Photoluminescence Efficiency Research Articles

Photoluminescence enhancement for blue-green emission in copper-alloyed lead-free cesium halide single crystals.

Recently, metal halides have received extensive attention because of the superior photophysical characteristics. Regardless of the superiority, the limited stability against heat and moisture and the toxicity problem of heavy lead metal are obstacles to the realization of wide range applications. In this case, it is necessary to develop eco-friendly alternatives, which could simultaneously maintain the excellent optoelectronic properties of lead materials. In this paper, the synthesis of lead-free one-dimensional Cs2AgBr3 and Cu(I)-alloyed Cs2AgBr3 single crystals (SCs) has been successfully realized. Experimental results demonstrated that the addition of applicable copper ions could greatly improve their luminescence intensity. A bright blue-green photoluminescence peaking at 510 nm was observed after incorporating Cu+ ions into Cs2AgBr3 SCs under UV irradiation. Theoretical calculation further proved that the incorporation of Cu+ could effectively modulate the materials' electronic band structure; the electronic states limited to the CuBr4 tetrahedron presented a strong localized property, which was beneficial to increase the photoluminescence efficiency. In addition, the SCs displayed favorable structure stability proofing moisture and oxygen under ambient conditions, proving that this material has good prospects for the development of optoelectronic fields.

Enhanced photoluminescence efficiency and stability of CsAgCl2 by a NaCl-assisted synthesis

Enhanced photoluminescence efficiency and stability of CsAgCl2 by a NaCl-assisted synthesis

Twisted and Disconnected Chains: Flexible Linear Tetracuprous Arrays and a Decanuclear CuI Cluster as Blue- and Green/Yellow-Light Emitters.

Defined arrays of transition metal ions embedded in tailored polydentate ligand scaffolds allow for a systematic design of their physical properties. Such molecular strings of closed-shell transition metal centers are particularly interesting for Group 11 metal ions in the oxidation state +1 if they undergo metallophilic d10···d10 contact interactions since these clusters are oftentimes efficient photoluminescence (PL) emitters. Copper is particularly attractive as a sustainable earth-abundant coinage metal source and because of the ability of several CuI complexes to serve as powerful thermally activated delayed fluorescence (TADF) emitters in molecular/organic light-emitting devices (OLEDs). Our combined synthetic, crystallographic, photophysical, and computational study describes a straight tetracuprous array possessing a centrally disconnected CuI2···CuI2 chain and a continuous helically bent CuI4 complex. This molecular helix undergoes a facile rearrangement in diethyl ether solution, yielding an unprecedented nanosized CuI10 cluster (2.9 × 2.0 nm) upon crystallization. All three clusters show either bright blue phosphorescence, TADF, or green/yellow multiband phosphorescence with quantum yields between 6.5 and 67%, which is persistent under hydrostatic pressure up to 30 kbar. Temperature-dependent PL investigations in combination with time-dependent density-functional theory (TD-DFT) calculations and void space analyses of the crystal packings complement a comprehensive correlation between the molecular structures and photoluminescence properties.

Synergistic Effect of Zn2+ Cation Doping and Te2− Anion Passivation on CsPbBrxI3‐x Nanocrystals for Efficient Perovskite Light‐Emitting Diodes

AbstractThe challenges of instability and surface defects in CsPbBrxI3‐x nanocrystals (NCs) pose significant limitations on their potential application in high‐performance pure‐red perovskite light‐emitting diodes (PeLEDs). Herein, a synergistic strategy of divalent cation (Zn2+) doping and anion (Te2−) passivation is proposed to solve these issues. Density functional theory analysis reveals that the synergistic effect can not only reduce the formation energy of CsPbBrxI3‐x NCs but also increase theiodide vacancy defect formation energy of CsPbBrxI3‐x NCs. Consequently, the optimized Zn2+/Te2− co‐modified CsPbBrxI3‐x NCs exhibit significantly enhanced stability with a near‐unity photoluminescence efficiency. Pure‐red PeLEDs based on these CsPbBrxI3‐x NCs possess outstanding spectral stability with a maximum external quantum efficiency and luminance of 16.1% and 1397.2 cd m−2, respectively. This synergistic strategy provides a new approach for enhancing the performance of mixed halide perovskite NCs and the corresponding optoelectronic devices.

