Nonradiative Recombination Centers Research Articles

Rapid Mg substitution to Ga-sites and slow defect recovery revealed by depth-resolved photoluminescence in Mg/N-ion-implanted GaN

Toward p-type GaN formation by Mg ion implantation (I/I) applicable to devices, depth-resolved photoluminescence (PL) revealed key behaviors during activation annealing for precise profile control, such as Mg substitution into Ga-sites (MgGa) and recovery of I/I defects. Depth profiles of the MgGa acceptor concentration were measured for Mg-I/I and Mg/N-I/I samples after ultra-high-pressure annealing at 1300 °C for 1–60 min. The cycle of low-damage dry etching and PL measurement was repeated over the I/I depth, and the MgGa concentration was estimated at each depth based on the calibration curve for the PL intensity ratio between acceptor-bound excitons (A0XA) and free excitons (FXA). In the region deeper than the I/I peak of 0.3 μm, almost all of the Mg atoms rapidly substituted into Ga-sites during the short annealing process. By contrast, the Mg substitution ratios in the shallower region were low when the annealing process was short but were improved by the sequential N-I/I. The low substitution ratio can be explained by MgGa bonding with nitrogen vacancy (VN)-related defects, while the implanted N-ions can compensate them. The PL intensity near the mean implantation depth of Mg/N-I/I was gradually improved as the annealing duration was increased to 60 min, indicating a slow reduction of nonradiative recombination centers. Simultaneously, the green luminescence associated with the VN-related defects decreased in intensity with increasing annealing time. Therefore, the main effect of prolonging annealing is the enhancement of slow defect recovery rather than enhancement of the Mg substitution as a fast process.

Roles of defects in perovskite CsPbX3 (X=I, Br, Cl): a first- principles investigation

Inorganic lead halide perovskite CsPbX3 (X=I, Br, Cl) have a promising application in optoelectronic fields due to their excellent photovoltaic properties. The defects, which have a significant impact on the performance of materials, are often introduced during the synthesis process. However, there is still a lack of systematic theoretical investigation of the effects of these defects. In this study, the effects of vacancies and H-atom interstitial point defects on the structural, electronic and optical properties of CsPbX3 are systematically investigated by using first-principles approach based on density-functional theory. The calculated results show that the introduction of different defects have significantly effect on the band gap, effective mass, semiconductor properties, ion migration and optical absorption coefficient of the perovskite materials. It is also found that VCs and VPb defects introduce shallow transition levels that do not negatively impact the optoelectronic properties. However, VX and interstitial H defects generate deep transition levels within the bandgap, which acts as non-radiative recombination centers and reduce the optoelectronic performance of the perovskite material. This study contributes to the understanding of the nature of halide chalcogenides and optimally regulating the performance of optoelectronic devices.

Effects of etching duration on silicon quantum dot size and photoluminescence quantum yield

Abstract The synthesis of silicon quantum dots (SiQDs) via thermal pyrolysis is considered promising due to its cost-effectiveness. The etching process in this method has the potential to control the size of SiQDs precisely and has thus garnered attention. However, there are varying observations regarding the effect of etching duration on SiQD size. Additionally, the impact of dioxonium hexafluorosilicate (DH), a byproduct of the etching process, on the photoluminescence (PL) quantum yield (QY) of SiQDs remains unclear. This study investigates the effect of etching duration on the physical and optical sizes as well as the PLQY of SiQDs. The results indicate that extending the etching duration decreases the physical size of SiQDs, while the optical size initially increases slightly before decreasing. The SiQDs transition through three phases with increasing etching duration: oxidation removal, shallow over-etching, and deep over-etching. Both amorphous silicon (a-Si) in the oxidation removal phase and DH in the deep over-etching phase act as non-radiative recombination centers, thereby reducing the PLQY of SiQDs. Therefore, optimizing the etching duration to achieve the shallow over-etching phase is essential. This study provides new insights into the effects of etching duration on SiQD size and PLQY, aiding in the preparation of higher-quality SiQDs.

