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This review describes the development history of group-III nitride light-emitting diodes (LEDs) for over 30 years, which has achieved brilliant achievements and changed people's lifestyles. The development process of group-III nitride LEDs is the sum of challenges and solutions constantly encountered with shrinking size. Therefore, this paper uses these challenges and solutions as clues for review. It begins with reviewing the development of group-III nitride materials and substrates. On this basis, some key technological breakthroughs in the development of group-III nitride LEDs are reviewed, mainly including substrate pretreatment and p-type doping in material growth, the proposal of new device structures such as nano-LED and quantum dot (QD) LED, and the improvement in luminous efficiency, from the initial challenge of high-efficiency blue luminescence to current challenge of high-efficiency ultraviolet (UV) and red luminescence. Then, the development of micro-LEDs based on group-III nitride LEDs is reviewed in detail. As a new type of display device, micro-LED has drawn a great deal of attention and has become a research hotspot in the current international display area. Finally, based on micro-LEDs, the development trend of nano-LEDs is proposed, which is greener and energy-saving and is expected to become a new star in the future display field.
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Realizing efficient and durable non-precious metal-based electrocatalysts for oxygen evolution reaction (OER) still remains a great challenge. Here, a multi-component composite of Co2P2O7-MoN/NC containing pyrophosphate, nitride, and nitrogen-doped carbon is successfully prepared via a facile two-step synthesis method. Combining the structural regulation between the active metal- and non-metal-based species, Co2P2O7-MoN/NC demonstrates superior activity and durability for OER, requiring an overpotential of 278 mV at a current density of 10 mA cm-2, a Tafel slope of 83.3 mV dec-1, and long-term stability over 100 h in an alkaline solution. Post-characterizations reveal that synergistic effect among stable Co2P2O7, partially dissolved MoN, N-doped carbon, and new-formed CoOOH nanosheets enable structural reconstruction, fast charge transfer, and formation of oxygen-containing intermediates, promoting the OER performance significantly. This work provides a promising pathway to tune multi-components to fabricate efficient transition-metal-based electrocatalysts in energy conversion applications.
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Computer atomistic simulations based on density functional theory were carried out to investigate strain induced phase transitions in aluminium nitride (AlN). The wurtzite to graphitic and graphitic to wurtzite transformations were investigated at the atomic level and their physical origins were identified. Both phase transitions were found to be of the first order. The wurtzite to graphitic phase transition takes place in the tensile regime at a strain value of +7%. The driving force for this transformation was identified to be an elastic instability induced by tensile strain. A hysteresis was demonstrated where the graphitic structure is separated from the wurtzite by a kinetic energy barrier. The origin of the observed hysteresis is due to the asymmetry of bond formation and bond breaking associated with the wurtzite to graphitic and graphitic to wurtzite transitions, respectively. A dynamic instability taking place at +3%, along the graphitic path, prevents the hysteresis to fully occur. The possible occurrence of the hysteresis has then to be taken into account when growing the graphitic phase by heteroepitaxy. Otherwise, maintaining the graphitic structure at low strain, through the hysteresis, offers new possibilities in the development of novel future applications.
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Hydrogen peroxide (H2O2) is a crucial chemical used in numerous industrial applications, yet its manufacturing relies on the energy-demanding anthraquinone process. Solar-driven synthesis of H2O2 is gaining traction as a promising research area, providing a sustainable method for its production. Herein, a controllable activation of n â π* electronic transition is presented to boost the photocatalytic H2O2 evolution in ionic carbon nitrides. This enhancement is achieved through the simultaneous introduction of structural distortions and defect sites (âC ≡ N groups and N vacancies) into the KPHI framework. The optimal catalyst (2%Ox-KPHI) reached an apparent quantum yield of 41% at 410 nm without the need for any cocatalysts, outperforming most previously reported carbon nitride-based photocatalysts. Extensive experimental characterizations and theoretical calculations confirm that a corrugated configuration and the presence of defects significantly broaden the light absorption profile, improve carrier separation and migration, promote O2 adsorption, and lower the energy barriers for H2O2 desorption. Transient absorption spectroscopy indicates that the enhanced photocatalytic performance of 2%Ox-KPHI is largely attributed to the preferential migration of electrons at defect sites over extended timescales, following the diffusion of geminate carriers across the PHI sheets.
