Radiative Recombination Research Articles

Recombination efficiency in c-plane (In,Ga)N/GaN quantum wells: Saturation of localisation sites versus Auger-Meitner recombination

Abstract Light emitting diodes based on c-plane (In,Ga)N/GaN quantum wells can have >90% emission efficiency at modest current densities but this drops significantly at higher excitation, an effect known as efficiency droop that limits device efficacy at high brightness. Several explanations for this have been proposed including the saturation of carrier localisation sites at high excitation densities, resulting in a greater exposure of carriers to defects and hence a significant increase in the associated non-radiative recombination processes. Here, power- and temperature-dependent photoluminescence spectroscopy of c-plane (In,Ga)N/GaN quantum wells is used to investigate the relationship between the saturation of localised states and emission efficiency. For the samples studied, we find that the saturation of localised sites broadly coincides with the onset of efficiency droop. However, it is also found that as the localised states saturate with increasing excitation, the relative contribution of defect-associated non-radiative processes to overall recombination decreases rather than increases. Based on these observations and on modelling of recombination processes in the quantum well, it is concluded that the saturation of localised states does not significantly contribute to the reduction in emission efficiency at high excitation. Our studies rather suggest that defect-related non-radiative recombination is out-competed by radiative and Auger-Meitner recombination at the carrier densities required for saturation.

Abnormal Temperature Dependence of Huang-Rhys Factor and Exciton Recombination Kinetics in CsPbBr3 Perovskite Quantum Dots.

Anomalous thermal behaviors of excitonic luminescence in CsPbBr3 perovskite quantum dots (PQDs) were observed. It is found that the main luminescence peak originated from the excitonic radiative recombination assisted by the longitudinal-optical (LO) phonon, and its integrated intensity first declines as the temperature varies from 10 to 150 K and then turns to increase at ∼160 K, reaching a maximum value at 300 K. A model considering the thermal detrapping and transfer of electrons from a trap level is developed to interpret these abnormal thermal behaviors of the luminescence from the PQDs. On the other hand, the quantum-mechanical multimode Brownian oscillator model was employed to unravel that the Huang-Rhys factor exclusively characterizing the exciton-phonon coupling in the studied CsPbBr3 PQDs decreases from 1.65 at 10 K to 1.31 at 200 K.

Dual-emissive carbon dots with high-color purity from sweet basil leaves: synthesis, characterization and optical properties

Abstract In this study, we synthesized dual-emission carbon dots (CDs) from sweet basil leaves dissolved in hexane using the hydrothermal method. Extensive analyses were carried out on their morphology, structure, and optical properties. The CDs show a spherical shape and highly disordered structure with an average diameter of 2 nm. They predominantly comprise carbon surrounded by a dense shell layer of oxygen and nitrogen-related functional groups. Under excitation at a single wavelength of 380 nm, the CDs emit two distinct peaks at 450 and 675 nm demonstrating a narrow bandwidth emission with full width at half maximum (FWHM) of 72 and 27 nm, respectively. The emission characteristics of the CDs are ascribed to the combined effects of radiative recombination of the carbon-core and fully passivated surface states, resulting in two distinct emission peaks and excitation-independent emission property. We present a highly effective and eco-friendly approach approach to fabricate luminescent CDs exhibiting dual emission properties derived from sustainable resources, holding promise for utilization in bioimaging.