Gamma-ray irradiation-induced effects on Er3+-doped Li2O-Bi2O3-B2O3-TeO2 glass: Structural, optical, luminescence, and radiation shielding properties

In the present study, we report the gamma (γ) ray irradiation-induced structural, optical, luminescence and radiation shielding properties of Er3+-doped Li2O-Bi2O3-B2O3-TeO2 glasses prepared by melt-quenching technique. It was evidence of the slight reductions in density and refractive index while maintaining stable optical properties upon the γ irradiation. Additionally, increased molar volume and polarizability indicated a less compact network. Raman spectroscopy shows broadened peaks and intensity reductions at key vibrational modes. The UV–Vis–NIR absorption spectra reveal the shift in the absorption edge and reduction in the intensities of Er³⁺ absorption bands (around 450, 520, 550, and 650 nm) with higher radiation doses, indicating radiation-induced damage. It was found that the band gap values decreased from 2.58 eV to 1.30 eV for un-irradiated glass to 90 kGy irradiated glass, and Urbach energy was found to increase from 0.18 to 1 eV respectively, indicating structural disorder and localized states within the band gap. PL emission spectra demonstrated intensity changes and peak shifts with γ radiation dose while maintaining a dominant green emission from 4S3/2 → 4I15/2 and 2H11/2 → 4I15/2 transitions, supported by the CIE diagram analysis. The NIR emission spectra also displayed a peak at 1530 nm with decreasing intensity, indicating defect-induced non-radiative recombination centres. Luminescence lifetime decay profiles indicated reduced lifetimes at higher γ doses, suggesting introduced non-radiative decay pathways. Furthermore, Phy-X software analysis highlighted effective γ-ray shielding influenced by chemical composition and photon flux, with MAC sharply decreasing to 1.8 cm2/g at 0.1 MeV and stabilizing, while LAC showed reduced attenuation efficiency at higher energies. HVL and TVL increased with energy, stabilizing around 4–5 cm and 15–16 cm, respectively, necessitating thicker materials for effective shielding at higher photon energies. MFP rapidly increased to 6–7 cm at 2 MeV, stabilizing at higher energies, while Zeff decreased sharply before stabilizing around 1 MeV. The EBF and EABF trends exhibited higher values at low energies, stabilizing at higher energies, indicating effective photon interaction and resonance effects.

Non-radiative recombination centres in InGaN/GaN nanowires revealed by statistical analysis of cathodoluminescence intensity maps and electron microscopy

The methodology of statistical analysis of cathodoluminescence (CL) intensity mappings on ensembles of several hundreds of InGaN/GaN nanowires (NWs) used to quantify non-radiative recombination centres (NRCs) was validated on InGaN/GaN NWs exhibiting spatially homogeneous cathodoluminescence at the scale of single NWs. Cathodoluminescence intensity variations obeying Poisson's statistics were assigned to the presence of randomly incorporated point defects acting as NRCs. Additionally, another type of NRCs, namely extended defects leading to spatially inhomogeneous cathodoluminescence intensity at the scale of single InGaN/GaN NWs are revealed by high resolution scanning transmission electron microscopy, geometrical phase analysis and two-beam diffraction conditions techniques. Such defects are responsible for deviations from Poisson's statistics, allowing one to achieve a rapid evaluation of the crystallographic and optical properties of several hundreds of NWs in a single cathodoluminescence intensity mapping experiment.

Passivating perovskite surface defects via bidentate chelation for high-performing solar cells

Surface defects seriously damage carrier transport by forming non-radiative recombination centers on the perovskite film, which negatively affect the power conversion efficiency (PCE) of perovskite solar cells (PSCs). Here we present a strong chelate coordination bond to anchor the surface of the perovskite film. Employing Bathophenanthroline (BPhen) as a π-conjugated bidentate chelator, the uncoordinated Pb2+ can be firmly anchored accompanying with the reduced surface recombination sites, giving rise to suppressed non-radiative recombination and enhanced charge carrier extraction. With the BPhen, the perovskite film shows an approximately threefold longer carrier lifetime than the control device, leading to a champion PCE of 24.09 % and a high stable performance with retained over 80 % of its initial efficiency after 1000 h exposed to relative humidity (RH) of 65 ± 5 %.