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This study examines the exciton dynamics in InGaN/GaN core-shell nanorods using time-resolved cathodoluminescence (TRCL), which provides nanometer-scale lateral spatial and tens of picoseconds temporal resolutions. The focus is on thick (>20 nm) InGaN layers on the non-polar, semi-polar and polar InGaN facets, which are accessible for study due to the unique nanorod geometry. Spectrally integrated TRCL decay transients reveal distinct recombination behaviours across these facets, indicating varied exciton lifetimes. By extracting fast and slow lifetime components and observing their temperature trends along with those of the integrated and peak intensity, the differences in behaviour were linked to variations in point defect density and the degree and density of localisation centres in the different regions. Further analysis shows that the non-polar and polar regions demonstrate increasing lifetimes with decreasing emission energy, attributed to an increase in the depth of localisation. This investigation provides insights into the intricate exciton dynamics in InGaN/GaN nanorods, offering valuable information for the design and development of optoelectronic devices.
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The realization of semiconductor heterostructures marks a significant advancement beyond silicon technology, driving progress in high-performance optoelectronics and photonics, including high-brightness light emitters, optical communication, and quantum technologies. In less than a decade since 1997, nanowires research has expanded into new application-driven areas, highlighting a significant shift toward more challenging and exploratory research avenues. It is therefore essential to reflect on the past motivations for nanowires development, and explore the new opportunities it can enable. The advancement of heterogeneous integration using dissimilar substrates, materials, and nanowires-semiconductor/electrolyte operating platforms is ushering in new research frontiers, including the development of perovskite-embedded solar cells, photoelectrochemical (PEC) analog and digital photonic systems, such as PEC-based photodetectors and logic circuits, as well as quantum elements, such as single-photon emitters and detectors. This review offers rejuvenating perspectives on the progress of these group-III nitride nanowires, aiming to highlight the continuity of research toward high impact, use-inspired research directions in photonics and optoelectronics.
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Nitrides and oxynitrides isostructural to α-Si3N4 (M-α-SiAlON, M = Sr, Ca, Li) possess superb thermally stable photoluminescence (PL) properties, making them reliable phosphors for high-power solid-state lighting. However, the synthesis of phase-pure Sr-α-SiAlON still remains a great challenge and has only been reported for Sr below 1.35 at.% as the large size of Sr2+ ions tends to destabilize the α-SiAlON structure. Here, we succeeded to synthesize the single-phase powders of a unique 'Sr-rich' polytypoid α-SiAlON (Sr3Si24Al6N40:Eu2+) phosphor with three distinctive Sr/Eu luminescence sites using a solid-state remixing-reannealing process. The Sr content of this polytypoid structure exceeds those of a few previously reported structures by over 200%. The phase purity, composition, structure, and PL properties of this phosphor were investigated. A single phase can be obtained by firing the stoichiometric mixtures of all-nitride precursors at 2050°C under a 0.92 MPa N2 atmosphere. The Sr3Si24Al6N40:Eu2+ shows an intense orange-yellow emission, with the emission maximum of 590 nm and internal/external quantum efficiency of 66%/52% under 400 nm excitation. It also has a quite small thermal quenching, maintaining 93% emission intensity at 150°C. In comparison to Ca-α-SiAlON:Eu2+, this Sr counterpart shows superior quantum efficiency and thermal stability, enabling it to be an interesting orange-yellow down-conversion luminescent material for white LEDs. The experimental confirmation of the existence of such 'Sr-rich' SiAlON systems, in a single-phase powder form, paves the way for the design and synthesis of novel 'Sr-rich' SiAlON-based phosphor powders with unparalleled properties.
A distinctive orange-yellow-emitting 'Sr-rich' α-SiAlON-based phosphor with quite small thermal quenching (93% PL intensity at 150°C) that can surprisingly be synthesized in a single-phase powder form for white LEDs.
