Conduction Band Electrons Research Articles

Titanium Superoxide as a Carrier of a "Long-Lived" Superoxide Anion: An Ab Initio Investigation.

The photoinduced generation of a superoxide anion on the surface of a semiconductor photocatalyst is usually attributed to the reduction of O2 with conduction-band electrons. In the current work, the reaction of TiO2 with O2 giving rise to TiO4 in superoxide and peroxide states has been investigated with ab initio (CAS, CCSD) and DFT (B3LYP) calculations. The ground triplet state and two substates (open-shell singlet (OSS) and closed-shell singlet (CSS)) of a doubly degenerate excited singlet state (a1Δg) are considered as reactive states of oxygen, participating in spontaneous or photoinduced processes, respectively. The triplet and OSS singlet states of TiO4 contain O2- as structural units and can be defined as titanium superoxides. Both states have energy less than the level of the initial pair TiO2+O2 by about 30 kcal/mol. The CSS state of TiO4 has a diperoxide structure Ti4+(O22-)2 and also lies in energy below the initial pair TiO2+3O2. Titanium superoxide is considered to be the carrier of an "exceptionally stable" and "long-lived" superoxide anion, which was earlier synthesized or detected on the surface of TiO2. The low-energy location of the conical intersections on the way from reagents to 3TiO4 allows us to explain the literature data on the spontaneous generation of the "long-lived" superoxide anion on the TiO2 surface.

DFT simulations of photovoltaic parameters of dye‐sensitized solar cells with new efficient sensitizer of indolo[3, 2‐b]carbazole complexes

AbstractDeveloping economical and high‐performing sensitizers is crucial in advancing dye‐sensitized solar cells (DSSCs) and optoelectronics. This research paper explores the potential of novel red light‐absorbing organic dyes based on Indolo[3,2‐b]carbazole (ICZ) as the donor applied in co‐sensitizer‐free DSSCs for breakthroughs in photovoltaic (PV) applications. DFT and TD‐DFT based computational methods were employed to calculate the conduction band levels, electron injection capabilities, and power conversion efficiency (PCE) of metal‐free organic dyes (ICZ1–ICZ9) having D‐A‐π‐A architecture. Comprehensive analyses included NBO, DOS, FMO, ICT, MEP, binding energy, and TDM analysis. Quantum chemical calculations of the structural, photochemical, and electrochemical properties, as well as the key parameters, reveals that all the designed dyes could be an excellent candidate for high‐efficiency DSSCs due the small energy gap (2.130–1.947 eV), longer wavelength absorption (759.47–520.63 nm), longer lifetimes (15.65–6.67 ns), a lower ΔGreg (0.29–0.14 eV), a significant dipole moment changes (31.489–16.195D), LHE (0.95‐0.46), the large qCT (0.962–0.689), small DCT (7.657, 4.897 Å), and VOC (1.13–0.86 eV). This quantum simulation showed that, when compared to reference D8, the photovoltaic dyes ICZ8, ICZ2, and ICZ7 are recognized as being eye‐catching. Furthermore, dye@(TiO2)9 cluster model results demonstrate promising prospects for enhancing the photovoltaic (PV) performance of ICZ1–ICZ9 dyes by electron injection and conduction band (CB) engineering. This study will help the experimentalists for developing ICZ‐based PVs as more efficient and sustainable energy solutions.

Electron Transfer Dynamics at Dye-Sensitized SnO2/TiO2 Core/Shell Electrodes in Aqueous/Nonaqueous Electrolyte Mixtures.

The dynamics of photoinduced electron transfer were measured at dye-sensitized photoanodes in aqueous (acetate buffer), nonaqueous (acetonitrile), and mixed solvent electrolytes by nanosecond transient absorption spectroscopy (TAS) and ultrafast optical-pump terahertz-probe spectroscopy (OPTP). Higher injection efficiencies were found in mixed solvent electrolytes for dye-sensitized SnO2/TiO2 core/shell electrodes, whereas the injection efficiency of dye-sensitized TiO2 electrodes decreased with the increasing acetonitrile concentration. The trend in injection efficiency for the TiO2 electrodes was consistent with the solvent-dependent trend in the semiconductor flat band potential. Photoinduced electron injection in core/shell electrodes has been understood as a two-step process involving ultrafast electron trapping in the TiO2 shell followed by slower electron transfer to the SnO2 core. The driving force for shell-to-core electron transfer increases as the flat band potential of TiO2 shifts negatively with increasing concentrations of acetonitrile. In acetonitrile-rich electrolytes, electron injection is suppressed due to the very negative flat band potential of the TiO2 shell. Interestingly, a net negative photoconductivity in the SnO2 core is observed in mixed solvent electrolytes by OPTP. We hypothesize that an electric field is formed across the TiO2 shell from the oxidized dye molecules after injection. Conduction band electrons in SnO2 are trapped at the core/shell interface by the electric field, resulting in a negative photoconductivity transient. The overall electron injection efficiency of the dye-sensitized SnO2/TiO2 core/shell photoanodes is optimized in mixed solvents. The ultrafast transient conductivity data illustrate the crucial role of the electrolyte in regulating the driving forces for electron injection and charge separation at dye-sensitized semiconductor interfaces.