Interfacial modification by 2-fluoroisonicotinic acid enabling high-efficiency and stable n-i-p perovskite solar cells

The power conversion efficiency (PCE) of organic-inorganic halide perovskite solar cells (PSCs) developed rapidly in recent years. However, the defects at the bulk grain boundaries and heterojunction interfaces acting as non-radiative recombination centres and the ion-migration channels severely hinder the charge transport and stability of the PVKs, resulting in low PCE and poor stability. One of the principal impediments to the commercialization of PSCs resides in the challenge posed by this particular aspect. In this work, we employed 2-fluoroisonicotinic acid (2-FINA) as a passivation agent to improve the PCE and stability of n-i-p PSCs by interfacial modification strategy. Owing to the presence of carboxyl (COOH) functional groups and pyridine groups, 2-FINA can strongly interact with uncoordinated Pb2+ and regulate the growth of perovskite crystals, which in turn reduces ion migration and suppress non-radiative recombination along with improves optical properties. Thanks to these improvements, the champion n-i-p PSC solar cell, treated with 2-FINA, showed a PCE of 20.92 %, whereas the untreated one in the same batch exhibited a PCE of 17.13 %. In long-term stability tests, we demonstrated that 2-FINA treatment significantly increases the moisture resistance of non-encapsulated devices.

Investigation of the growth rate on optical and crystal quality of InGaAs/AlGaAs multi-quantum wells and InGaAs single layer grown by molecular beam epitaxy (MBE)

The impact of growth rate on the optical and crystal quality of InGaAs/AlGaAs multi-quantum wells (MQWs) and InGaAs single layer grown by molecular beam epitaxy (MBE) is studied. Photoluminescence (PL) and high-resolution X-ray diffraction (HRXRD) are applied for evaluation of the optical, crystal quality and interfaces smoothness. The room-temperature PL integral intensity increases by 220 % when the growth rate decreases from 2 to 1 Å/s. HRXRD analysis reveals the growth rate of 1 Å/s improves crystal and interface quality of MQWs, as well as significantly enhances PL intensity. But further reduce growth rate to 0.5 Å/s, the PL integral intensity decreases, instead. At lower growth rate, more impurities can incorporate into InGaN layer and act as nonradiative recombination centers. Growth rate can effectively control crystal quality, interfaces smoothness and impurity content and thus determine the optical quality of InGaAs/AlGaAs MQWs.

External quantum efficiency enhancement of GaN-based blue LEDs by treating their full-M-sided hexagonal mesa with TMAH solution.

In recent years, III-Nitride-based micro light-emitting diodes (micro-LEDs) have emerged in many fields and gained more attention. However, fabricating high-efficiency micro-LEDs still remains a challenge due to the presence of sidewall damage. In this study, a GaN-based single blue micro-LED with a full-M-sided hexagonal mesa was prepared. The mesa has a circumradius of 10 µm and was treated with a tetramethylammonium hydroxide (TMAH) solution. Experimental results show that the sidewall defects introduced by dry etching damage act as non-radiative recombination centers and greatly impair the performance of the device. By constructing a full-M-sided hexagonal structure and soaking in a TMAH solution, the etching damage on the sidewall can be eliminated to the greatest extent, thereby reducing sidewall defects. In consequence, the peak EQE of the devices treated with the TMAH solution exceeded 10% at low current density, an increase of 9% compared with the untreated samples. This work provides, to our knowledge, a new approach to improving the efficiency of GaN-based micro-LEDs.

Variation of carrier lifetime with optical excitation power density in micro-LEDs

GaN-based micro-LEDs are applied to visible light communication due to their high modulation bandwidth with reduced chip size. It requires a deep understanding of recombination processes and their impact on the bandwidth, which is mainly determined by the carrier lifetime. We employed confocal time-resolved photoluminescence (TRPL) to characterize the variation of carrier lifetime with optical excitation power density on micro-LEDs. We observed an initial increase followed by a sudden decrease within the power density range of 96.7 kW/cm2 to 546 kW/cm2 on a blue micro-LED with a chip size of 80 µm. We attribute this phenomenon to increased optical excitation power, gradually saturating the defect-dominated non-radiative recombination centers, with radiative recombination processes gradually taking over. We compared the power density at the inflection point for different regions on the sample and the samples with different sizes and sidewall structures. The power density for the lifetime inflection point at the center of the sample is smaller than that at the edge. We also find that the value is smaller for the sample with a chip size of 40 µm which prompts fewer total defects. The power density for sudden lifetime drop on samples with inclined sidewall structures is also smaller than those with vertical sidewall structures. Furthermore, we find that the excitation power density corresponding to the highest luminous efficiency is higher than that corresponding to the sudden drop at the beginning of the lifetime. This opens up possibilities for simultaneously achieving high modulation bandwidth and high efficiency between the two inflection points.

