Holes In Band Research Articles

Construction of Z-type heterojunction by depositing CuO nanoparticles on NiO nanosheets for visible-light-enhanced catalytic ammonia borane methanolysis

The development of effective and cost-efficient catalysts for the hydrogen production through methanolysis of ammonia borane (AB) is a hot topic in the field of energy catalysis. In this study, a simple method has been developed to construct a low-cost Z-type heterojunction by depositing CuO nanoparticles on the surface of NiO nanosheets. The as-prepared CuO/NiO composites exhibit prominent activity towards AB methanolysis. The hydrogen generation rate (HGR) is 3.00 Lhydrogen min−1 gcat.−1 when the optimal CuO/NiO sample functions as a catalyst, which is increased to 3.93 Lhydrogen min−1 gcat.−1 with the assistance of visible light illumination. The enhancement of catalytic activity are attributed to the variation of the electronic structure of the catalysts. With the formation of Z-type heterojunction, the valence band electrons of CuO and NiO are excited and transfer to their respective conduction bands under light illumination. Subsequently, the conduction band electrons of CuO recombine with the valence band holes of NiO, leading to an accumulation of electrons at the conduction band of NiO. Consequently, the electron density of the Ni sites is increased, which enhances AB methanolysis. This study can provide new insights for the design and synthesis of cost-effective and highly efficient direct Z-type heterojunction catalysts for hydrogen production through AB methanolysis. Moreover, this study is also helpful for the understanding of how visible light enhances AB methanolysis.

Cation Vacancy-Mediated Ultrafast Hole Transport in CuBi2O4 Photocathodes.

In this study, the ultrafast transport dynamics of the valence band hole states in CuBi2O4 (CBO) photocathodes were investigated by varying the atomic composition and manipulating their p-type character. As a comprehensive ultrafast optical transient absorption spectroscopy (TAS) investigation of compositionally manipulated CBO that combines both ex situ and in situ TAS experiments with photoelectrochemical (PEC) performance tests, the study reveals the polaron formation tendencies of the valence band (VB) holes at cationic vacancy sites. Therefore, it draws a complete picture of the ultrafast hole transport dynamics and provides valuable insights into the hindrance of the photocurrent generated in CBO.

One-step fabrication of Bi2MoO6 nanowires-g-C3N4 composites for outstanding photocatalytic performance in cyclohexane oxidation

Selective oxidation of cyclohexane into cyclohexanone (K) and cyclohexanol (A) stands as a pivotal process in industrial chemistry. However, the challenges associated with activating the C-H bond and the vulnerability of KA oil to over-oxidation detract from the economic significance of this reaction. This study focuses on the preparation of a bismuth molybdate ultrathin nanowires-carbon nitride (Bi2MoO6-g-C3N4) heterojunction through a one-step hydrothermal approach for significantly improving the photocatalytic oxidation of cyclohexane. Bi2MoO6 ultrafine nanowires with the diameter of 6 nm were adhered tightly on the surface of g-C3N4 nanosheets with the assistance of oleyl amine. The type II heterojunction of Bi2MoO6-g-C3N4 composite facilitated a more efficient separation of charges and boosted the photocatalytic performance in the cyclohexane oxidation. The Bi2MoO6-g-C3N4 composite demonstrated outstanding photocatalytic performance with a 10.66 % conversion rate of cyclohexane, surpassing the individual efficiencies of Bi2MoO6 and g-C3N4 by 1.9 and 2.2 times, respectively. Moreover, it demonstrated an outstanding KA oil selectivity of 99.32 %, showcasing exceptional levels of both conversion and selectivity simultaneously. Through the utilization of photoelectrochemical analysis, research on band structures, experiments on radical trapping and monitoring, we have extensively investigated the mechanism of photocatalysis. The type II charge transfer in Bi2MoO6-g-C3N4 heterojunction restricted the redox capacity of electrons in the conduction band and holes in the valence band, effectively curbing over-oxidation reactions of KA oil, thus achieving remarkable KA oil selectivity. It offers a valuable insight into the creation of heterojunctions to boost the efficiency of photocatalytic oxidation of cyclohexane, showing promise for advancing the field of photocatalysis.