Dual Passivation Strategy for Highly Stable Blue-Luminescent CsPbBr3 Nanoplatelets.

Blue-emitting colloidal CsPbX3 (X = Br, Cl, or I) perovskite nanocrystals have emerged as one of the most fascinating materials for optoelectronic applications. However, their applicability is hindered by poor stability and a low photoluminescence efficiency. Herein, highly stable CsPbBr3 nanoplatelets exhibiting intense blue luminescence are fabricated by employing a strategy in which the morphology is regulated and the surface is subjected to dual passivation through the incorporation of zirconium acetylacetonate [Zr(acac)4]. The passivated CsPbBr3 nanocrystals exhibit adjustable light emission from green to dark blue and a controllable morphology from nanocubes (NCs) to nanoplatelets (NPLs) and nanorods accomplished by varying the content of Zr(acac)4. The optimized NPLs are characterized by a bright blue emission with a central wavelength of 459 nm and a high photoluminescence quantum yield of 90%. The addition of Zr(acac)4 in the synthesis of CsPbBr3 induces oriented growth with a two-dimensional morphology. The Zr(acac)4 can repair the surface defects of the nanocrystal surface, and the surface is also capped with the Zr(OH)4 cluster layer. Therefore, the passivated blue-emitting NPLs exhibit outstanding stability compared to that of pristine NPLs during long-term storage and exposure to light. This work provides a novel strategy for fabricating highly stable PNCs with deep-blue emission and widens their potential applications in blue-emitting optoelectronic devices.

Photoluminescence Sensing of Lead Halide Perovskite Nanocrystals and Their Two-Dimensional Structural Materials

In recent years, the development of new efficient, fast, and intuitive materials and methods for photoluminescence (PL) sensing has become a research hotspot in analytical chemistry. Lead halide perovskite (LHP) materials have the characteristics of adjustable PL properties, high PL efficiency, and a variety of synthesis methods. Their PL is also sensitive to the change in specific factors in the environment. Based on these characteristics, LHP has shown good application prospects in the field of optical sensing. The study of the structural dimension, organic composition, or doped ions of LHP is helpful in exploring its sensing potential and proposing new sensing mechanisms, which have important research significance to promote sensing applications. In this review, the PL characteristics and sensing mechanisms, as well as their sensing applications of two- and three dimensional LHP, are discussed and summarized.

Circularly Polarized Perovskite Luminescence in Composite Films with High Flexibility and Stability

AbstractFlexible circularly polarized luminescence (CPL) exhibits significant potential for applications in smart wearable devices and high‐end anti‐counterfeiting. However, existing technologies suffer from low dissymmetry factor (glum) and poor mechanical reliability. Here, a metal halide perovskite is employed as the emitter to construct efficient and robust flexible CPL films through a facile strategy of bilayer stacking, which comprises a layer of perovskite nanocrystalline embedded polymer film and a layer of photonic crystal film based on polymerized chiral liquid crystals (LCs). The photoluminescence efficiency of perovskite nanocrystals in polyacrylonitrile (PAN) matrix is improved by incorporating an appropriate amount of phenylethylammonium bromide (PEABr) as a passivation agent, and the helical arrangement and optical activity of free‐standing flexible photonic crystal films are found to be highly related to the supporting substrates. Upon stacking, the resulting flexible composite film exhibits extremely high |glum| values of up to 1.81, representing the highest value among reported flexible CPL‐active films. Moreover, the composite films demonstrate remarkable mechanical robustness, which shows negligible degradation in terms of glum value even after 1000 bending cycles at a bending radius of 2 mm. Based on the flexible CPL‐active films, advanced anti‐counterfeit labels with switchable patterns under circular polarizers are demonstrated.

Achieving Record External Quantum Efficiency of 11.5 % in Solution-Processable Deep-Blue Organic Light-Emitting Diodes Utilizing Hot Exciton Mechanism.