Dimensionally Intact Construction of Ultrathin S-Scheme CuFe2O4/ZnIn2S4 Heterojunctional Photocatalysts for CO2 Photoreduction.

The conversion of CO2 into carbon-neutral fuels such as methane (CH4) through selective photoreduction is highly sought after yet remains challenging due to the slow multistep proton-electron transfer processes and the formation of various C1 intermediates. This research highlights the cooperative interaction between Fe3+ and Cu2+ ions transitioning to Fe2+ and Cu+ ions, enhancing the photocatalytic conversion of CO2 to methane. We introduce an S-scheme heterojunction photocatalyst, CuFe2O4/ZnIn2S4, which demonstrates significant efficiency in CO2 methanation under light irradiation. The CuFe2O4/ZnIn2S4 heterojunction forms an internal electric field that aids in the mobility and separation of exciton carriers under a wide solar spectrum for exceptional photocatalytic performance. Remarkably, the optimal CuFe2O4/ZnIn2S4 heterojunction system achieved an approximately 68-time increase in CO2 conversion compared with ZnIn2S4 and CuFe2O4 nanoparticles using only pure water, with nearly complete CO selectivity and yields of CH4 and CO reaching 172.5 and 202.4 μmol g-1 h-1, respectively, via a 2-electron oxygen reduction reaction (ORR) process. The optimally designed CuFe2O4/ZnIn2S4 heterojunctional system achieved approximately 96% conversion of BA and 98.5% selectivity toward benzaldehyde (BAD). Additionally, this photocatalytic system demonstrated excellent cyclic stability and practical applicability. The photogenerated electrons in the CuFe2O4 conduction band enhance the reduction of Fe3+/Cu2+ to Fe2+/Cu+, creating a microenvironment conducive to CO2 reduction to CO and CH4. Simultaneously, the appearance of holes in the ZnIn2S4 valence band facilitates water oxidation to O2. The synergistic function within the CuFe2O4/ZnIn2S4 heterojunction plays a pivotal role in facilitating charge transfer, accelerating water oxidation, and thereby enhancing CO2 reduction kinetics. This study offers valuable insights and a strategic framework for designing efficient S-scheme heterojunctions aimed at achieving carbon neutrality through solar fuel production.

Enhanced photocatalytic activity of g-C3N4/Bi2WO6 heterojunction via Z-scheme charge-transfer mechanism

In this study, g-C3N4/Bi2WO6 (CN/BWO) photocatalytic composite materials were prepared using a combination of calcination and solvothermal methods. The coiled sheet CN and the nanosheet BWO are coupled to form Z-scheme semiconductor junctions. For the close alignment between BWO conduction band (CB) and CN valence band (VB), photogenerated electrons originating from the BWO CB readily recombine with holes from the CN VB, which results in the accumulation of photogenerated holes in the BWO VB, exhibiting remarkable oxidation capability, and photogenerated electrons in the CN CB, displaying strong reducibility. This mechanism plays a pivotal role in the generation of ·O2– and ·OH radicals, optimizing the photocatalytic performance. As the atomic proportion of CN/BWO was 9:20, it exhibits a degradation degree of 90.2 % for rhodamine B (RhB) after 60 min illumination, significantly higher than pure BWO (44.0 %). Repetitive experiment results demonstrated the sample's good stability. Additionally, based on electrochemical tests and active species experiment results, the photocatalytic mechanism of the CN/BWO Z-scheme semiconductor structure involving photogenerated charge separation, migration, and photocatalysis was proposed.