Interaction-Induced Crystalline Topology of Excitons.

We apply the topological theory of symmetry indicators to interaction-induced exciton band structures in centrosymmetric semiconductors. Crucially, we distinguish between the topological invariants inherited from the underlying electron and hole bands and those that are intrinsic to the exciton wave function itself. Focusing on the latter, we show that there exists a class of exciton bands for which the maximally localized exciton Wannier states are shifted with respect to the electronic Wannier states by a quantized amount; we call these excitons shift excitons. Our analysis explains how the exciton spectrum can be topologically nontrivial and sustain exciton edge states in open boundary conditions even when the underlying noninteracting bands have a trivial atomic limit. We demonstrate the presence of shift excitons as the lowest energy neutral excitations of the Su-Schrieffer-Heeger model in its trivial phase when supplemented by local two-body interactions.

Highly Efficient Sunlight‐Driven Photocatalytic Activity of Cu‐Doped BiOBr/g‐C3N4 Nanocomposite via Z‐Scheme Design

AbstractPharmaceutical pollutants introduce highly intricate compounds into the environment due to extensive structural and functional alterations resulting in adverse health effects on organisms. Herein, a novel nanocomposite is designed comprising Cu‐doped BiOBr nanoflakes and g‐C3N4 to form a dual absorber based on the organic‐inorganic electronic interface for photocatalytic degradation of tetracycline (TC). With incorporating Cu in BiOBr and compositing with g‐C3N4, the band gap decreased from 2.74 eV to 2.36 eV for BiOBr:Cu/g‐C3N4, and also light harvesting ability increased. The investigation into the degradation rate considered factors such as pH, TC concentration, photocatalyst dosage, and irradiation time, resulting in a TC degradation efficiency of 98 % within 60 min. In the prepared nanocomposite, photo‐generated electrons of BiOBr can recombine via Cu atoms as a mediator with holes in the valence band of g‐C3N4 due to their band structure position which leads to improved electron/hole separation and enhanced photocatalytic activity. The predominant active species involved in the degradation process were found to be superoxide radicals. Additionally, the photocatalyst exhibited excellent stability, retaining 88 % of its photocatalytic activity after four cycles.

First‐Principle Investigation of zb‐TiGe: A Promising Narrow Bandgap Semiconductor

Using first‐principle calculations, a new compound semiconductor based on titanium (Ti) is predicted. It has been observed that Ti when alloyed with germanium (Ge) can crystallize in the zincblende symmetry, and exhibits semiconducting nature with a narrow bandgap. To test the robustness of the semiconducting nature, the structural properties and electronic band structure have been modeled using three different exchange–correlation functionals, namely, local density approximation, generalized gradient approximation, and Perdew‐Burke‐Ernzerhof for solids. With a nominal composition of 1:1, TiGe exhibits a direct bandgap of 0.58 eV at the “X” point of the Brillouin zone. From lattice dynamics, the structural stability of the compound has been established. The new semiconductor is characterized in detail for its electronic band structure, carrier effective mass, charge density distribution, and linear optical properties. Zb‐TiGe exhibits large effective mass for conduction band holes and tentatively becomes a prototype system to study heavy holes resulting in carrier condensation at the bottom of the conduction band. The linear optical properties of the TiGe are found to be suitable for photosensitive devices in the infrared region. In addition, TiGe may find application in deep‐UV and far‐UV regions because of the surface plasmon resonance at 6.4 eV.