High performance solution-processable deep-blue emitters with a Commission International de l'Eclairage (CIE) coordinate of CIEy≤0.08 are highly desired in ultrahigh-definition display. Although, deep-blue materials with hybridized local and charge-transfer (HLCT) excited-state feature are promising candidates, their rigidity and planar molecular structures limit their application in solution-processing technique. Herein, four novel deep-blue solution-processable HLCT emitters were first proposed by attaching rigid imide aliphatic rings as functional units onto the HLCT emitting core. The functional units not only improve solubility, enhance thermal properties and morphological stability of the emitting core, but also promote photoluminescence efficiency, balance charge carrier transport, and inhibit aggregation-caused quenching effect due to the weak electron-withdrawing property as well as steric hindrance. The corresponding solution-processable organic light-emitting diodes (OLEDs) substantiate an unprecedented maximum external quantum efficiency (EQEmax) of 11.5 % with an emission peak at 456 nm and excellent colour purity (full width at half maximum=56 nm and CIEy=0.09). These efficiencies represent the state-of-the-art device performance among the solution-processable blue OLEDs based on the "hot exciton" mechanism. This simple strategy opens up a new avenue for designing highly efficient solution-processable deep-blue organic luminescent materials.

Achieving Record External Quantum Efficiency of 11.5 % in Solution‐Processable Deep‐Blue Organic Light‐Emitting Diodes Utilizing Hot Exciton Mechanism

AbstractHigh performance solution‐processable deep‐blue emitters with a Commission International de l′Eclairage (CIE) coordinate of CIEy≤0.08 are highly desired in ultrahigh‐definition display. Although, deep‐blue materials with hybridized local and charge‐transfer (HLCT) excited‐state feature are promising candidates, their rigidity and planar molecular structures limit their application in solution‐processing technique. Herein, four novel deep‐blue solution‐processable HLCT emitters were first proposed by attaching rigid imide aliphatic rings as functional units onto the HLCT emitting core. The functional units not only improve solubility, enhance thermal properties and morphological stability of the emitting core, but also promote photoluminescence efficiency, balance charge carrier transport, and inhibit aggregation‐caused quenching effect due to the weak electron‐withdrawing property as well as steric hindrance. The corresponding solution‐processable organic light‐emitting diodes (OLEDs) substantiate an unprecedented maximum external quantum efficiency (EQEmax) of 11.5 % with an emission peak at 456 nm and excellent colour purity (full width at half maximum=56 nm and CIEy=0.09). These efficiencies represent the state‐of‐the‐art device performance among the solution‐processable blue OLEDs based on the “hot exciton” mechanism. This simple strategy opens up a new avenue for designing highly efficient solution‐processable deep‐blue organic luminescent materials.

Investigations of structural, photoluminescence, colorimetric, lifetime, and luminous efficiency of Tb3+ and Sm3+ co-doped calcium tungstate for WLEDs

Structure, photoluminescence, colorimetric, and thermoluminescence analysis of Ca1-x-yTb2x/3Sm2y/3WO4; x = 0.01; y = 0.01–0.05 ceramics are reported in this manuscript. The materials are made by the use of the solid-state method. Reitveld refinements of the obtained X-ray diffraction patterns are done by using the Fullprof Suite software. The obtained results denoted that the synthesized materials have a tetragonal structure and I41/a space group. Energy bandgaps are found in the UV–visible absorbance spectra. Photoluminescence investigations of the phosphors are done. The critical quenching concentrations of the phosphor are found to be x = 0.01; and y = 0.04. Moreover, the critical distance of energy shift with the adjacently presented ions is computed. Dexter’s theory is employed to elucidate that the dipole-dipole electronic interactions are the imperative reasons for the transfer of energy in the phosphor. The white color of emission is achieved for x = 0.01, y = 0.04 Tb, and Sm doped CaWO4 material. Moreover, great values in color purity, correlated color temperature, color rendering index as well as luminous efficiency of radiation are obtained from the CIE Chromaticity coordinates. Quantum yield efficiency of x = 0.01, y = 0.04 Tb & Sm codoped CaWO4 is measured. Photoluminescence decay analysis of all the samples is done to study the long-after glow properties and also the average lifetime values are evaluated. This is an indication of the suitable usage of the prepared materials in the white light-emitting diodes. Concentration as well as dose-dependent Thermoluminescence spectroscopy is investigated thoroughly. Kinetic parameters are calculated by deconvoluting the spectra of x = 0.01; y = 0.01 Tb & Sm codoped CaWO4 irradiated with 15 min of UV excitation dose. These results are denoted by high trap depth, second-order kinetics, and low UV dosimetry of the phosphor.

