Nonradiative Surface Recombination Research Articles

Impact of crystallographic facet of InGaN micro-LED sidewalls on electro-optical characteristics

InGaN micro-LEDs (μLEDs) with their potential high-volume applications have attracted substantial research interest in the past years. In comparison to other III–V semiconductors, InGaN exhibits a reduced susceptibility toward non-radiative surface recombination. However, efficiency degradation becomes more prominent as dimensions shrink to a few μm or less. Due to the high surface-to-volume ratio of the miniaturized devices, the non-radiative recombination increases and reduces the internal quantum efficiency. While many groups focus on surface passivation to mitigate surface defects, the influence of crystallographic orientation of the μLED sidewall on the efficiency remains unexplored. This study addresses this gap by investigating the impact of crystallographic orientation of the sidewalls on the emission properties of the μLEDs. Hexagonal and elongated μLEDs with dimensions as small as 3.5 μm and sidewalls with crystallographically well-defined m- and a-planes were fabricated. Electrical and optical properties were investigated using photo- and electroluminescence. External quantum efficiency (EQE) is assessed based on well-known carrier recombination models. It can be shown that μLED performance intrinsically depends on the crystallographic orientation of the sidewalls. Comparing hexagonal μLED structures with a-plane and m-plane sidewalls, an increase in the EQE by 33% was observed for structures with a-plane sidewalls, accompanied by reduction in the current density of the peak EQE by a nearly two orders of magnitude compared to structures with m-plane sidewalls. By analyzing the EQE characteristics at the μLED center and near the sidewalls, the improvements can be directly attributed to the increased radiative recombination from sidewalls with a-plane orientation.

Impact of crystallographic facet of InGaN micro-LED sidewalls on electro-optical characteristics

InGaN micro-LEDs (μLEDs) with their potential high-volume applications have attracted substantial research interest in the past years. In comparison to other III–V semiconductors, InGaN exhibits a reduced susceptibility toward non-radiative surface recombination. However, efficiency degradation becomes more prominent as dimensions shrink to a few μm or less. Due to the high surface-to-volume ratio of the miniaturized devices, the non-radiative recombination increases and reduces the internal quantum efficiency. While many groups focus on surface passivation to mitigate surface defects, the influence of crystallographic orientation of the μLED sidewall on the efficiency remains unexplored. This study addresses this gap by investigating the impact of crystallographic orientation of the sidewalls on the emission properties of the μLEDs. Hexagonal and elongated μLEDs with dimensions as small as 3.5 μm and sidewalls with crystallographically well-defined m- and a-planes were fabricated. Electrical and optical properties were investigated using photo- and electroluminescence. External quantum efficiency (EQE) is assessed based on well-known carrier recombination models. It can be shown that μLED performance intrinsically depends on the crystallographic orientation of the sidewalls. Comparing hexagonal μLED structures with a-plane and m-plane sidewalls, an increase in the EQE by 33% was observed for structures with a-plane sidewalls, accompanied by reduction in the current density of the peak EQE by a nearly two orders of magnitude compared to structures with m-plane sidewalls. By analyzing the EQE characteristics at the μLED center and near the sidewalls, the improvements can be directly attributed to the increased radiative recombination from sidewalls with a-plane orientation.

Designing Surface Passivators Through Intramolecular Potential Manipulation for Efficient and Stable Perovskite Solar Cells.

The conjugation of terminal ammonium salt groups with perovskite surfaces is a frequently employed technique that aims to enhance the overall performance of perovskite materials, encompassing both bulk and surface properties. Particularly, it exhibits heightened efficacy when applied to surface modification, due to its ability to mitigate defect accumulation and facilitate facile binding with the receptive sites inherent to the perovskite structure. However, the interaction of the bulk ammonium group with PbI2 has the potential to form a low-dimensional phase of perovskite, which may obstruct carrier extraction at the interface. Therefore, the surface passivators (MeO-PFACl) are designed through intramolecular potential manipulation. The combinations of the electron-donating methoxy group and π-π conjugation of the phenyl ring reduce the local potential at the reactive site of formamidinium group, making it less likely to form a low-dimension phase with perovskite. This surface passivation strategy effectively suppresses the surface nonradiative recombination and promotes the interface carrier extraction. The devices treated with MeO-PFACl have demonstrated exceptional performance, achieving a peak power conversion efficiency (PCE) of 25.88%, with an average PCE of 25.37%. These works offer a novel principle for enhancing both the efficiency and stability of PSCs using ammonium-incorporated molecules without the induction of an additional phase layer.