Quantum-optical radiative recombination between electrons and ions analyzed with a semiclassical picture

Quantum-optical radiative recombination between electrons and ions analyzed with a semiclassical picture

Structural and electrical characterization of nickel sulfide nanoparticles

Nickel sulfide nanoparticles were successfully synthesized through a meticulous process involving a well-mixed powder of Ni(CH3COO)2∙2H2O and Thiourea. The X-ray diffraction analysis provided insights into the structural nature of NiS, revealing its polycrystalline characteristics with a hexagonal system. This information is fundamental, as it forms the basis for understanding the material’s behavior and functionality in various applications. Determining the average values of mean crystallite size, microstrain, and dislocation Nickel sulfide nanoparticles were successfully synthesized through a careful process involving a well-mixed powder of Ni(II)2∙2H2O and Thiourea. The X-ray diffraction analysis provided insights into the structural nature of NiS, revealing its polycrystalline characteristics with a hexagonal system. This information is crucial as it forms the basis for understanding the material’s behavior and functionality in various applications. Determining the average values of mean crystallite size, microstrain, and dislocation density for the (100) plane (32.62 nm, 0.000296, and 0.000939 nm-2, respectively) contributes to a comprehensive understanding of the material’s structural features. The photoluminescence spectrum of NiS in the visible region revealed split peaks at 405.8 and 428.25 nm, shedding light on the radiative recombination process between electrons and holes. The confirmation of thermal stability through a thermogravimetry diagram is essential for applications in elevated temperature environments, ensuring the material’s reliability under varying conditions. Analyzing the stoichiometry of NiS using energy dispersive spectroscopy attached to transmission electron microscopy provides insights into the material’s composition. Cyclic voltammetry results indicating a diffusion coefficient greater than that of NiS added to carbon hold significance for electrochemical applications. The unique characteristic peaks observed in cyclic voltammetry for fuel cell applications suggest the potential use of NiS in energy conversion technologies, broadening its scope of application. The confirmation of NiS’s ability to elucidate the physical and electronic properties of electrochemical systems through electrochemical impedance spectroscopy underlines its importance as a versatile material in various research and practical domains.

Laser-assisted radiative recombination beyond the dipole approximation

Laser-assisted radiative recombination beyond the dipole approximation

Mechanism of frequency-dependent gate breakdown in p-GaN/AlGaN/GaN HEMTs

In this Letter, time-dependent gate breakdown (TDB) characteristics under dynamic switching conditions were investigated in p-GaN/AlGaN/GaN high-electron-mobility transistors (HEMTs) with either Schottky-type or Ohmic-type gates. The dynamic TDB of the Schottky-type devices increased with frequencies ranging from 100 Hz to 100 kHz, while that of the Ohmic-type devices remained frequency-independent. This was analyzed by the frequency-dependent electroluminescence (EL) characteristics on both types of devices with semi-transparent gate electrodes. The electroluminescence (EL) emission intensity of Schottky-type devices increased with elevated frequencies, notably for blue and ultraviolet emissions, which exhibited a pronounced positive correlation with frequency. In contrast, the EL emissions of Ohmic-type devices were frequency-independent. Energy band diagrams were drawn to explain the different TDB and EL behaviors between two types of devices. The frequency-enhanced EL emissions of the Schottky-type devices indicated the frequency-enhanced hole injection and radiative recombination, which then suppressed the hot-electron effects on the metal/p-GaN junction and enhanced the dynamic TDB in p-GaN/AlGaN/GaN HEMTs.

Highly Diffusive Nonluminescent Carriers in Hybrid Phase Lead Triiodide Perovskite Nanowires.

Crystal structural rearrangements unavoidably introduce defects into materials, where even these small changes in local lattice structure could arouse a prominent impact on the overall nature of crystals. Contrary to the traditional notion that defects obstruct carrier transport, herein, we report a promoted transport mechanism of nonluminescent carriers in single-crystalline CH3NH3PbI3 nanowires (1345.2 cm2 V-1 s-1, about a 14-fold improvement), enabled by the phase transition induced defects (PTIDs). Carriers captured by PTIDs evade both the radiative and non-radiative recombinations during the incomplete tetragonal-to-orthorhombic phase transition at low temperatures, forming a specific nonluminescent state that exhibits an efficient long-distance transport and thereby realize a prominent enhancement of photocurrent responsivity for photodetector applications. The findings provide broader insights into the carrier transport mechanism in perovskite semiconductors and have significant implications for their rational design for photoelectronic applications at varied operating temperatures.