Pressure-controlled luminescence in fast-response barium fluoride crystals

Cross-luminescence (CL) in a barium fluoride (BaF2) scintillator arising from the recombination of a valence band electron and a core band hole results in a fast picosecond decay time. However, the CL emission wavelength in the vacuum ultraviolet region is difficult to detect, and intrinsically intense and slow nanosecond self-trapped exciton (STE) luminescence occurs. Herein, we report a redshift in the CL emission wavelength with high-pressure application. The wavelength of the CL emission shifted from 221 nm to 240 nm when 5.0 GPa was applied via a sapphire anvil cell. Increasing the pressure decreases the core-valence bandgap due to the downward expansion of the valence band, resulting in a decrease in the valence band minimum. The onset of a phase transition from a cubic crystal structure to an orthorhombic crystal structure at 3.7 GPa inhibited the recombination of conduction band electrons and self-trapped holes, leading to the disappearance of the STE emission. Manipulating the band structure of BaF2 by high-pressure application enables control of its luminescence emission, providing a pathway toward solving the problems inherent in this leading fast-response scintillator.

Enhancing the hole utilization efficiency of Ti–Fe2O3 photoelectrode by decorating CoCu-ZIF for efficient photo-assisted rechargeable zinc air batteries

To enhance the oxygen evolution reaction (OER) performance of the zinc-air battery (ZAB), reduce charging voltage, and improve energy utilization efficiency, a sunlight-assisted strategy has been implemented. The photo-assisted rechargeable ZAB was proposed, featuring Ti–Fe2O3 decorated with Co0·8Cu0.2-ZIF as the air electrode. Upon illumination, valence band holes were generated in Ti–Fe2O3, oxidizing Co2+ in Co0·.8Cu0.2-ZIF to Co3+/Co4+, enhancing OER performance, reducing the charging voltage from 2 V to 1.3 V and effectively narrowing the charging-discharging voltage gap from approximately 1.15 V–0.45 V. The Ti–Fe2O3/Co0·8Cu0.2-ZIF structure maintains a round-trip efficiency of 65.3% after 300 cycles. This result demonstrates the successful integration of photoelectrochemical principles with ZAB technology, showcasing its efficacy in solar energy storage and light energy conversion.

Light harvesting S-scheme g-C3N4/TiO2/M photocatalysts for efficient removal of hazardous moxifloxacin

The development of advanced photocatalysts with enhanced efficiency for environmental remediation is critical for addressing persistent organic pollutants like Moxifloxacin. In this study, we present a novel S-scheme heterojunction g-C3N4/TiO2/M photocatalyst designed to optimize light harvesting and charge separation for the effective degradation of Moxifloxacin. The innovative S-scheme configuration enables superior charge transfer dynamics by retaining potent photogenerated electrons in the conduction band of TiO2 and holes in the valence band of g-C3N4, significantly improving photocatalytic performance compared to conventional Type-II systems. Heterogeneous photocatalysis, particularly using TiO2-based materials, offers a promising approach. Here, we synthesized TiO2 hybridized with metal-doped g-C3N4 (GCNTM) via a simple hydrothermal method. The fabricated nanocomposites were characterized using SEM, XRD, FTIR, and UV–Vis (DRS). These GCNTM nanocomposites were employed for the degradation of hazardous Moxifloxacin (MXF) under visible light. Detailed analysis of the photocatalytic mechanism reveals that the synergistic interaction between g-C3N4, TiO2, and the co-catalyst M not only broadens the light absorption spectrum but also enhances the separation and lifespan of charge carriers. Among the synthesized materials, GCNTLa demonstrated the highest degradation efficiency, achieving 96 % removal of MXF. This enhanced activity is attributed to the effective suppression of charge recombination, leading to the generation of reactive species responsible for MXF degradation. Additionally, GCNTM showed remarkable stability and reusability, with only a 6 % reduction in efficiency after five cycles, confirming its high reusability and mechanical stability. Our S-scheme photocatalyst demonstrates a marked increase in the degradation rate of Moxifloxacin under visible light irradiation, highlighting its potential for practical environmental applications.