Reduced Surface Recombination in Extended-Perimeter LEDs toward Electroluminescent Cooling.

III-V semiconductor light-emitting diodes (LEDs) are a promising candidate for demonstrating electroluminescent cooling. However, exceptionally high internal quantum efficiency designs are paramount to achieving this goal. A significant loss mechanism preventing unity internal quantum efficiency in GaAs-based devices is nonradiative surface recombination at the perimeter sidewall. To address this issue, an unconventional LED design is presented, in which the distance from the central current injection area to the device's perimeter is extended while maintaining a constant front contact grid size. This approach effectively moves the perimeter beyond the lateral spread of current at an operating current density of 101-102 A/cm2. In p-i-n GaAs/InGaP double heterojunction LEDs fabricated with varying sizes and perimeter extensions, a 19% relative increase in external quantum efficiency is achieved by extending the perimeter-to-contact distance from 25 to 250 μm for a front contact grid size of 450 × 450 μm2. Utilizing an in-house developed Photon Dynamics model, the corresponding relative increase in internal quantum efficiency is estimated to be 5%. These results are ascribed to a significant reduction in perimeter recombination due to a lower perimeter-to-surface area (P/A) ratio. However, in contrast to lowering the P/A ratio by increasing the front contact grid size of LEDs, the present method enables these improvements without affecting the required maximum current density in the microscopic active LED area under the front contact grid. These findings aid in the advancement of electroluminescent cooling in LEDs and could prove useful in other dedicated semiconductor devices where perimeter recombination is limiting.

Localized Oxidation Embellishing Strategy Enables High-Performance Perovskite Solar Cells.

Perovskite solar cell (pero-SC) has attracted extensive studies as a promising photovoltaic technology, wherein the electron extraction and transfer exhibit pivotal effect to the device performance. The planar SnO2 electron transport layer (ETL) has contributed the recent record power conversion efficiency (PCE) of the pero-SCs, yet still suffers from surface defects of SnO2 nanoparticles which brings energy loss and phase instability. Herein, we report a localized oxidation embellishing (LOE) strategy by applying (NH4 )2 CrO4 on the SnO2 ETL. The LOE strategy builds up plentiful nano-heterojunctions of p-Cr2 O3 /n-SnO2 and the nano-heterojunctions compensate the surface defects and realize benign energy alignment, which reduces surface non-radiative recombination and voltage loss of the pero-SCs. Meanwhile, the decrease of lattice mismatch released the lattice distortion and eliminated tensile stress, contributing to better stability of the devices. The pero-SCs based on α-FAPbI3 with the SnO2 ETL treated by the LOE strategy realized a PCE of 25.72 % (certified as 25.41 %), along with eminent stability performance of T90 >700 h. This work provides a brand-new view for defect modification of SnO2 electron transport layer.

Response of InGaN/GaN multiple quantum well structure to UV-C and vacuum UV optical excitation

We report on the behavior of InGaN/GaN multiple quantum well structure during excitation in UV-C and vacuum UV spectral region. Photoluminescence excitation spectra show peaks with positions different to the peaks in absorption spectra. The very high absorption coefficient in order of 107 cm−1 at energies above 6.9 eV causes the excitation in the surface region which enhances the non-radiative surface recombination. The mechanism explains the differences between absorption and excitation spectra measured in a studied range of energies between 5.8 and 40 eV.