Enhancing exciton-to-Mn2+ energy transfer and emission efficiency in Mn2+-doped CsPbCl3 perovskite nanocrystals via CaCl2 post-treatment

Mn2+-doped CsPbCl3 perovskite nanocrystals (NCs) exhibit a significant Stokes shift and emit bright orange-red light, making them promising candidates for optoelectronic devices. However, these NCs are prone to surface defects during multiple purification steps, which hinder the transfer of energy from excitons to Mn2+ and reduce luminescence efficiency. Herein, we introduce a post-treatment method using a CaCl2 ethanol solution to passivate surface defects in Mn2+-doped CsPbCl3 NCs. This treatment enhances the energy transfer from excitons to Mn2+ and boosts luminescence performance, achieving a photoluminescence quantum yield of up to 96 % and maintaining stability through several washing cycles. In this process, Ca2+ ions, as a Lewis acid, replace oleic acid molecules on NC surfaces, leading to stronger binding. The Cl− from the CaCl2 solution fill vacancies on NC surfaces, effectively passivating surface defects. This reduces non-radiative recombination centers, increases energy transfer efficiency from 83 % to 87 %, and accelerates the radiative recombination rates of excitons and Mn2+. The post-treated NCs also retain their PL against continuous heat and ultraviolet irradiation. The passivation of surface defects on perovskite NCs achieved through this post-processing strategy enhances the energy transfer from excitons to doped ions, providing guidance for achieving efficient and stable doped perovskite NCs.

Interfacial Passivation of Kesterite Solar Cells for Enhanced Carrier Lifetime: Ab Initio Nonadiabatic Molecular Dynamics Study

AbstractNonradiative recombination at the front contact interface of kesterite solar cells hinders the extraction of photo‐generated carriers, significantly restricting the efficiency enhancement. However, identifying the recombination centers and proposing effective passivation strategies remain open questions. First‐principles calculations combining with nonadiabatic molecular dynamics (NAMD) simulations unveil that the interfacial translational symmetry breaking in elemental valence states leads to a detrimental donor‐like Cu2ZnSnS4/CdS interface with deep states originating from the interfacial Sn‐5s orbital, which serve as significant nonradiative recombination centers. Here, two mechanisms are proposed for eliminating the deep interface states: 1) directly replacing Sn‐5s with higher outer orbital levels by substituting group IIIA elements (In and Ga) for the interfacial Sn atom; 2) introducing an extra defect‐level coupling with Sn‐5s by substituting group VA elements (N, P, and As) for the S atoms bonded with the interfacial Sn atom. The representative InSn and PS acceptor defects, which are energetically favorable at the detrimental donor‐like interface, effectively passivate the deep interface states, markedly improving the carrier lifetimes by weakening nonadiabatic coupling between the band edge and the interfacial states. This study reveals the origin of the interfacial nonradiative recombination of kesterite solar cells and offers insights into interfacial passivation in semiconductor devices.

Impact of oxygen plasma power on the performance of Ga2O3 passivated GaN ultraviolet photodetectors

The role of oxygen plasma power on the extent of surface passivation of Gallium Nitride (GaN) epitaxial layers and the photo-response of Au/Ni/GaN Schottky detectors is investigated. The surface morphology is found to be preserved in oxide passivated GaN at intermediate plasma power which significantly deteriorates at higher power. The photoluminescence spectrum shows a fall in the intensity of band edge and defects related yellow luminescence at higher power indicating the generation of non-radiative recombination centres. The chemical and electronic structures of the passivated layer investigated by x-ray photoelectron spectroscopy revealed the formation of stoichiometric Ga2O3 up to intermediate plasma power and partial decomposition of Ga2O3 along with formation of gallium sub-oxides at higher power. This leads to an enhancement in the responsivity of the photodetector after passivation at an intermediate plasma power followed by a considerable reduction at higher power. From the electrical transport measurement across the Au/Ni/GaN Schottky diode, it is observed that the diode manifests more Schottky (Ohmic) character after oxygen plasma treatment at intermediate (higher) power. The present investigations provide a clear guideline on the selection of oxygen plasma power for surface passivation on GaN, which is highly beneficial in optimizing the performance of GaN-based optoelectronic and power devices.

