photocatalytic activities of 62% and 48% than the commercial TiO2 nanoparticles (∼21 nm diameter) in the continuous flow mode and closed-circulation mode, respectively, leading to an efficient degradation of gaseous acetaldehyde under UV-light irradiation. This behavior may be attributed to the effective TiO2 HNs with specific surface area of 85.1 m2/g and lower radiative recombination of self-trapped excitons, enabling an effective electron-hole separation.

Low temperature luminescence of ZnMoO4 single crystals grown by low temperature gradient Czochralski technique

ZnMoO4 single crystals of high optical quality were grown using low temperature gradient Czochralski technique and their luminescence properties were studied. At low temperatures two overlapping luminescence bands with the maxima 1.93eV and 2.45eV were detected at Eex>3.9eV. The bands are attributed to the radiative recombination of self-trapped excitons of MoO42- parentage. High-intensity non-elementary peak of thermostimulated luminescence (TSL) observed at 65K is due to the thermal release of self-trapped holes. The threshold of TSL excitation spectrum at 6.2eV exceeds the bandgap value by 1.9eV and corresponds to electronic transitions from the valence band to the upper subband of the conduction band.

Emission features of Ho 3+ ion in Nb 2O 5, Ta 2O 5 and La 2O 3 mixed Li 2O–ZrO 2–SiO 2 glasses

Li 2O–ZrO 2–SiO 2: Ho 3+ glasses mixed with three interesting d-block elemental oxides, viz., Nb 2O 5, Ta 2O 5 and La 2O 3, were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The luminescence spectra of Nb 2O 5 and Ta 2O 5 mixed Li 2O–ZrO 2–SiO 2 glasses (free of Ho 3+ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Ta 5+ and Nb 5+ ions in the glass network. The Judd–Ofelt theory was successfully applied to characterize Ho 3+ spectra of all the three glasses. From this theory various radiative properties, like transition probability A, branching ratio β r and the radiative lifetime τ r, for 5S 2 emission levels in the spectra of these glasses have been evaluated. The radiative lifetime for 5S 2 level of Ho 3+ ions has also been measured and quantum efficiencies were estimated. Among the three glasses studied the La 2O 3 mixed glass exhibited the highest quantum efficiency. The reasons for such higher value have been discussed based on the relationship between the structural modifications taking place around the Ho 3+ ions.