Study on the Influence of KOH Wet Treatment on Red μLEDs

InGaN-based red micro-light-emitting diodes (µLEDs) of different sizes were prepared in this work. The red GaN epilayers were grown on 4-inch sapphire substrates through metal-organic chemical vapor deposition (MOCVD). Etching, sidewall treatment, and p- and n-contact deposition were involved in the fabrication process. Initially, the etching process would cause undesirable damage to the GaN sidewalls, which leads to an increase in leakage current. Hence, we employed KOH wet treatment to rectify the defects on the sidewalls and conducted a comparative and systematic analysis of electrical as well as optical properties. We observed that the µLEDs with a size of 5 µm exhibited a substantial leakage current, which was effectively mitigated by the application of KOH wet treatment. In terms of optical performance, the arrays with KOH demonstrated improved light output power (LOP). Additionally, while photoelectric performance exhibited a decline with increased current density, the devices treated with KOH consistently outperformed their counterparts in terms of optoelectronic efficiency. It is noteworthy that the optimized devices displayed enhanced photoelectric characteristics without significantly altering their original peak wavelength and FWHM. Our findings point to the elimination of surface non-radiative recombination by KOH wet treatment, thereby enhancing the performance of small-sized red µLEDs, which has significant potential in realizing full-color micro-displays in near-eye projection applications.

3.5 × 3.5 μm2 GaN blue micro-light-emitting diodes with negligible sidewall surface nonradiative recombination

Micro-light-emitting diode displays are generating considerable interest as a promising technology for augmented-reality glasses. However, the fabrication of highly efficient and ultra-small ( <3 μm) micro-light-emitting diodes, which are required for augmented-reality applications, remains a major technical challenge due to the presence of strong sidewall nonradiative recombination. In this study, we demonstrate a 3.5 × 3.5 μm2 blue GaN micro-light-emitting diode with negligible sidewall nonradiative recombination compared with bulk nonradiative recombination. We achieve this by using an ultralow-damage dry etching technique, known as neutral beam etching, to create the micro-light-emitting diode mesa. Our 3.5 × 3.5 μm2 micro-light-emitting diode exhibits a low decrease in external quantum efficiency of only 26% at a current density of 0.01 A/cm2, compared with the maximum external quantum efficiency that is reached at the current density of ∼3 A/cm2. Our findings represent a significant step towards realizing micro-light-emitting diode displays for augmented-reality glasses.

Dislocation Suppresses Sidewall‐Surface Recombination of Micro‐LEDs

AbstractNonradiative recombination rate that consists of dislocation‐related nonradiative recombination rate (A0) and surface recombination rate (As) is one of the major parameters determining the performance of microlight‐emitting diodes (µLEDs). Recent demonstrations improving the efficiency of blue InGaN or red AlGaInP µLEDs using specific methods such as atomic layer deposition or chemical treatment confirm the suppression of As. However, it is hardly found that those methods effectively improve the efficiency of red InGaN µLEDs so far. Here, it is discovered that the dislocation leads to an ineffective As. First, an intrinsic As degrades the external quantum efficiency (EQE) of blue InGaN µLEDs, resulting in EQE decreases with shrinking size. Second, panchromatic cathodoluminescence finds evidence that most of the carriers can be trapped before reaching the sidewall due to high A0. This results in shortened diffusion length of carriers and reduces the number of carriers reaching the sidewall. Consequently, the opposite trend of increasing EQE with shrinking size occurs in the case of red InGaN µLEDs due to an ineffective As. Furthermore, an 8.3 nm quantum well of InGaN with 13% Indium content that can reach a ≈690 nm wavelength at the low current is shown.

Mitigating Surface Deficiencies of Perovskite Single Crystals Enables Efficient Solar Cells with Enhanced Moisture and Reverse‐Bias Stability

AbstractMetal halide perovskite single crystals are promising for diverse optoelectronic applications due to their outstanding properties. In comparison to the bulk, the crystal surface suffers from high defect density and is moisture sensitive; however, surface modification strategies of perovskite single crystals are relatively deficient. Herein, solar cells based on methylammonium lead triiodide (MAPbI3) thin single crystals are selected as a prototype to improve single‐crystal perovskite devices by surface modification. The surface trap passivation and protection against moisture of MAPbI3 thin single crystals are achieved by one bifunctional molecule 3‐mercaptopropyl(dimethoxy)methylsilane (MDMS). The sulfur atom of MDMS can coordinate with bare Pb2+ of MAPbI3 single crystals to reduce surface defect density and nonradiative recombination. As a result, the modified devices show a remarkable efficiency of 22.2%, which is the highest value for single‐crystal MAPbI3 solar cells. Moreover, MDMS modification mitigates surface ion migration, leading to enhanced reverse‐bias stability. Finally, the cross‐link of silane molecules forms a protective layer on the crystal surface, which results in enhanced moisture stability of both materials and devices. This work provides an effective way for surface modification of perovskite single crystals, which is important for improving the performance of single‐crystal perovskite solar cells, photodetectors, X‐ray detectors, etc.