Influence of low-temperature cap layer thickness on the structure and luminescence of InGaN/GaN multiple quantum wells

In order to effectively regulate the luminescence performance of MQW and enhance its optical quality, it is crucial to investigate the InGaN/GaN MQW's structure and luminescence properties. In this study the focus is how they are affected by low-temperature cap (LT-cap) layer's thickness which is grown above each InGaN well layer during growth process of InGaN/GaN multiple quantum well (MQW) samples in MOCVD system. This was achieved by analyzing high resolution X-ray diffraction (HRXRD) spectra, electroluminescence (EL) spectra, temperature-dependent photoluminescence (TDPL) spectra, and micro-area fluorescence imaging of these samples. The results show that changes in LT-cap layer's thickness even have no significant impact on some structural parameters of MQW, such as the thickness of the well layer, but have an influence on the In component of the well layer. Due to the existence of LT-cap layer, dissociation of InGaN can be effectually reduced. In addition, the augmentation of LT-cap layer's thickness will make polarization effect of the QW sample more remarkable, so that the blue shift of the EL peak with the augmentation of current injection increases. The change of LT-cap layer's thickness will also influence distribution of the tail states of the quantum wells, which leads to a different localization states for injected carriers. As LT-cap layer becomes getting thicker, the material's internal quantum efficiency (IQE) tends to decrease, which may result from an increase in non-radiative recombination centers.

Nonlinear Dynamics of Silicon-Based Epitaxial Quantum Dot Lasers under Optical Injection

For silicon-based epitaxial quantum dot lasers (QDLs), the mismatches of the lattice constants and the thermal expansion coefficients lead to the generation of threaded dislocations (TDs), which act as the non-radiative recombination centers through the Shockley–Read–Hall (SRH) recombination. Based on a three-level model including the SRH recombination, the nonlinear properties of the silicon-based epitaxial QDLs under optical injection have been investigated theoretically. The simulated results show that, through adjusting the injection parameters including injection strength and frequency detuning, the silicon-based epitaxial QDLs can display rich nonlinear dynamical states such as period one (P1), period two (P2), multi-period (MP), chaos (C), and injection locking (IL). Relatively speaking, for a negative frequency detuning, the evolution of the dynamical state with the injection strength is more abundant, and an evolution path P1-P2-MP-C-MP-IL has been observed. Via mapping the dynamical state in the parameter space of injection strength and frequency detuning under different SRH recombination lifetime, the effects of SRH recombination lifetime on the nonlinear dynamical state of silicon-based epitaxial QDLs have been analyzed.

Atomic-level quantum well degradation of GaN-based laser diodes investigated by atom probe tomography

Gallium nitride (GaN)- based lasers are extensively employed in display, lighting, and communication applications due to their visible laser emission. Despite notable advancements in their performance and reliability, sustained device functionality over extended periods remains a challenge. Among the diverse mechanisms contributing to degradation, the deterioration of quantum wells poses a persistent obstacle. In this study, we investigated the atomic-level degradation of quantum wells within GaN-based laser diodes utilizing atom probe microscopy. Our analysis revealed a substantial increase in indium fluctuation, accompanied by the formation of indium protrusions at the quantum well interfaces, which provides a credible explanation for the observed increase in FWHM (full width at half maximum) of the spontaneous spectra of lasers following prolonged operation. Additionally, magnesium analysis yielded no evidence of diffusion into the quantum well region. Combined with prior studies, we attribute the degradation of quantum wells primarily to the formation of indium-related non-radiative recombination centers.

Cathodoluminescence studies of the optical properties of a zincblende InGaN/GaN single quantum well

Zincblende GaN has the potential to improve the efficiency of green- and amber-emitting nitride light emitting diodes due to the absence of internal polarisation fields. However, high densities of stacking faults are found in current zincblende GaN structures. This study presents a cathodoluminescence spectroscopy investigation into the low-temperature optical behaviour of a zincblende GaN/InGaN single quantum well structure. In panchromatic cathodoluminescence maps, stacking faults are observed as dark stripes, and are associated with non-radiative recombination centres. Furthermore, power dependent studies were performed to address whether the zincblende single quantum well exhibited a reduction in emission efficiency at higher carrier densities—the phenomenon known as efficiency droop. The single quantum well structure was observed to exhibit droop, and regions with high densities of stacking faults were seen to exacerbate this phenomenon. Overall, this study suggests that achieving efficient emission from zinc-blende GaN/InGaN quantum wells will require reduction in the stacking fault density.