Realizing Near-Unity Photoluminescence Efficiency in Antimony-Doped Indium-Based Halides Induced by Strong Electron-Phonon Coupling.

Exploring a zero-dimensional (0D) hybrid halide with a large Stokes shift and efficient broad-band emission is highly desirable due to its enormous potential for solid-state lighting (SSL) application. However, it is still challenging to develop a highly emissive 0D hybrid halide with low toxicity and remarkable stability. Herein, we developed a novel indium-based metal halide A5In2Cl16·4H2O (A = doubly protonated 1,4-diaminobutane) whose inorganic octahedrons are completely isolated by the organic cations to form the 0D structure. Experimental and theoretical studies confirmed that Sb-doped A5In2Cl16·4H2O exhibits broad yellow emission with a photoluminescence quantum yield (PLQY) of up to 98%. The intense yellow emission can be attributed to the radiative recombination of triplet self-trapped excitons (STEs) in [SbCl6]3- octahedrons caused by the strong electron-phonon coupling. Benefiting from the excellent stability and photoluminescence performance, A5In2Cl16·4H2O:15%Sb was used as the yellow phosphor to prepare a white-light-emitting diode (WLED) device with a color rendering index of 87.8 and a luminous efficiency of up to 36.18 lm/W, demonstrating its potential in SSL applications. This work provides a guidance for developing environmentally friendly, efficient, and stable ultraviolet (UV)-excited broad-band emission materials.

A 326 nm pure ultraviolet light sources achieved in a Ga[formula omitted]O[formula omitted] microwire heterojunction through interface optimization and surface-modification

Low-dimensional Ga2O3 single-crystals have caused widespread attentions in the potential of developing ultraviolet light sources due to its ultrabroad bandgap, low-budget, high thermally stable, high breakdown voltage and others. Herein, we exhibit a significant route to construct one-dimensional Ga2O3 microwire heterojunction deep-ultraviolet light-emitting diode (LED). The resulting electroluminescence is positioned at 326 nm with a narrow linewidth of about 22.5 nm, which is the shortest wavelengths once published for the Ga2O3-related light sources. In the well-fabricated LED, an intermediate AlN layer enables appropriately to manipulate band alignment of n-Ga2O3/p-GaN heterojunction, thus achieving efficient confinement of electron–holes spreading and radiative recombination within the Ga2O3 microwire active medium. Benefited from surface-modified Pt nanoparticles, the LED’s electroluminescence efficiency and brightness can be plasmonically boosted. More importantly, the peak energy at 3.8 eV obtained under forward bias, which is smaller than the Ga2O3 bandgap, could be resulted from radiative recombination of weakly-bounded electron–holes inside the Ga2O3 microwires. Therefore, the Ga2O3 monocrystalline wires synthesized using high-temperature carbothermal reduction, are expected as promising-looking candidates to develop environmentally friendly, easy miniaturization, highly-stable deep-ultraviolet light sources and photonic devices.

Visible-Light Photodetection by Zero-Dimensional Hybrid Indium-Halide with Minimal Structural Distortion and Reduced Band Gap.

Perovskite-inspired zero-dimensional (0D) hybrid halides exhibit impressive light emission properties; however, their potential in photovoltaics is hindered by the absence of interconnection between the inorganic polyhedra, leading to acute radiative recombination and insufficient charge separation. We demonstrate that incorporating closely-spaced dissimilar polyhedral units with minimal structural distortion leads to a remarkable enhancement in visible-light photodetection capability. We designed 0D C24H72N8In2Br14 (HIB) with a tetragonal crystal system, replacing the Cs+ of Cs2InBr5.H2O (CIB) with 1,6-hexanediammonium (HDA) cation. HIB comprises [InBr6]3- octahedra, and [InBr4]- tetrahedra units spaced 3.9 Å apart by the HDA linker. The [InBr4]- unit is additionally linked to HDA via intercalated bromine through hydrogen and halogen bonding interactions, respectively. This structural arrangement lowers the dielectric confinement, thereby enhancing carrier density and mobility, and increasing the diffusion coefficient compared to CIB. With 3.6 % bromine vacancy within the [InBr4]- block, mid-gap states are created, reducing the direct band gap to 2.19 eV. HIB demonstrates an unprecedently high responsivity of 9975.9±201.6 mA W-1 under 3 V potential bias at 485 nm wavelength, among low-dimensional hybrid halides. In the absence of potential bias, the self-powered photodetection parameters are 81.2±3.0 mA W-1 and (6.98±0.21)×109 Jones.