Nonblinking Core–Multishell InP/ZnSe/ZnS Quantum Dot Bioconjugates for Super-resolution Imaging

Colloidal quantum dots (QDs) are vital fluorescent probes with several optical features superior to those found in organic dyes for microscopy imaging. However, the emission blinking behavior of a single QD is an intrinsic drawback for stimulated emission depletion microscopy (STED) or structured illumination microscopy techniques. Herein, we present a rational strategy for the synthesis of a type of deterministic, environmentally friendly, small nonblinking core–multishell InP/ZnSe/ZnS QD using a hydrofluoric acid (HF) etching passivation. The strategy includes four steps: synthesis of the InP core, synthesis of oil-phase core–multishell InP/ZnSe/ZnS QDs using hydrogen fluoride and trioctylphosphine etching passivation, promotion of the water solubility of QDs modified by 3-mercaptopropionic acid (MPA), and enhanced biotargeting of core–multishell InP/ZnSe/ZnS QDs by surface coupling technology. The suppressed blinking mechanism was primarily attributed to surface wrapping shells and HF etching passivation of surface dangling bonds, which reduced surface nonradiative recombination. Nonblinking QDs exhibit high fluorescence efficiency (∼90%), good photostability (>20 min), a large Stokes shift (>135 nm), biocompatibility of the cell viability (>90%), and high targeting. Furthermore, super-resolution multifocal structured illumination microscopy imaging of subcellular structures labeled using these QDs confirmed a resolution improvement of greater than 2.6-fold compared to wide-field microscopy. The results indicate that the nonblinking QDs can function as excellent probes for use in the long-term super-resolution visualization of subcellular dynamics.

Atomic layer deposition of diethylzinc/zinc oxide on InAs surface quantum dots: Self-clean-up and passivation processes

Passivation capping of molecular beam epitaxy (MBE)-grown InAs surface quantum dots (SQDs) is achieved by ex situ atomic layer deposition (ALD)-grown ZnO using diethylzinc (DEZ) as the zinc precursor, the main passivation agent, and oxygen plasma. Photoluminescence (PL) intensity is enhanced by 2-fold as the DEZ/ZnO passivation cap thickness reached 30 nm. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) show that contrary to conventional wet chemistry passivation or MBE capping, in which InAs SQDs can be damaged or be shrunken by intermixing of In and Ga, DEZ/ZnO passivation capping almost preserves the shape of the underlying SQDs. The cross-sectional analysis with transmission electron microscopy (TEM) reveals the formation of the ZnO grains on top of the sample accompanied by slight SQD height and width reduction, which are presumably related to the removal of the InAs native oxides. The DEZ “self-clean-up” passivation mechanism, where zinc precursor is responsible for reduction of the surface non-radiative recombination sites, is studied by X-ray photoelectron spectroscopy (XPS). The factors that control the DEZ “self-clean-up” efficiency such as the chain of chemical reactions, steric hindrance, decomposition activation energy, Gibbs reactivity, or Lewis acidity, are evaluated. The results are discussed in comparison with trimethylaluminum (TMA), a precursor used for Al2O3 deposition. We find that the “self-cleaning” by DEZ and TMA occurs through processes of different chemical nature.

A polarization mismatched p-GaN/p-Al0.25Ga0.75N/p-GaN structure to improve the hole injection for GaN based micro-LED with secondary etched mesa

A low hole injection efficiency for InGaN/GaN micro-light-emitting diodes (μLEDs) has become one of the main bottlenecks affecting the improvement of the external quantum efficiency (EQE) and the optical power. In this work, we propose and fabricate a polarization mismatched p-GaN/p-Al0.25Ga0.75N/p-GaN structure for 445 nm GaN-based μLEDs with the size of 40 × 40 μm2, which serves as the hole injection layer. The polarization-induced electric field in the p-GaN/p-Al0.25Ga0.75N/p-GaN structure provides holes with more energy and can facilitate the non-equilibrium holes to transport into the active region for radiative recombination. Meanwhile, a secondary etched mesa for μLEDs is also designed, which can effectively keep the holes apart from the defected region of the mesa sidewalls, and the surface nonradiative recombination can be suppressed. Therefore, the proposed μLED with the secondary etched mesa and the p-GaN/p-Al0.25Ga0.75N/p-GaN structure has the enhanced EQE and the improved optical power density when compared with the μLED without such designs.