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This review paper focuses on group IVB transition metal nitrides (TMNs) such as titanium nitride (TiN), zirconium nitride (ZrN), and hafnium nitride (HfN) and as alternative plasmonic materials to noble metals like gold and silver. It delves into the fabrication methods of these TMNs, particularly emphasizing thin film fabrication techniques like magnetron sputtering and atomic layer deposition, as well as nanostructure fabrication processes applied to these thin films. Overcoming the current fabrication and application-related challenges requires a deep understanding of the material properties, deposition techniques, and application requirements. Here, we discuss the impact of fabrication parameters on the properties of resulting films, highlighting the importance of aligning fabrication methods with practical application requirements for optimal performance. Additionally, we summarize and tabulate the most recent plasmonic applications of these TMNs in fields like biosensing, photovoltaic energy, and photocatalysis, contributing significantly to the current literature by consolidating knowledge on TMNs.
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Developing long-lasting humidity sensors is essential for sustainable advancements in nanotechnology. Prolonged exposure to high humidity can cause sensors to drift from their calibration points, leading to long-term accuracy issues. Our research aims to develop a fabrication method that produces stable sensors capable of withstanding the environmental challenges faced by humidity sensors. Traditional iron-based nanoparticles often require complex treatments, such as chemical modification or thermal annealing, to maintain their properties. This study introduces a novel, one-step synthesis method for iron-based thin films with exceptional stability. The synthesized films were thoroughly characterized using X-ray photoelectron spectroscopy (XPS) to evaluate their phase stability and nitride formation. The method proposed in this study employs an electrical sparking discharge process within a pure nitrogen atmosphere under a 0.2 T magnetic field, producing thin films composed of nanoparticles approximately 20 nm in size. The resulting films demonstrate superior performance in humidity sensing applications compared to conventional methods. This straightforward and efficient approach offers a promising path toward robust and sustainable humidity sensors.
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Using the example of III-V nitrides crystallizing in a wurtzite structure (GaN, AlN, and InN), this review presents the special role of hydrostatic pressure in studying semiconductor properties. Starting with a brief description of high-pressure techniques for growing bulk crystals of nitride compounds, we focus on the use of hydrostatic pressure techniques in both experimental and theoretical investigations of the special properties of nitride compounds, their alloys, and quantum structures. The bandgap pressure coefficient is one of the most important parameters in semiconductor physics. Trends in its behavior in nitride structures, together with trends in pressure-induced phase transitions, are discussed in the context of the behavior of other typical semiconductors. Using InN as an example, the pressure-dependent effects typical of very narrow bandgap materials, such as conduction band filling or effective mass behavior, are described. Interesting aspects of bandgap bowing in In-containing nitride alloys, including pressure and clustering effects, are discussed. Hydrostatic pressure also plays an important role in the study of native defects and impurities, as illustrated by the example of nitride compounds and their quantum structures. Experiments and theoretical studies on this topic are reviewed. Special attention is given to hydrostatic pressure and strain effects in short periods of nitride superlattices. The explanation of the discrepancies between theory and experiment in optical emission and its pressure dependence from InN/GaN superlattices led to the well-documented conclusion that InN growth on the GaN substrate is not possible. The built-in electric field present in InGaN/GaN and AlGaN/GaN heterostructures crystallizing in a wurtzite lattice can reach several MV/cm, leading to drastic changes in the physical properties of these structures and related devices. It is shown how hydrostatic pressure modifies these effects and helps to understand their origin.
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Selective photocatalytic CO2 reduction to high-value hydrocarbons using graphitic carbon nitride (g-C3N4) polymer holds great practical significance. Herein, the cyano-functionalized g-C3N4 (CN-g-C3N4) with a high local electron density site is successfully constructed for selective CO2 photoreduction to CH4 and C2H4. Wherein the potent electron-withdrawing cyano group induces a giant internal electric field in CN-g-C3N4, significantly boosting the directional migration of photogenerated electrons and concentrating them nearby. Thereby, a high local electron density site around its cyano group is created. Moreover, this structure can also effectively promote the adsorption and activation of CO2 while firmly anchoring *CO intermediates, facilitating their subsequent hydrogenation and coupling reactions. Consequently, using H2O as a reducing agent, CN-g-C3N4 achieves efficient and selective photocatalytic CO2 reduction to CH4 and C2H4 activity, with maximum rates of 6.64 and 1.35 µmol g-1 h-1, respectively, 69.3 and 53.8 times higher than bulk g-C3N4 and g-C3N4 nanosheets. In short, this work illustrates the importance of constructing a reduction site with high local electron density for efficient and selective CO2 photoreduction to hydrocarbons.