Identification and Dynamics of Microsecond Long-Lived Charge Carriers for CsPbBr3 Perovskite Quantum Dots, Featuring Ambient Long-Term Stability.

We analyze the stability and photophysical dynamics of CsPbBr3 perovskite quantum dots (PeQDs), fabricated under mild synthetic conditions and embedded in an amorphous silica (SiOx) matrix (CsPbBr3@SiOx), underscoring their sustained performance in ambient conditions for over 300 days with minimal optical degradation. However, this stability comes at the cost of a reduced photoluminescence efficiency. Time-resolved spectroscopic analyses, including flash-photolysis time-resolved microwave conductivity and time-resolved photoluminescence, show that excitons in CsPbBr3@SiOx films decay within 2.5 ns, while charge carriers recombine over approximately 230 ns. This longevity of the charge carriers is due to photoinduced electron transfer to the SiOx matrix, enabling hole retention. The measured hole mobility in these PeQDs is 0.880 cm2 V-1 s-1, underscoring their potential in optoelectronic applications. This study highlights the role of the silica matrix in enhancing the durability of PeQDs in humid environments and modifying exciton dynamics and photoluminescence, providing valuable insights for developing robust optoelectronic materials.

High-Resolution X-ray Image from Copper-Based Perovskite Hybrid Polymer.

Cs3Cu2I5 nanocrystals (NCs) are considered to be promising materials due to their high photoluminescence efficiency, lack of lead toxicity, and X-ray responsiveness. However, during the crystallization process, NCs are prone to agglomeration and exhibit uneven size distribution, resulting in several light scattering that severely affect their imaging resolution. Herein, we successfully developed a high-resolution scintillator film by growing copper-based perovskite NCs within a hybrid polymer matrix. By leveraging the ingenious integration of polyvinylidene fluoride (PVDF) and polymethyl methacrylate (PMMA), the size and distribution uniformity of Cs3Cu2I5 NCs can be effectively controlled. Consequently, a high spatial resolution of 14.3 lp mm-1 and a low detection limit of 105 nGy s-1 are achieved, and the scintillator film has excellent flexibility and stability. These results highlight the promising application of Cs3Cu2I5 scintillator films in low-cost, flexible, and high-performance medical imaging.

Embedding Te4+ into Sn4+-Based Metal Halide To Passivate Structure Defects for High-Performance Light-Emitting Application.

Low-dimensional lead-halide hybrids are an emerging class of optical functional material but suffer the problems of toxicity and poor air stability. Among lead-free metal halides, tin(IV)-based metal halides are promising optoelectronic materials due to their robust structure and environmental friendliness. However, their photoluminescence (PL) properties are poor, and the underlying mechanisms are still elusive. Herein, a stable Sn4+-based halide hybrid, (C4H7N2)2SnCl6, was developed, which however exhibits poor PL properties at room temperature (RT) due to the lattice defects and the robust crystal structure. To enhance its PL efficiency, the Te4+ ion with a stereoactive 5s2 lone pair has been introduced into the lattice. As a result, Te4+-doped (C4H7N2)2SnCl6 displays broadband orange emission (∼640 nm) with a PL efficiency of ∼46% at RT. Interestingly, Te4+-doped (C4H7N2)2SnCl6 shows triple emission bands at 80 K, which could be due to the synergistic effect of the organic cations and the self-trapped state induced by Te4+. Additionally, high-performance white light-emitting diodes were prepared using Te4+-doped (C4H7N2)2SnCl6, revealing the potential of this material for lighting applications. This study provides new insight into the PL mechanism of Sn4+-based metal-halide hybrids and thus facilitates the design and development of eco-friendly light-emitting metal halides.