N-doped TiO2 nanotubes synthesized by atomic layer deposition for acetaminophen degradation

Titanium dioxide (TiO2) is widely used in photocatalysis applications for wastewater treatment. Investigations demonstrated that titanium dioxide structure strongly contributes to increase micropollutant degradation efficiency. Indeed, pollutant degradation rates are enhanced when using photocatalysts with highly ordered structures and high specific surface area, such as TiO2 nanotubes (NTs) synthesized by atomic layer deposition (ALD). Here, TiO2 NTs, fabricated by ALD followed by nitrogen doping via thermal treatment, were compared with TiO2 nanofibers (NFs), prepared by electrospinning. Their morphology and structure were investigated by scanning and transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Photoluminescence measurements showed that TiO2 NT photoluminescence intensity was lower than that of TiO2 NFs, due to lower electron-hole pair recombination, and consequently their degradation efficiency was higher. As the surface to volume ratio was higher in TiO2 NTs than NFs, the rate of non-radiative surface recombination also was higher in TiO2 NTs. Comparison of their performance for photocatalytic degradation of acetaminophen showed higher degradation activity with TiO2 NTs than TiO2 NFs. TiO2 NT doping with nitrogen (N-TiO2 NTs) further enhanced their photocatalytic activity that was 5 times higher than that of TiO2 NFs (degradation rates: 0.05 and 0.01 mg.L−1.min−1, respectively). The N-TiO2 NT photocatalyst was stable after four cycles of acetaminophen degradation. Acute toxicity assays confirmed the release of harmful by-products during the first hours of acetaminophen degradation, but toxicity strongly decreased after 5 h.

Interplay of sidewall damage and light extraction efficiency of micro-LEDs.

This Letter describes the impact of shape on micro light-emitting diodes (µLEDs), analyzing 400 µm2 area µLEDs with various mesa shapes (circular, square, and stripes). Appropriate external quantum efficiency (EQE) can yield internal quantum efficiency (IQE) which decreases with increasing peripheral length of the mesas. However, light extraction efficiency (ηe) increased with increasing mesa periphery. We introduce analysis of Jpeak (the current at peak EQE) since it is proportional to the non-radiative recombination. Etching the sidewalls using tetramethylammonium hydroxide (TMAH) increased the peak EQE and decreased the sidewall dependency of Jpeak. Quantitatively, the TMAH etching reduced non-radiative surface recombination by a factor of four. Hence, shrinking µLEDs needs an understanding of the relationship between non-radiative recombination and ηe, where analyzing Jpeak can offer new insights.

GaN‐Based Deep‐Nano Structures: Break the Efficiency Bottleneck of Conventional Nanoscale Optoelectronics

AbstractConventional semiconducting nanowire optoelectronic devices generally exhibit low efficiency, due to dominant nonradiative surface recombination. Here, it is shown that such a critical challenge can be potentially addressed by exploiting semiconducting structures in the deep‐nanoregime. The epitaxy and structural and optical characteristics of GaN‐based micro‐network nanostructures grown on Si wafer are studied. These complex nanostructures have lateral dimensions as small as a few nanometers. Detailed scanning transmission electron microscopy studies suggest that the self‐assembled micro‐network nanostructures are monocrystalline, despite the porous nature. Significantly, such micro‐network nanostructures exhibit ultrabright emission in the visible spectrum. Compared to conventional InGaN nanowire structures with similar surface area, the surface recombination velocity of such deep‐nanostructures is reduced by nearly two orders of magnitude, which is evidenced by the extremely bright luminescence emission as well as the long carrier lifetime measured under low excitation conditions. This study offers a new path for the design and development of next generation high efficiency nanoscale optoelectronic devices.

Decreased surface defects and non-radiative recombination via the passivation of the halide perovskite film by 2-thiophenecarboxylic acid in triple-cation perovskite solar cells.