Trinuclear iron-oxo cocatalyst regulating new electron transfer pathway in Pt loaded bismuth oxychloride for efficient photocatalytic hydrogen production

BiOCl, a traditional p-type semiconductor, finds extensive application in photocatalytic oxidation and degradation, whereas it is less common in photocatalytic water splitting and hydrogen production. Here, the photocatalytic hydrogen production performance of black BiOCl has been examined by the introduction of noble metal platinum and cocatalyst trinuclear iron-oxo cluster. During the 5-h photocatalytic process, the established system significantly augments the hydrogen production efficiency of black BiOCl by an estimated factor of 8.53. Under illumination, trinuclear iron-oxo clusters provide electron recombination with holes in the valence band of the catalyst, thereby increasing the utilization of photogenerated electrons. Additionally, since the specific energy level structure has a significant impact on the cocatalyst function, trinuclear iron-oxo clusters can be suitable in a variety of photocatalytic systems. This new endeavor might present creative design approaches and low-cost cocatalyst alternatives for the photocatalytic hydrogen evolution from the water splitting of conventional p-type semiconductor materials.

Photocatalytic H2 production over CoxNi0.85-xSe decorated TiO2 S-scheme heterojunction

The construction of an S-scheme heterojunction facilitates the efficient separation of charges and preserves its high REDOX potential. In this study, a series of CoxNi0.85-xSe(x=0.05,0.1,0.2,0.3and0.4) and TiO2 nanoparticles were both prepared using solvothermal method, and then Co0.3Ni0.55Se was combined with TiO2 to form Co0.3Ni0.55Se/TiO2 heterojunction through a solvent evaporation strategy for efficient photocatalytic H2 production. It found that the H2 production rate of 10 wt%-Co0.3Ni0.55Se/TiO2 composite can reach 10,070.9 µmol∙g−1∙h−1 with TEOA as a sacrificial agent under a simulated sunlight irradiation, which is 307.9, 33.5and 3.3 times higher than those of pure Co0.3Ni0.55Se,TiO2 and 10 wt%-Ni0.85Se/TiO2, respectively. This enhanced performance is primarily attributed to the formation of an S-scheme heterojunction between TiO2 and Co0.3Ni0.55Se, which effectively enhances light absorption capacity and facilitates charge separation and migration during light irradiation processes. Especially, the S-scheme charge separation can retain the active REDOX capacity of electrons in the conduction band of CoxNi0.85-xSe and the holes in the valance band of TiO2, thereby promoting H2 generation. This study demonstrates that CoxNi0.85-xSe serves as a reducing photocatalyst that offers a viable approach for achieving ideal S-scheme heterojunctions.

Self–Trapped Exciton versus Band–Edge Electron Transitions: Insights of the Factors Affecting the Optical Properties of Lead–Free Sn–Halide Perovskites

AbstractLead–free Sn–halide perovskites (Sn–HPs) are attractive photomaterials due to their lower toxicity, and some of them with higher stability against moisture and water, compared to their Pb‐based analogous. Interestingly, Sn‐HPs can exhibit two types of optical characteristics: the first scenario is known as band‐edge electron transitions [or band‐to‐band (b‐b) emission], where accumulated electrons in the conduction band recombine with holes in the valence band, providing a close separation between the absorption edge/photoluminescence (PL) peak (small Stokes shift). The second scenario is denominated as self‐trapped exciton (STE), where intraband gap energy states are formed to trap photocarriers generated in the perovskite, producing a broadband PL and a large Stokes shift. These optical features have been suitable for developing prominent devices, but there is no consolidated explanation about the key factors influencing the emergence of b–b emission or STE in Sn‐HPs, mainly the presence of these PL mechanisms in a particular perovskite system. This review highlights how the chemical composition, structural defects, and synthetic procedures are pivotal to producing Sn‐HPs with specific b–b or STE features. This will allow the preparation of Sn‐HPs with better quality/stability, and facile modulation of their PL properties, expanding their future applicability in LCD technologies.

Enhanced Photocatalytic Paracetamol Degradation by NiCu-Modified TiO2 Nanotubes: Mechanistic Insights and Performance Evaluation.