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Bacterial infections claim millions of lives every year, with the escalating menace of microbial antibiotic resistance compounding this global crisis. Nanozymes, poised as prospective substitutes for antibiotics, present a significant frontier in antibacterial therapy, yet their precise enzymatic origins remain elusive. With the continuous development of nanozymes, the applications of elemental N-modulated nanozymes have spanned multiple fields, including sensing and detection, infection therapy, cancer treatment, and pollutant degradation. The introduction of nitrogen into nanozymes not only broadens their application range but also holds significant importance for the design of catalysts in biomedical research. The synergistic interplay between W and N induces pivotal alterations in electronic configurations, endowing tungsten nitride (WN) with a peroxidase-like functionality. Furthermore, the introduction of N vacancies augments the nanozyme activity, thus amplifying the catalytic potential of WN nanostructures. Rigorous theoretical modeling and empirical validation corroborate the genesis of the enzyme activity. The meticulously engineered WN nanoflower architecture exhibits an exceptional ability in traversing bacterial surfaces, exerting potent bactericidal effects through direct physical interactions. Additionally, the topological intricacies of these nanostructures facilitate precise targeting of generated radicals on bacterial surfaces, culminating in exceptional bactericidal efficacy against both Gram-negative and Gram-positive bacterial strains along with notable inhibition of bacterial biofilm formation. Importantly, assessments using a skin infection model underscore the proficiency of WN nanoflowers in effectively clearing bacterial infections and fostering wound healing. This pioneering research illuminates the realm of pseudoenzyme activity and bacterial capture-killing strategies, promising a fertile ground for the development of innovative, high-performance artificial peroxidases.
Assuntos
Antibacterianos , Nitrogênio , Antibacterianos/farmacologia , Antibacterianos/química , Nitrogênio/química , Testes de Sensibilidade Microbiana , Compostos de Tungstênio/química , Compostos de Tungstênio/farmacologia , Peroxidase/metabolismo , Peroxidase/química , Animais , Tungstênio/química , Tungstênio/farmacologia , Materiais Biomiméticos/química , Materiais Biomiméticos/farmacologia , Infecções Bacterianas/tratamento farmacológico , Camundongos , Catálise , Nanoestruturas/química , Escherichia coli/efeitos dos fármacos , HumanosRESUMO
Nitridophosphates are subject of current research, as they have a broad spectrum of properties and potential applications, such as ion conductors or luminescent materials. Yet, the subclass of imidonitridophosphates has been studied less extensively. The primary reason is that the controlled N-H functionalization of nitridophosphates is not straight forward, making targeted synthesis more challenging. Inspired by the high-pressure (HP) post-synthetic modification of nitridophosphates, we present the topochemical HP deprotonation of phosphorus nitride imides using the high-pressure polymorph ß-PN(NH) as an example. Additional incorporation of Zn2+ results in the first quaternary transition metal imidonitridophosphate ZnH2P4N8. The crystal structure was elucidated by single-crystal X-ray diffraction (SCXRD), energy-dispersive X-ray spectroscopy (EDX), powder X-ray diffraction (PXRD) and solid-state magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). In addition, the presence of H as part of an imide group was confirmed by IR spectroscopy. The potential of this defunctionalization approach for controlling the N-H content is demonstrated by the preparation of partially deprotonated intermediates ZnxH4-2xP4N8 (x≈0.5, 0.85). This topochemical high-pressure reaction represents a promising way to prepare, control and manipulate new imide-based materials without altering their overall anionic framework.