Valence instability and collapse of ferromagnetism in EuB[formula omitted] at high pressures

Despite the simplicity of their cubic crystal lattice, rare-earth hexaborides display complex physical properties including a (long debated) onset of metallization via magnetic polaron formation at Tc1≈ 15 K preceding ferromagnetic ordering at Tc2≈ 12 K. In this work, we used applied pressure to tune the interplay between electronic structure and magnetism in EuB6. We probed the magnetism, valence, and structure of EuB6 under quasi-hydrostatic pressures up to 30 GPa using X-ray techniques. Our findings show evidence for collapse of ferromagnetism above 20 GPa following a monotonic increase of mean Eu valence. While X-ray diffraction measurements in the paramagnetic state at room temperature show that the lattice retains cubic symmetry, a measurable quadrupole interaction seen by time-domain synchrotron Mössbauer spectroscopy suggests a lowering of symmetry associated with magnetic ordering, becoming more prominent across the magnetic transition. The interplay between conduction band electron count and magnetism observed under applied pressure in EuB6 opens possibilities for fine-tuning metallization and magnetic properties of similar Eu-based semi-metal systems.

Plasmon-Induced Hot Electrons in Nanostructured Materials: Generation, Collection, and Application to Photochemistry.

Plasmon refers to the coherent oscillation of all conduction-band electrons in a nanostructure made of a metal or a heavily doped semiconductor. Upon excitation, the plasmon can decay through different channels, including nonradiative Landau damping for the generation of plasmon-induced energetic carriers, the so-called hot electrons and holes. The energetic carriers can be collected by transferring to a functional material situated next to the plasmonic component in a hybrid configuration to facilitate a range of photochemical processes for energy or chemical conversion. This article centers on the recent advancement in generating and utilizing plasmon-induced hot electrons in a rich variety of hybrid nanostructures. After a brief introduction to the fundamentals of hot-electron generation and decay in plasmonic nanocrystals, we extensively discuss how to collect the hot electrons with various types of functional materials. With a focus on plasmonic nanocrystals made of metals, we also briefly examine those based upon heavily doped semiconductors. Finally, we illustrate how site-selected growth can be leveraged for the rational fabrication of different types of hybrid nanostructures, with an emphasis on the parameters that can be experimentally controlled to tailor the properties for various applications.

Impact of Photo-remediation on Anthracene PAHs in treated wastewater using ZnO/TiO2/H2O2 Catalysis

The remediation of carcinogenic Polycyclic Aromatic Hydrocarbons )PAHs( such as Anthracene (3 Rings) in different sources of wastewater was examined using a mix of Zink Oxide, Titanium Oxide, and Hydrogen peroxide (ZnO/ TiO2/H2O2). Eleven wastewater sources were collected from different industrial wastewater and treated wastewater (5 Farms, Main treatment plant, Tanning factory treated wastewater, Tanning factory non-treated wastewater, Carton factories, Factories Lake, and Grease refining plants. Anthracene was extracted by QuEChERS methodology and Analyzed by GCMSMS/TQD. Remediation techniques were applied by using different UV wavelengths irradiation on photolysis of PAHs under two wavelengths (254 and 306 nm) UV irradiation with ZnO + TiO2+ H2O2catalysts for 10 h. Also, the influence of remediation time and several parameters on Anthracene photolysis have been studied. The results indicate that Tanning factory non-treated wastewater had the highest concentration of Anthracene PAHs. The average recovery of Anthracene ranged from 92-96% and Detection Limit (DL) was 5 µg/l. The results of Anthracene concentration in tested wastewater ranged from 21.09 -223.69 µg/l. Also, the results show the anthracene was not detected after 5, 8, and 10h after the remediation using UV 254nm ZnO + TiO2+ H2O2. On the other side, the Anthracene was not detected after 3, 5, and 8h after the remediation using UV 254nm/ZnO + TiO2+ H2O2. Generally, the results of Photoremediation were effective and sufficient for the Anthracen. The impact of photocatalytic illumination of ZnO + TiO2 + H2O2yields valence band holes and conduction band electrons, which interact with the surface adsorbed molecular oxygen to give superoxide radical anions, and finally, the water produces radicals of HO•. These radicals oxidize the target molecule (Anthracene) to Anthraquinone.

Insights into the Crystallinity-Dependent Photochemical Productions of Reactive Oxygen Species from Iron Minerals.