Anodic TiO2 nanotube arrays decorated with Ni, Cu, and NiCu alloy thin films were investigated for the first time for the photocatalytic degradation of paracetamol in water solution under UV irradiation. Metallic co-catalysts were deposited on TiO2 nanotubes using magnetron sputtering. The influence of the metal layer composition and thickness on the photocatalytic activity was systematically studied. Photocatalytic experiments showed that only Cu-rich co-catalysts provide enhanced paracetamol degradation rates, whereas Ni-modified photocatalysts exhibit no improvement compared with unmodified TiO2. The best-performing material was obtained by sputtering a 20 nm thick film of 1:1 atomic ratio NiCu alloy: this material exhibits a reaction rate more than doubled compared with pristine TiO2, enabling the complete degradation of 10 mg L-1 of paracetamol in 8 h. The superior performance of NiCu-modified systems over pure Cu-based ones is ascribed to a Ni and Cu synergistic effect. Kinetic tests using selective holes and radical scavengers unveiled, unlike prior findings in the literature, that paracetamol undergoes direct oxidation at the photocatalyst surface via valence band holes. Finally, Chemical Oxygen Demand (COD) tests and High-Resolution Mass Spectrometry (HR-MS) analysis were conducted to assess the degree of mineralization and identify intermediates. In contrast with the existing literature, we demonstrated that the mechanistic pathway involves direct oxidation by valence band holes.

Correlating Chemical Structure and Charge Carrier Dynamics in Phenanthrocarbazole‐Based Hole Transporting Materials for Efficient Perovskite Solar Cells

ABSTRACTPolymeric hole transport materials (HTMs) have emerged because of their potential to produce dopant‐free, efficient, and stable perovskite solar cells (PSCs). Therefore, we engineered 10 novel donor materials (SMH1–SMH10) containing phenanthrocarbazole‐based polymeric structures for organic and PSCs. These molecules underwent bridging‐core modifications using different spacers, such as furan (N1), pyrrole (N2), benzene (N3), pyrazine (N4), dioxane (N5), isoxazole (N6), isoindole (N7), indolizine (N8), double bond (N9), and pyrimidine (N10), in comparison to reference molecule R. The study examined the structure–property relationship and the impact of these modifications on the optical, photovoltaic, photophysical, and optoelectronic characteristics of the newly designed SMH1–SMH10 series. Density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT) calculations were conducted to analyze frontier molecular orbitals, density of states, reorganization energies, open‐circuit voltage, transition density matrix, and charge transfer processes. Results show that the newly designed molecules (SMH1–SMH10) exhibited superior optoelectronics characteristics compared to the R molecule. Among these, SMH4 is the most promising candidate, with a small band gap (2.79 eV), low electron and hole mobility (λe 0.0028 eV, λh 0.0020 eV), lower binding energy (Eb 0.58 eV), high λmax values (656.42 nm in gas, 573.34 nm in chlorobenzene), and a high Voc of 1.30 V. Therefore, this study demonstrated that bridging‐core modifications offer a simple and effective strategy for designing desirable characteristics molecules for photovoltaic applications.

Oxidation cocatalyst/S-scheme junction cooperatively assists photocatalytic H2 production in ternary hybrid: The case of PdO@TiO2-Cu2O