Role of surface treatments and localized surface plasmon nanoparticles on internal quantum efficiency of 800 nm diameter blue GaN/InGaN nano light emitting diodes

Arrays of nanorod multi-quantum-well (MQW) blue light emitting diodes (nLEDs) with diameter 800 nm were prepared by reactive ion etching (RIE) with subsequent surface treatment by KOH etching alone, and KOH etching followed by SiO2 passivation with the SiO2 prepared by the sol-gel technique. In addition, the effects of Ag/SiO2 core/shell nanoparticles prepared by sol-gel were studied for all surface treatments. For as etched nLEDs, the Internal Quantum Efficiency (IQE) of photoluminescence was low, 5.5 %, because of the impact of surface damage introduced by RIE. KOH etching and KOH plus SiO2 passivation produced an increase of IQE to respectively 5.7 and 6.8 %. When the Ag/SiO2 core/shell nanoparticles known to produce localized surface plasmon resonance at the wavelength well-matched to the light emission from the MQWs were added to the polymer filling the gaps between the MQW nanorods, the result was found to depend on finding a proper balance between the enhancement due to the interaction Ag/SiO2 nanoparticles adjacent to the MQW nanorods and the absorption by “idle” Ag/SiO2 particles in the bulk of the polymer. When optimal concentrations of LSP NPs giving rise to maximal enhancement of the MQW PL intensity were used, a considerable improvement of performance was obtained, with IQE of 10.6 %.

Deterministic Areal Enhancement of Interlayer Exciton Emission by a Plasmonic Lattice on Mirror.

The emergence of interlayer excitons (IX) in atomically thin heterostructures of transition metal dichalcogenides (TMDCs) has drawn great attention due to their unique and exotic optical and optoelectronic properties. Because of the spatially indirect nature of IX, its oscillator strength is 2 orders of magnitude smaller than that of the intralayer excitons, resulting in a relatively low photoluminescence (PL) efficiency. Here, we achieve the PL enhancement of IX by more than 2 orders of magnitude across the entire heterostructure area with a plasmonic lattice on mirror (PLoM) structure. The significant PL enhancement mainly arises from resonant coupling between the amplified electric field strength within the PLoM gap and the out-of-plane dipole moment of IX excitons, increasing the emission efficiency by a factor of around 47.5 through the Purcell effect. This mechanism is further verified by detuning the PLoM resonance frequency with respect to the IX emission energy, which is consistent with our theoretical model. Moreover, our simulation results reveal that the PLoM structure greatly alters the far-field radiation of the IX excitons preferentially to the surface normal direction, which increases the collection efficiency by a factor of around 10. Our work provides a reliable and universal method to enhance and manipulate the emission properties of the out-of-plane excitons in a deterministic way and holds great promise for boosting the development of photoelectronic devices based on the IX excitons.

Effect of DC poling on transparency and photoluminescence in Pr:PMN-PT transparent ceramics

Electric poling could significantly influence the transparency and the photoluminescence (PL) intensities in transparent ferroelectric PL ceramics. This work applied direct current (DC) poling on a highly transparent 0.75PMN-0.25PT:0.015Pr3+ ceramic, observed the domain configurations in a direction perpendicular to poling direction. Lamellar domains perpendicular to electric field were observed after poling and decreased the transmittance by changing the propagation path of incident light. Besides, the enhancement of PL intensities by poling was found as high as 62 %, mainly due to the following reasons: the change of light propagation path by the lamellar domains is supposed to increase the absorption of exciting light; and the reduced crystal symmetry may increase the PL efficiency. This work revealed the effects of DC poling on transparency and PL properties in transparent ferroelectric PL ceramics.

Eu2+ doped cesium alkaline earth chloride nanocrystals in glass for X-ray imaging

High-performance and low-cost metal halide perovskite scintillator materials have important applications in X-ray detection and imaging. However, large-sized perovskite scintillator panel with high transmittance, low toxicity and long-term stability is still lacking. Herein, Eu2+ doped cesium alkaline earth chloride nanocrystals (Eu2+: CsCaCl3, Eu2+: CsSrCl3, and Eu2+: Cs2BaCl4 NCs) embedded in glasses through conventional melt-quenching and subsequent heat-treatment were developed. These NCs doped glasses exhibited highly efficient and narrowband photoluminescence in blue region. Benefitting from the large X-ray absorption coefficient and high photoluminescence quantum yied, these Eu2+: CsCaCl3 NCs doped glass scintillator shows light yield of ∼9300 photons/MeV, detection limit of ∼213.8 μGy/s, and spatial resolution of 30.0 lp/mm. These results demonstrated that glasses containing Eu2+ doped cesium alkaline earth chloride nanocrystals are promising for X-ray detection and imaging.