Visible‐Light Photodetection by Zero‐Dimensional Hybrid Indium‐Halide with Minimal Structural Distortion and Reduced Band Gap

AbstractPerovskite‐inspired zero‐dimensional (0D) hybrid halides exhibit impressive light emission properties; however, their potential in photovoltaics is hindered by the absence of interconnection between the inorganic polyhedra, leading to acute radiative recombination and insufficient charge separation. We demonstrate that incorporating closely‐spaced dissimilar polyhedral units with minimal structural distortion leads to a remarkable enhancement in visible‐light photodetection capability. We designed 0D C24H72N8In2Br14 (HIB) with a tetragonal crystal system, replacing the Cs+ of Cs2InBr5.H2O (CIB) with 1,6‐hexanediammonium (HDA) cation. HIB comprises [InBr6]3− octahedra, and [InBr4]− tetrahedra units spaced 3.9 Å apart by the HDA linker. The [InBr4]− unit is additionally linked to HDA via intercalated bromine through hydrogen and halogen bonding interactions, respectively. This structural arrangement lowers the dielectric confinement, thereby enhancing carrier density and mobility, and increasing the diffusion coefficient compared to CIB. With 3.6 % bromine vacancy within the [InBr4]− block, mid‐gap states are created, reducing the direct band gap to 2.19 eV. HIB demonstrates an unprecedently high responsivity of 9975.9±201.6 mA W−1 under 3 V potential bias at 485 nm wavelength, among low‐dimensional hybrid halides. In the absence of potential bias, the self‐powered photodetection parameters are 81.2±3.0 mA W−1 and (6.98±0.21)×109 Jones.

High-Voltage Stable Perovskite Light-Emitting Diodes Enabled by an Optoelectric-Tunable Sandwiched Nanostructure.

While metal halide light-emitting diodes (PeLEDs) with unique optoelectronic properties are promising emitters for next-generation displays, their performance degrades rapidly due to severe ion migration during continuous operation, especially at high voltages. Here, we realize highly stable PeLEDs by designing inorganic dielectric/perovskite semiconductor emitter/organic dielectric sandwiched nanostructures to mitigate ion migration via regulating the electric field distribution. The bilateral cesium carbonate (Cs2CO3) and tetraoctylammonium bromide (TOAB) thin interlayers can not only largely reduce the voltage imposed on the perovskite layer by serving as series resistors and, thus, mitigate the ion migration but also regulate the charge carrier transfer to improve the radiative recombination efficiency. In addition, the underneath inorganic Cs2CO3 film also provides more heterogeneous nucleation sites for growing high-crystallinity perovskite crystals, while the atop TOAB with bifunctional groups (organic amino and Br- ions) refines the morphology and enhances the optical properties of the perovskite film. As a result, efficient and stable green PeLEDs based on such an optoelectric-tunable nanostructure exhibit extremely slow efficiency decay as the applied voltage increases, and the external quantum efficiencies were maintained over 10% at a high bias up to 20 V.