Organic-inorganic lead halide perovskite solar cells (PSCs) attract great research interest due to their significant device performance and optoelectronic properties. However, reducing charge recombination and efficiency loss due to surface defects of the perovskite layer are still big issues to overcome for PSCs. Herein, we have employed a simple molecule, 2-thiophenecarboxylic acid (2TiCOOH), via post-treatment to passivate the uncoordinated Pb2+ on the perovskite film surface and improve the stability at the perovskite/Spiro-OMeTAD interface. The spectral results illustrate that the 2TiCOOH passivated devices exhibit higher carrier lifetime, charge extraction, and minimized defect induced recombination. Also, solar cells with 2TiCOOH show better charge collection, improved JSC, FF, and outstanding power conversion efficiency (PCE). In addition, 2TiCOOH passivated solar cells show tremendously stable performance output with less than 1% PCE drop after 100 days. This work provides a facile surface passivation strategy for fabricating highly efficient, low cost, and stable perovskite solar cells, which can be used for large scale technology and commercialization.

Enhanced photoelectric performance of GaN-based Micro-LEDs by ion implantation

As the new display technology, Micro-LEDs are of the advantages of low power consumption, high brightness, high resolution and fast response time. However, the strong surface non-radiative recombination significantly reduces their efficiency. Some techniques such as epitaxial growth or wet sulfide have been introduced to inhibit the surface recombination, but these expensive or unstable methods ignore the operability of industrial production. Herein, we use an ion implantation method to modify the high-density surface defects on the sidewall, thereby improve the luminous efficiency effectively by inhibiting carrier surface non-radiative recombination. The photoelectric performances of GaN-based Micro-LEDs after N ion implantation were studied. The characterization results indicated that the photoluminescence intensity of Micro-LEDs was increased by 7 times after passivation, which was attributed to the significant elimination of sidewall damage. In addition, the removal of the surface dangling bonds and oxidized nitrides (Ga–N or Ga-OH bonds) after the passivation process were further proved by Auger electron spectroscopy characterization. As a result of the N ion implantation, the external quantum efficiency of packaged Micro-LEDs chip increased about 33%. Therefore, this manuscript will provide a new direction for improving the photoelectric performance of Micro-LEDs.

Organic Halide PEACl for Surface Passivation and Defects Suppression in Perovskite Solar Cells

In recent times, mixed cation-based perovskite has gained a lot of popularity in high-performance solar cells. However, the mixed cations based on the FAxMA1–xPbI3 absorber layer still exhibit a higher trap state density, which decreases the overall performance, especially in the open-circuit voltage (VOC) and fill factor (FF). Herein, we show that surface passivation by the organic halide PEACl is an effective way to reduce the trap state density. This efficient PEACl treatment reduces the halide deficiency present at the perovskite surface and reduces surface defects and nonradiative recombination. The resultant perovskite solar cell exhibits a higher VOC (1.15 V), 92% of the Shockley-Queisser limit (1.25 V), and a higher FF than standard perovskite.

Hydrophobic π-conjugated organic small molecule as a multi-functional interface material enables efficient and stable perovskite solar cells

Surface treatment of perovskite films with interface materials is an effective strategy to resolve trap-mediated nonradiative recombination toward high efficiency and stability of perovskite solar cells (PSCs). However, interface materials for multi-functional treatment have been rarely investigated in PSCs. In this work, a novel pyrene-based organic material (TAAPyr) is first introduced as a defect passivation layer and a protect layer against moisture for PSCs application. With the TAAPyr interfacial modification, both perovskite surface defects and nonradiative recombination are effectively decreased as well as the carrier transport in device is also enhanced, As a consequence, the best power conversion efficiencies (PCE) up to 22.45% for TAAPyr-based device was obtained, clearly outperforming the control one (20.37%). Moreover, it was found that the π-conjugated TAAPyr can promote intermolecular face-to-face stacking on the surface perovskite film, which is favorable to making the perovskite surface more hydrophobic and consequently enhance PSCs long-term stability. The un-encapsulated PSCs can retain 92% of the initial PCE after storage for 600 h at ∼65% RH, in comparison with 64% efficiency retention of the device without TAAPyr under the same conditions. This work presents a new strategy to enhance the efficiency and stability of PSCs by multi-functional π–conjugated passivator.