Photoluminescence Emission Efficiency Analysis Methodology by Integrating Raman Spectroscopy of the A1(LO) and E2(high) Phonons in a GaInN/GaN Heterostructure

Microscopic lattice vibration images of the E2(high) mode (E2H) and another mode of A1(LO) (A1L) or the higher energy branch of LO‐phonon−plasmon coupling mode (LOPC+) in a Ga0.95In0.05N film on a GaN template are obtained by Raman scattering spectroscopy using a 325 nm laser. The increase in temperature by increasing the laser power is obtained from the decrease in the energy of E2H and the theoretical formula comprising two terms based on the mode energy variation of the bulk material and the thermal strain effect. Using the obtained temperature and the energy shift of the LOPC+, the mapping images of the temperature and electron density in the x–y plane are simultaneously obtained. This image provides the spatial variation of photoluminescence (PL) emission efficiency, given as PL intensity per electron. This method enables the quantitative discussion on photo‐emission efficiency even in the regions of low or high carrier density affected by carrier transport. In the investigated area, a region with a lower PL efficiency is found despite a higher electron density and lower temperature increase than the surrounding region. This imaging analysis is feasible in integrating the carrier and thermal energy transports and recombination processes in carrier dynamics study.

Constructing ZnTe Spherical Quantum Well for Efficient Light Emission.

ZnTe colloidal semiconductor nanocrystals (NCs) have shown promise for light-emitting diodes (LEDs) and displays, because they are free from toxic heavy metals (Cd). However, so far, their low photoluminescence (PL) efficiency (∼30%) has hindered their applications. Herein, we devised a novel structure of ZnTe NCs with the configuration of ZnSe (core)/ZnTe (spherical quantum well, SQW)/ZnSe (shell). The inner layer ZnTe was grown at the surface of ZnSe core with avoiding using highly active and high-risk Zn sources. Due to the formation of coherently strained heterostructure which reduced the lattice mismatch, and the thermodynamic growth of ZnTe, the surface or interface defects were suppressed. A high PL efficiency of >60% was obtained for the green light-emitting ZnSe/ZnTe/ZnSe SQWs after ZnS outer layer passivation, which is the highest value for colloidal ZnTe-based NCs. This work paves the way for the development of novel semiconductor NCs for luminescent and display applications.

Effects of high-temperature annealing on vacancy complexes and luminescence properties in multilayer periodic structures with elastically strained GeSiSn layers

Effects of postgrowth high-temperature annealing on vacancy complexes and photoluminescence (PL) from GeSiSn/Si multiple quantum wells (MQWs) are studied. The series of PL peaks related to the vacancy-tin complexes was observed for as-grown samples including different structures, such as GeSiSn/Si MQWs, multilayer periodic structure with GeSiSn quantum dots (QDs), GeSn cross-structures upon GeSiSn/Si MQWs, and thick GeSiSn layers. The PL band intensity is significantly reduced after annealing at 700 °C corresponding to the reduction in vacancy density, as demonstrated by the positron annihilation spectroscopy (PAS) data. Such annealing also results in the appearance of the PL signal related to the interband optical transitions in GeSiSn/Si MQWs. However, the high temperature could negatively impact the sharpness of heterointerfaces due to Sn diffusion, thus limiting the PL efficiency. To improve the luminescence properties of GeSiSn/Si structures, we proposed a two-stage technique combining both the annealing and subsequent treatment of samples in a hydrogen plasma at 200 °C. The plasma treatment significantly reduces the PL band of vacancy-related defects, whereas annealing at a moderate temperature of ∼600 °C prevents the blurring of heterointerfaces. As a result, we demonstrate an increase in the relative efficiency of interband PL of type II GeSiSn/Si MQW structures emitting in the range of 1.5–2 μm.