Solar-driven photocatalytic hydrogen production from water splitting holds significant potential in addressing the energy crisis and environmental pollution. However, rapid recombination of photogenerated carriers and insufficient surface catalytic reaction kinetics hinder the photocatalytic process. Constructing the catalytic systems with multi-channel charge-separation can effectively alleviate those issues. In this work, ternary PdO@TiO2-Cu2O composites have been synthesized through precursor calcination and low-temperature reduction, where PdO and Cu2O nanoparticles couple with the TiO2 nanorods. Comparing to single TiO2, binary PdO@TiO2 and TiO2-Cu2O, the PdO@TiO2-Cu2O hybrid exhibits enhanced photocatalytic hydrogen production performance (5831μmol g-1h−1), with a hydrogen production rate more than three times that of single TiO2. Based on the band structures of TiO2 and Cu2O, along with the photochemical/electrochemical, in-situ EPR, Photoluminescence (PL) tests, and work function calculations, the formation of an S-scheme heterojunction at the TiO2-Cu2O interface under light illumination facilitates the recombination of electrons in the conduction band (CB) of TiO2 with holes in the valence band (VB) of Cu2O. In this regard, the established built-in electric field significantly accelerates the transfer of photogenerated charges while preserving their respective strong oxidation and reduction capabilities. Meanwhile, the introduction of PdO enriches the holes and further enhances the rate of charge separation. This S-scheme heterojunction with directional charge transfer and oxidation cocatalyst collectively form multi-channels of charge separation, optimizing charge migration and enabling efficient hydrogen production, thus improving the photocatalytic capability of pristine TiO2. This study provides a rational approach to construct efficient S-scheme heterojunction/oxidation cocatalyst multi-component catalytic systems for water splitting into hydrogen.

(Invited) Luminescent InP Quantum Dots: They're Not Just Like CdSe

Time-resolved photoluminescence (PL) and transient absorption (TA) spectroscopy have been used to elucidate the electron and hole dynamics in high quality InP/ZnSe/ZnS quantum dots (QDs) at room temperature. These dynamics depend critically on the overall In:P ratio. Stoichiometric QDs (those having an In:P ratio close to unity), have PL quantum yields of > 90% and exhibit dynamics that are very simple: both electron and hole relaxation to the bandedge is fast compared to the ~ 40 ps time-correlated photon-counting instrument response and the PL follows a single exponential decay having a time constant of about 26 ns. However, QDs having an In:P ratio greater than about 1.1 maintain PL quantum yields > 90%, but show much more complicated PL kinetics. In the non-stoichiometric QDs, a significant fraction of the PL exhibits a slower risetime. The PL rises over a range of timescales varying from close to the instrument response to approximately 2.0 ns. The time constant of the slowest component increases with increasing InP core size and the fraction of the PL that has the slow risetime increases with excess indium in the particle. The slow risetime is absent in the TA results, indicating that the slow dynamics may be assigned to relaxation in the valence band. The risetime increases with the thickness of the ZnSe shell, varying from < 40 ps for the thinnest (1.1 nm) to about 2.0 ns for the thickest (2.7 nm) ZnSe shells. In addition to the slow risetime, the QDs having excess indium show a significant long-lived (>100 ns) decay component. The magnitude and time constant of this slow decay also increases with ZnSe shell thickness.These results suggest that holes are transiently trapped at sites associated with indium dopants in the ZnSe shell. The trapped hole has negligible overlap with the conduction band electron, making this an optically dark state. The holes are in an equilibrium between the shell traps and the valence band, giving rise to the delayed emission. Several possible assignments of the trapping species can be considered, and a substitutional indium adjacent to a zinc vacancy, In3+/VZn 2-, is the most likely. This assignment is consistent with the observation that trapping occurs only when the QD has excess indium and is supported by experiments showing that the addition of zinc oleate or acetate decreases the extent of trapping, presumably by filling some of the vacancy traps. Further experiments show that addition of alkyl carboxylic acids causes increased trapping, presumably by the formation of zinc oleate, thereby creating additional zinc vacancies. Chloride ion is a common impurity in the synthesis of InP/ZnSe/ZnS QDs and the possibility of In3+/Cl- impurities acting as the hole trap can be also considered. However, additional experimental data on InP/ZnSe/ZnS QDs synthesized in the absence of chloride show the same PL risetimes and delayed emission, eliminating this possibility. Density functional theory calculations further corroborate assignment of the trapping species to In3+/VZn 2-. These calculations show that either a single In2+ ion or an In2+-In3+ dimer is much too easily oxidized to form the reversible traps observed experimentally, while In3+ is far too difficult to oxidize. However, a zinc vacancy adjacent to a substitutional indium is calculated to have its highest occupied orbitals about 1 eV above the top of the valence band of bulk ZnSe, in the appropriate energy range to act as reversible traps for quantum confined holes in the InP valence band.