Iron minerals are widespread in earth's surface water and soil. Recent studies have revealed that under sunlight irradiation, iron minerals are photoactive on producing reactive oxygen species (ROS), a group of key species in regulating elemental cycling, microbe inactivation, and pollutant degradation. In nature, iron minerals exhibit varying crystallinity under different hydrogeological conditions. While crystallinity is a known key parameter determining the overall activity of iron minerals, the impact of iron mineral crystallinity on photochemical ROS production remains unknown. Here, we assessed the photochemical ROS production from ferrihydrites with different degrees of crystallinity. All examined ferrihydrites demonstrated photoactivity under irradiation, resulting in the generation of hydrogen peroxide (H2O2) and hydroxyl radical (•OH). The photochemical ROS production from ferrihydrites increased with decreasing ferrihydrite crystallinity. The crystallinity-dependent photochemical •OH production was primarily attributed to conduction band reduction reactions, with the reduction of O2 by conduction band electrons being the rate-limiting key process. Conversely, the crystallinity of iron minerals had a negligible influence on photon-to-electron conversion efficiency or surface Fenton-like activity. The difference in ROS productions led to a discrepant degradation efficiency of organic pollutants on iron mineral surfaces. Our study provides valuable insights into the crystallinity-dependent ROS productions from iron minerals in natural systems, emphasizing the significance of iron mineral photochemistry in natural sites with abundant lower-crystallinity iron minerals such as wetland water and surface soils.

Conduction Band Electron Density Variation Leads to Different Degrees of Ultrafast Laser Ablation of Aluminum-Silver Bimetals in Double Distilled Water

Conduction Band Electron Density Variation Leads to Different Degrees of Ultrafast Laser Ablation of Aluminum-Silver Bimetals in Double Distilled Water

Highly intrinsic carrier mobility in tin diselenide crystal accessed with ultrafast terahertz spectroscopy

Tin diselenide (SnSe2), a layered transition metal dichalcogenide (TMDC), stands out among other TMDCs for its extraordinary photoactive ability and low thermal conductivity. Consequently, it has stimulated many influential researches on photodetectors, ultrafast pulse shaping, thermoelectric devices, etc. However, the carrier mobility in SnSe2, as determined experimentally, remains limited to tens of cm2V-1s-1. This limitation poses a challenge for achieving high-performance SnSe2-based devices. Theoretical calculations, on the other hand, predict that the carrier mobility in SnSe2 can reach hundreds of cm2V-1s-1, approximately one order of magnitude higher than experimental value. Interestingly, the carrier mobility could be underestimated significantly in long-range transportation measurements due to the presence of defects and boundary scattering effects. To address this discrepancy, we employ optic pump terahertz probe spectroscopy to access the photoinduced dynamical THz photoconductivity of SnSe2. Our findings reveal that the intrinsic carrier mobility in conventional SnSe2 single crystal is remarkably high, reaching 353.2 ± 37.7 cm2V-1s-1, consistent with the theoretical prediction. Additionally, dynamical THz photoconductivity measurements reveal that the SnSe2 crystal containing rich defects efficiently capture photoinduced conduction-band electrons and valence-band holes with time constants of ∼20 and ∼200 ps, respectively. Meanwhile, we observe an impulsively stimulated Raman scattering at 0.60 THz. Our study not only demonstrates ultrafast THz spectroscopy as a reliable method for determining intrinsic carrier mobility and detection of low frequency coherent Raman mode in materials but also provides valuable reference for the future application of high-performance SnSe2-based devices.

Promoting the optoelectronic and nonlinear optics properties of MoS2 nanosheets via metal Al anchoring

Molybdenum disulfide (MoS2) has attracted much attention in the field of optoelectronic materials due to its stability and adjustable bandgap structure. However, improving the optoelectronic properties of MoS2 is still a challenging research. Herein, Al doped MoS2 (AMS) films were prepared by a simple single-step magnetron sputtering method. The bonding modes of Al implantation and auxiliary MoS2 were investigated by adjusting metal Al anchoring. The successful synthesis of AMS films was confirmed by the analysis of X-ray diffraction and X-ray photoelectron spectroscopy measurements to investigate the diffraction peaks of Al and Al2S3 and the valence electron structures of Al3+. Compared to MoS2, the A1g Raman peaks of AMS films are slightly blue-shifted, and the peak positions of both Mo3d and S2p are slightly shifted towards higher binding energies. This is attributed to the surface plasmon resonance effect produced by Al doping resulting in a large amount of electron transfer to the conduction band (CB) of MoS2. In addition, the density functional theory calculations reveal that Al doping of MoS2 results in a higher concentration of electrons in CB of MoS2, the band gap of MoS2 can be adjusted by changing the doping concentration of Al. The Z-scan results illustrated that MoS2 was converted from saturable absorption to reverse saturable absorption (RSA) by adjusting the sputtering power of Al. This is attributed to the fact that Al doping increases the electron concentration in the CB of MoS2, which promotes the RSA of the excited states and doping energy levels of AMS films. The values of the nonlinear absorption coefficients of AMS films are 2–5 times higher than those of MoS2, which significantly improves the nonlinear absorption performance of MoS2. The carrier relaxation process and kinetic mechanism of AMS films were investigated by transient absorption spectroscopy, moderate doping of Al can effectively improve the carrier lifetime. This implies that AMS films have good optoelectronic properties and have a wide application potential in optoelectronic devices.