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Multi-mode emissive materials with stimuli-responsive producing invisible signals are very attractive for advanced security applications, but development of such materials remains highly challenging. In this work, oxygen-doped carbon nitrides (O-CNs) are prepared via microwave-assisted heating of urea, which exhibit ultraviolet (UV) solid-state fluorescence (SSFL), visible room temperature phosphorescence (RTP) and thermal-stimuli production of invisible UV delayed fluorescence (DF) properties. Further studies confirmed that the SSFL and RTP could be attributed to the introduction of oxygen functional group (e. g., C=O) in the skeleton of O-CNs, thus minimizing the aggregation caused quenching effect, facilitating intersystem crossing, and stabilizing the excited triplet states. The specific thermal-stimuli production of UV DF is deemed to be the relatively large energy gap between ground and excited singlet states as well as an effective triplet-triplet annihilation. Notably, the emission maximum of UV DF locates at ~310â nm with an ultra-narrow full width at half maximum (FWHM) down to 19â nm, so it is completely invisible to the naked eyes, but detectable by a UV camera. To employ the unique characteristics of O-CNs, security protection strategies with superior concealment by virtue of the thermal-stimuli quenching visible RTP and meanwhile producing invisible UV DF are demonstrated.
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The research for wurtzite-type ternary nitride semiconductors containing earth abundant elements with a stoichiometry of 1 : 1 : 2 was focused on metals like Mg or Zn, so far. The vast majority of these Grimm-Sommerfeld analogue compounds crystallize in the ß-NaFeO2 structure, although a second arrangement in space group Pmc21 is predicted to be a viable alternative. Despite extensive theoretical and experimental studies, this structure has so far remained undiscovered. Herein, we report on BeGeN2 in a Pmc21 structure, synthesized from Be3N2 and Ge3N4 using a high-pressure high-temperature approach at 6â GPa and 800 °C. The compound was characterized by powder X-ray diffraction (PXRD), solid state nuclear magnetic resonance (NMR), Raman and energy dispersive X-ray (EDX) spectroscopy, temperature-dependent PXRD, second harmonic generation (SHG) and UV/Vis measurements and in addition also compared to its lighter homologue BeSiN2 in all mentioned analytic techniques. The synthesis and investigation of both the first beryllium germanium nitride and the first ternary wurtzite-type nitride crystallizing in space group Pmc21 open the door to a new field of research on wurtzite-type related structures.
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The difficulty of nitride modification is to develop simple and efficient strategies to induce defects and efficiently capture Ru atoms. With these in mind, this work innovatively constructed a Ru-Co3O4/CoN-L catalyst with abundant anion defects (oxygen vacancies (VO) and nitrogen vacancies (VN)) using the nitridation-quenching-Ru doping strategy. Surprisingly, the porous structure provided more active sites, and the VN and VO were conducive to promoting the anchoring of Ru atoms. These significantly improved the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances of the Ru-Co3O4/CoN/NF-L catalyst. The density functional theory results showed that the anion defects optimized the hydrogen adsorption capacity of the Ru active sites for the HER. Furthermore, Ru dopants and anion defects reduced the OER energy barrier of the Co-active sites, accelerating the HER and OER kinetics. This study proposes a new concept for defect construction and nitride-structure optimization.
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We report on the synthesis, crystal, and electronic structure, as well as the magnetic, and electric properties of the phosphorus-containing tantalum nitride P1-xTa8+xN13 (x=0.1-0.15). A high-pressure high-temperature reaction (8â GPa, 1400 °C) of Ta3N5 and P3N5 with NH4F as a mineralizing agent yields the compound in the form of black, rod-shaped crystals. Single-crystal X-ray structure elucidation (space group C2/m (no. 12), a=16.202(3), b=2.9155(4), c=11.089(2)â Å, ß=126.698(7)°, Z=2) shows a network of face- and edge-sharing Ta-centered polyhedra that contains small vacant channels and PN6 octahedra strands. Atomic resolution transmission electron microscopy reveals an unusual P/Ta disorder. Mixed-valent tantalum atoms exhibit interatomic distances similar to those in metallic tantalum, however, the electrical resistivity is quite high in the order of 101â Ω cm. The density of states and the electron localization function indicate localized electrons in both covalent and ionic bonds between P/Ta and N atoms, combined with less localized electrons that do not contribute to interatomic bonds.