Investigation of structural and optical properties of ZnTiO3 thin films irradiated with 50 MeV oxygen ions

This paper aims to investigate the effects of high-energy ion irradiation on the structural, morphological, optical, and luminescent characteristics of ZnTiO3 (ZTO) films. ZTO films were grown on silicon and quartz substrates via RF magnetron sputtering in pure argon ambiance and annealed at 800 °C for crystallization. The annealed (pristine) samples were irradiated with 50 MeV oxygen ions at three distinct fluences: 1 × 1012, 5 × 1012, and 1 × 1013 ions/cm2. X-ray diffraction (XRD) data demonstrates that the intensity of highly oriented (311) peak first increases with fluence up to 5 × 1012 and then decreases at 1 × 1013 ions/cm2. The root mean square roughness (RMS) increases initially from 8.22 (pristine) to 9.10 nm (1 × 1012 ions/cm2) and decreases to 8.25 nm for 1 × 1013 ions/cm2 fluence. Transmittance spectra indicate an enhancement in the transmission of irradiated films. The calculated band gap of pristine and irradiated films lies in the range of 3.93–3.84 eV. X-ray photoelectron spectroscopy (XPS) analysis reveals a reduction in oxygen vacancies up to a fluence of 5 × 1012 and then rises at 1 × 1013 ions/cm2. The enhancement of peak intensity is observed in photoluminescence (PL) spectra on increasing the ion fluence due to a reduction in the non-radiative recombination centers.

Growth of AlGaN alloys with ∼ 90 % AlN mole fraction by plasma-assisted molecular beam epitaxy: Indication of phase-segregation effects

AlGaN alloys with very high AlN mole fraction (∼90 %) were grown by plasma-assisted molecular beam epitaxy (PA-MBE) and their alloy properties were investigated by high-resolution X-ray diffraction (HR-XRD) measurements. Growth was carried out employing a series of group III/V ratios and for samples grown under a high group-III regime, phase-segregation in the alloy was evident from a characteristic splitting of the AlGaN (0002) peak in the HR-XRD pattern. With decreasing excess group-III conditions the separation of peak positions continuously reduced, till a single peak was observed. However, for samples where such splitting was absent, spontaneous superlattice peaks were seen at lower incident angles of the XRD patterns indicating the presence of long-range atomic ordering (LRAO). Thus, for AlGaN alloys with extremely high Al content, effects of phase-segregation, or of LRAO were observed, depending on the kinetics of growth. These results on phase-segregation effects are expected to promote the development of high-efficiency deep ultraviolet emitters for skin-safe germicidal action by mitigating the detrimental effect of dislocations and related non-radiative recombination centers through carrier localization processes at potential minima.

Biomaterial Improves the Stability of Perovskite Solar Cells by Passivating Defects and Inhibiting Ion Migration.

With the rapid improvement of power conversion efficiency (PCE), perovskite solar cells (PSCs) have broad application prospects and their industrialization will be the next step. Nevertheless, the performance and long-term stability of the devices are limited by the defect-induced nonradiative recombination centers and ions' migration inside the perovskite films. Here, usnic acid (UA), an easy-to-obtain and efficient natural biomaterial with a hydroxyl functional group (-OH) and four carbonyl groups (-C═O) was added to MAPbI3 perovskite precursor to regulate the crystallization process by slowing the crystallization rate, thereby expanding the crystal size and preparing perovskite films with low defect density. In addition, UA anchors the uncoordinated Pb2+ and suppresses the migration of I-ions, which enhances the stability of the perovskite film. Consequently, an impressive PCE exceeding 20% was achieved for inverted structure MAPbI3-based PSCs. More impressively, the optimized PSCs maintained 78% of the initial PCE under air with high humidity (RH ≈ 65%, 25-30 °C) for 1000 h. UA can be extracted from the plant, usnea, making it inexpensive and easy to obtain. Our work demonstrates the application of the plant material in PSCs and their industrialization, which is significant nowadays.