Intense violet electroluminescence of thin SiO2 layers with SnO2 nanocrystals

It has been shown that Sn implantation with subsequent annealing in air leads to an increase in the electroluminescence (EL) intensity of SiO2/Si structure by two orders of magnitude. Intense violet EL with a maximum at 3.21 eV was observed at room temperature by the naked eye at forward bias. The observed emission was attributed to radiative recombination in SnO2 nanocrystals synthesized in SiO2 layers. The external quantum efficiency (EQE) increased with decreasing Sn concentration The maximum external quantum efficiency was found to be 0.7 % for the silica film Sn-implanted at the lowest fluence of 2.5 × 1016cm−2. The non-radiative charge transport (shunt current) through the sample and mechanism of EL excitation are discussed. It has been concluded that the Poole–Frenkel mechanism, or tunneling between traps are the most likely mechanisms of charge transport to light-emitting centers.

Coherence Programming for Efficient Linearly Polarized Perovskite Light-Emitting Diodes.

Although quasi-two-dimensional (quasi-2D) perovskites are ideal material platforms for highly efficient linearly polarized electroluminescence owing to their anisotropic crystal structures, so far, there has been no practical implementation of these materials for the demonstration of linearly polarized perovskite light-emitting diodes (LP-PeLEDs). This scarcity is due to difficulty in orientation and phase distribution control of the quasi-2D perovskites while minimizing the defects, all of which are required to manifest aligned transition dipole moments (TDMs). To achieve this multifaceted goal, herein, we introduce a synergistic strategy to quasi-2D perovskites by incorporating both a trimethylolpropane triacrylate anchoring layer and 18-Crown-6 molecular passivator into the film fabrication process. It is found that the interfacial anchoring layer guides the oriented growth of perovskites along the (110) plane, whereas the molecular passivator reduces the number of defects and homogenizes the crystal phase. As a result, a quasi-2D perovskite film with macroscopically aligned TDM that renders high radiative recombination and the degree of linear polarization (DoLP) is constructed. This "coherence-programmed emission layer" demonstrates highly efficient LP-PeLEDs, not only achieving a maximum external quantum efficiency of ∼23.7%, a brightness of ∼36,142 cd/m2, and a DoLP of ∼38%, but also significantly improving the signal-to-interference-and-noise ratio in a multi-cell visible light communication system.

A Novel Upside-Down Thermal Annealing Method Toward High-Quality Active Layers Enables Organic Solar Cells with Efficiency Approaching 20.

The emerging non-fullerene acceptors with low voltage losses have pushed the power conversion efficiency of organic solar cells (OSCs) to ≈20% with auxiliary morphology optimization. Thermal annealing (TA), as the most widely adopted post-treatment method, has been playing an essential role in realizing the potential of various material systems. However, the procedure of TA, i.e., the way that TA is performed, is almost identical among thousands of OSC papers since ≈30 years ago other than changes in temperature and annealing time. Herein, a reverse thermal annealing (RTA) technique is developed, which can enhance the dielectric constant of active layer film, thereby producing a smaller Coulomb capture radius (14.93 nm), meanwhile, forming a moderate nano-scale phase aggregation and a more favorable face-on molecular stacking orientation. Thus, this method can reduce the decline in open circuit voltage of the conventional TA method by achieving decreased radiative (0.334 eV) and non-radiative (0.215 eV) recombination loss. The power conversion efficiency of the RTA PM6:L8-BO-X device increases to 19.91% (certified 19.42%) compared to the TA device (18.98%). It is shown that this method exhibits a superb universality in 4 other material systems, revealing its dramatic potential to be employed in a wide range of OSCs.

White Light Emission in Zero-Dimensional Indium Hybrid with Hydrogen Bond.