Construction of Ag3PO4/g-C3N4 Z-Scheme Heterojunction Composites with Visible Light Response for Enhanced Photocatalytic Degradation.

Ag3PO4/g-C3N4 photocatalytic composites were synthesized via calcination and hydrothermal synthesis for the degradation of rhodamine B (RhB) in wastewater, and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and diffuse reflectance spectroscopy (DRS). The degradation of RhB by Ag3PO4/g-C3N4 composites was investigated to evaluate their photocatalytic performance and cyclic degradation stability. The experimental results showed that the composites demonstrated notable photocatalytic activity and stability during degradation. Their high degradation efficiency is attributed to the Z-scheme transfer mechanism, in which the electrons in the Ag3PO4 conduction band and the holes in the g-C3N4 valence band are annihilated by heterojunction recombination, which greatly limits the recombination of photogenerated electrons and holes in the catalyst and enhances the activity of the composite photocatalyst. In addition, measurements of photocurrent (PC) and electrochemical impedance spectroscopy (EIS) confirmed that the efficient charge separation of photo-generated charges stemmed from strong interactions at the close contact interface. Finally, the mechanism for catalytic enhancement in the composite photocatalysts was proposed based on hole and radical trapping experiments, electron paramagnetic resonance (EPR) analysis, and work function evaluation.

(Invited) III-Nitride Ultraviolet LEDs and Lasers for Applications in Biology and Medicine

Ultraviolet (UV) light emitters with large-energy photons are being developed for emerging biology and medicine applications such as sterilization, water/air purification, and medical treatments, as a replacement for mercury vapor lamps. Solid-state UV light-emitting diodes (LEDs) and lasers based on wide bandgap III-Nitrides offer compact sizes, wavelength tuning, long lifetimes, and sustainability over mercury vapor lamps. While visible LEDs and lasers with longer emission wavelengths find widespread commercial uses for solid-state lighting and display, UV emitters with AlGaN heterostructures struggle with poor external quantum efficiencies of typically less than 10%, which drop further when wavelengths get shorter. Therefore, it is extremely challenging to realize high-efficiency UV emitters despite the demand for compact UV light source, especially for disinfection and sterilization from the pandemic as those high-energy photons can break DNA/RNA bonds and deactivate virus/bacteria. Here, I will discuss our recent developments toward realization of high-efficiency UV LEDs and lasers.To enhance the radiative recombination rate (R sp) from the AlGaN quantum well (QW) active region, we had pursued novel QW design to overcome issues from the existence of valence subbands crossover. Specifically, the arrangement of the three energy-degenerate valence subbands - heavy hole (HH), light hole (LH), and the crystal-field split-off hole (CH) bands for high Al-content and low Al-content AlGaN QWs are completely different. The ordering of the valence bands strongly affects the optical matrix element via the oscillator strength, as well as the direction of the photon emission. Our work has proposed promising solution on the use of delta-QW design to address the valence subbands crossover issue, in order to significantly boost up the R sp. In addition, to enhance the extraction efficiency of UV emitters, we demonstrated the realization and characterization of top-down fabricated, electrically driven UV micropillar array LEDs emitting at 286 nm with a narrow, 9 nm linewidth and output power densities up to 35 mW/cm2. Top-down fabrication allows for formation of perfectly uniform arrays of micropillars with easily tunable diameter and pitch, which cannot be achieved with epitaxially grown nanowires without the use of selective area epitaxy. Dry etch damage induced surface losses were avoided through the use of a two-step etch process combining a Cl dry etch and a hydroxyl-based wet etch to form the micropillar arrays. We also revealed that the unique inverse-taper profile of our micropillars could produce significant enhancements in the extraction efficiency with the increased taper angle. Lastly, our developed III-Nitride wet etch by the use of hydroxyl-based chemicals such as potassium hydroxide (KOH) investigated the effects of temperature, concentration, and the damage recovery aspects of hydroxyl etching of III-Nitride nano and micro structures, leading to important smooth surface profiles for micropillar/nanowire LEDs and optimized mirror facets for ridge-emitting UV lasers.