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The state-of-the-art ammonothermal method for the growth of nitrides is reviewed here, with an emphasis on binary and ternary nitrides beyond GaN. A wide range of relevant aspects are covered, from fundamental autoclave technology, to reactivity and solubility of elements, to synthesized crystalline nitride materials and their properties. Initially, the potential of emerging and novel nitrides is discussed, motivating their synthesis in single crystal form. This is followed by a summary of our current understanding of the reactivity/solubility of species and the state-of-the-art single crystal synthesis for GaN, AlN, AlGaN, BN, InN, and, more generally, ternary and higher order nitrides. Investigation of the synthesized materials is presented, with a focus on point defects (impurities, native defects including hydrogenated vacancies) based on GaN and potential pathways for their mitigation or circumvention for achieving a wide range of controllable functional and structural material properties. Lastly, recent developments in autoclave technology are reviewed, based on GaN, with a focus on advances in development of in situ technologies, including in situ temperature measurements, optical absorption via UV/Vis spectroscopy, imaging of the solution and crystals via optical (visible, X-ray), along with use of X-ray computed tomography and diffraction. While time intensive to develop, these technologies are now capable of offering unprecedented insight into the autoclave and, hence, facilitating the rapid exploration of novel nitride synthesis using the ammonothermal method.
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Group-III nitrides have transformed solid-state lighting and are strategically positioned to revolutionize high-power and high-frequency electronics. To drive this development forward, a deep understanding of fundamental material properties, such as charge carrier behavior, is essential and can also unveil new and unforeseen applications. This underscores the necessity for novel characterization tools to study group-III nitride materials and devices. The optical Hall effect (OHE) emerges as a contactless method for exploring the transport and electronic properties of semiconductor materials, simultaneously offering insights into their dielectric function. This non-destructive technique employs spectroscopic ellipsometry at long wavelengths in the presence of a magnetic field and provides quantitative information on the charge carrier density, sign, mobility, and effective mass of individual layers in multilayer structures and bulk materials. In this paper, we explore the use of terahertz (THz) OHE to study the charge carrier properties in group-III nitride heterostructures and bulk material. Examples include graded AlGaN channel high-electron-mobility transistor (HEMT) structures for high-linearity devices, highlighting the different grading profiles and their impact on the two-dimensional electron gas (2DEG) properties. Next, we demonstrate the sensitivity of the THz OHE to distinguish the 2DEG anisotropic mobility parameters in N-polar GaN/AlGaN HEMTs and show that this anisotropy is induced by the step-like surface morphology. Finally, we present the temperature-dependent results on the charge carrier properties of 2DEG and bulk electrons in GaN with a focus on the effective mass parameter and review the effective mass parameters reported in the literature. These studies showcase the capabilities of the THz OHE for advancing the understanding and development of group-III materials and devices.
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We study recombination processes in nitride LEDs emitting from 270 to 540 nm with EQE ranging from 4% to 70%. We found a significant correlation between the LEDs' electro-optical properties and the degree of nanomaterial disorder (DND) in quantum wells (QWs) and heterointerfaces. DND depends on the nanoarrangement of domain structure, random alloy fluctuations, and the presence of local regions with disrupted alloy stoichiometry. The decrease in EQE values is attributed to increased DND and excited defect (ED) concentrations, which can exceed those of Shockley-Read-Hall defects. We identify two mechanisms of interaction between EDs and charge carriers that lead to a narrowing or broadening of electroluminescence spectra and increase or decrease EQE, respectively. Both mechanisms involve multiphonon carrier capture and ionization, impacting EQE reduction and efficiency droop. The losses caused by these mechanisms directly affect EQE dependencies on current density and the maximum EQE values for LEDs, regardless of the emission wavelength. Another manifestation of these mechanisms is the reversibility of LED degradation. Recombination processes vary depending on whether QWs are within or outside the space charge region of the p-n junction.