Low-dimensional organic-inorganic metal halides (OIMHs) have been explored as single-component white light emitters for applications in solid-state lighting. Herein, we report a zero-dimensional (0D) In-based OIMH (TMPDA)[InCl5(H2O)] (TMPDA = N,N,N',N'-tetramethyl-1,4-phenylenediamine), which crystallizes in the noncentrosymmetric P212121 space group and contains hydrogen bonds between the adjacent [InCl5(H2O)]2- octahedra in structure. It exhibits a large optical band gap (4.10 eV) and dual-band emission under UV light. Spectroscopic analysis and theoretical calculation indicate that the high (404 nm)- and low (513 nm)-energy emissions are attributed to the bound excitons in organic ligands and self-trapped excitons in [InCl5(H2O)]2- units, respectively. It is found that Sb doping in this 0D hybrid provides additional orange (590 nm) emission assigned to the 3P1 → 1S0 triplet radiative recombination. By adjusting the doping level, the emission color can be turned from turquoise to orange, and interestingly, a single-component white-light emission is realized by balancing the high-energy emission from organic ligand, the turquoise emission from [InCl5(H2O)]2-, and the orange one from [SbCl5(H2O)]2-. This work not only provides a new OIMH showing the single-component white light emission but also demonstrates the potential of In-based hybrids with hydrogen bonds for solid-state luminescence.

Suppression of the hole trap for high-quality amino-phosphine based InP quantum dots

InP quantum dots (QDs) have emerged as promising nanomaterials in various fields due to their exceptional optical properties. However, its wide emission linewidth limits further application. In this study, we synthesized high-quality InP/ZnSe/ZnS QDs by suppressing hole defects. The unreacted In precursors during nucleation easily enter ZnSe in the subsequent shelling process, forming a hole trapping center that adversely affects the photo-excitons radiative recombination. Our results demonstrate that the presence of In ions in ZnSe shell enhances exciton-phonon coupling, broadens the fluorescence emission spectrum, and weakens exciton binding energy. The optimized InP QDs exhibit a line width of 44 nm and 90% PLQY at 630 nm. Furthermore, our investigation into the interaction between shell hole defects and core exciton function provides valuable insights for designing and preparing another high-performance core-shell heterojunction QDs.

Nanoheteroepitaxy of Ge and SiGe on Si: role of composition and capping on quantum dot photoluminescence.

We investigate the nanoheteroepitaxy of SiGe and Ge quantum dots (QDs) grown on nanotips substrates realized in Si(001) wafers. Due to the lattice strain compliance, enabled by the nanometric size of the tip and the limited dot/substrate interface area, which helps to reduce dot/substrate interdiffusion, the strain and SiGe composition in the QDs could be decoupled. This demonstrates a key advantage of the nanoheteroepitaxy over the Stranski-Krastanow growth mechanism. Nearly semi-spherical, defect-free, ∼100 nm wide SiGe QDs with different Ge contents were successfully grown on the nanotips with high selectivity and size uniformity. On the dots, thin dielectric capping layers were deposited, improving the optical properties by the passivation of surface states. Intense photoluminescence was measured from all samples investigated with emission energy, intensity, and spectral linewidth dependent on the SiGe composition of the QDs and the different capping layers. Radiative recombination occurs in the QDs, and its energy matches the results of band-structure calculations that consider strain compliance between the QD and the tip. The nanotips arrangement and the selective growth of QDs allow to studying the PL emission from only 3-4 QDs, demonstrating a bright emission and the possibility of selective addressing. These findings will support the design of optoelectronic devices based on CMOS-compatible emitters.

Real-space perspective on dephasing in solid-state high harmonic generation

We develop and demonstrate a fully real-space perspective on high harmonic generation (HHG) in crystals. Due to the Wannier-Stark localization induced on subcycle timescales in the presence of a strong field, real-space descriptions are natural for strongly driven solids. Our approach allows us to address the origin of the extremely short dephasing times, which appear necessary for agreement between experimental HHG measurements and theoretical calculations generally performed in reciprocal space. We develop a physically transparent model of real-space dephasing which relates its rate to the distance between different sites in a laser-driven lattice. Our approach leads to well-structured high harmonic spectra at the microscopic level, reproduces the results of macroscopic propagation, and demonstrates that the requirement for ultrafast dephasing times stems from the need for suppressing recombination events with large electron-hole separations during radiative recombination. Published by the American Physical Society 2024