(Keynote) Light Driven H2 Generation in Pt-Tipped CdS Nanorods: Dependence on the Pt Size and CdS Rod Length

Colloidal quantum confined semiconductor-metal nano-heterostructures are a promising class of photocatalysts for solar energy conversion. In these photocatalysts, the semiconductor domain serves as the light absorber and the metal as the catalyst. Such photocatalysts combine the superior light absorption and charge transport properties of the semiconductor with the superior catalytic activity and selectivity of the metal. Furthermore, both domains can be independently tuned to enhance the photocatalytic performance of the heterostructure. Among various semiconductor/metal heterostructures, metal-tipped colloidal semiconductor nanorods have attracted extensive interest because they have been reported to have high quantum efficiencies of light driven H2 generation and their morphology can be systematically tuned. The overall light driven H2 generation process involves multiple elementary charge separation and recombination steps in the semiconductor and across the semiconductor/metal interface as well as proton-coupled electron transfer reactions at the catalytic center. The change of the semiconductor or metal domains can often have effects on multiple competing processes involved in the overall reaction. As a result of these complexities, the mechanisms for the morphological dependence of the observed H2 generation efficiencies are not fully understood, hindering the rational design of these photocatalysts. In this talk, we use Pt tipped CdS nanorods (CdS-Pt) as a model system to examine the effect of Pt size and CdS rod length on their light driven H2 generation efficiency. We show that increasing the Pt particle size increases the overall H2 generation quantum efficiency through both increasing the rate of electron transfer from the CdS to Pt and enhancing the efficiency of water/proton reduction; H2 generation efficiency increases at longer CdS rod length by suppression of charge recombination across the Pt/CdS interface. Furthermore, because of rapid trapping of valence band holes, multi-exciton states in CdS nanorods can be long lived, enabling efficient multi-electron transfer to the Pt. Our work demonstrates that through systematic in situ study of elementary processes involved in the overall H2 generation, it is possible to rationally design and improve semiconductor-metal hybrid photocatalysts.

Photoelectric Studies as the Key to Understanding the Nonradiative Processes in Chromium Activated NIR Materials.

In this study, we synthesized a series of Ga1.98-xInxO3:0.02Cr3+ materials with varying x values from 0.0 to 1.0, focusing on their broadband near-infrared emission and photoelectric properties. Interestingly, photocurrent excitation spectra exhibited behavior consistent with the absorption spectra, indicating the promotion of carriers into the band structure by the 4T1, and 4T2 states of Cr3+ ions. This association suggests that photocurrent in this material is influenced not only by valence to conduction band transitions but also by transitions involving Cr3+ dopants. Our investigation of luminescence quenching mechanisms revealed that nonradiative processes were not directly linked to thermally induced relaxation from the excited state 4T2 to the ground state 4A2, as usually suggested in the literature for this type of material. Instead, we linked it to the thermal ionization of Cr3+ ions. Unexpectedly, this process is unrelated to the transfer of electrons from Cr3+ impurities to the conduction band but is associated with the formation of holes in the valence band. This study provided novel evidence of luminescence quenching via the hole-type thermal quenching process in Cr3+-doped oxides, suggesting potential applicability to other transition metal ions and host materials. Finally, we demonstrated the dual-purpose nature of Ga1.98-xInxO3:0.02Cr3+ as a practical emitter for NIR-pc-LEDs and effective photocurrent for UV detectors. This versatility underscores these materials' practicality and broad application potential in optoelectronic devices designed for near-infrared and ultraviolet applications.