Visible-light driven photodegradation of low-density polyethylene (LDPE) using BiOCl–ZrO2 nanocomposite: A sustainable strategy for mitigating plastic pollution

This study aims to reduce plastic pollution by decomposing low-density polyethylene (LDPE) through an environmentally friendly approach using a novel BiOCl–ZrO2 nanocomposite under visible-light irradiation at room temperature. Visible-light irradiation is a form of clean energy, so we explored the feasibility and prospective solution for plastic waste mitigation by utilizing visible-light to attain sustainable development goal 7 (SDG 7). To fabricate photodegradable LDPE, it was blended with BiOCl nanoparticles (NPs) and its nanocomposite (BiOCl–ZrO2) separately via a facile solution casting method. The fabricated samples were assessed for the degradation of LDPE before and after 24 days of visible-light irradiation at room temperature. The prepared nanocomposites were thoroughly characterized by different analytical techniques, including XRD, FT–IR, XPS, FE–SEM, TGA, BET and UV–Vis DRS. The successful photodegradation of low-density polyethylene (LDPE) using a BiOCl–ZrO2 nanocomposite is supported by the presence of a higher carbonyl index, as evidenced by FT–IR analysis. The field-emission scanning electron microscopy (FE–SEM) analysis unveiled numerous perforations and prominent coarse morphological attributes, suggesting significant decomposition and disintegration of the LDPE film across the active surface sites of BiOCl–ZrO2. The weight reduction of LDPE@BiOCl–ZrO2 (600 ˚C) (10 wt%) composite film reached 48.67% under visible-light irradiation for 24 days at room temperature. The degradation rate exhibited significant sensitivity to variations in the concentration of the BiOCl–ZrO2 nanocomposite within the LDPE film. Investigation of the photodegradation mechanism suggested the formation of a type–II heterojunction–based photocatalytic system. The relatively low bandgap energy of ZrO2 (3.1 eV), facilitates the rapid migration of conduction band electrons to the conduction band of BiOCl. This migration process is facilitated by the favourable energy level alignment between the conduction bands of ZrO2 and BiOCl, enabling efficient electron transfer between the two materials. The large band gap of BiOCl (3.56 eV) permits the movement of valence band holes to the ZrO2 valance band. The spontaneous circulation of charge carriers within the heterostructure crystal maintains the charge separation and defers the recombination rate for an extended period. The photodegraded LDPE fragments are biodegradable and help to reduce plastic pollution. The environmental friendliness of the BiOCl–ZrO2 nanocomposite-assisted plastic waste remediation process was investigated using carbon footprint measurement. A tentative estimation suggested that the remediation process of 100 Kg of plastic waste may contribute to around 0.133 tons of carbon footprint.

Gadolinium modified g-C3N4 for S-Scheme heterojunction with monoclinic-WO3: Insights from DFT studies and related charge carrier dynamics

Modifying the surface structures of g-C3N4 through interfacial coupling with other semiconductors has been spotlighted as an efficient approach for improving photocatalytic efficiency. With the surge of S-scheme heterojunctions, the research is intensified towards designing this kind of composite for energy-environmental-related applications. In this context, a new approach involving surface modifications of g-C3N4 through Gd species and integrating with monoclinic-WO3 via a wet chemical approach to form S-scheme heterojunctions is investigated. The characterization results attested that the adopted protocol promotes the better dispersion of Gd species over the g-C3N4 surface and rigidly integrates with WO3. The optical response of the composite spanned a significant portion of the visible region in the solar spectrum. The computational studies and the findings of the Mott-Schottky plot collectively suggested that the position of band edges qualifies for the formation of S-scheme heterojunction. The results derived from photocurrent response measurements and photoluminescence technique attribute to the effective charge carrier separation in the heterostructure. The rate constant of Gd-g-C3N4/WO3 was 1.48 × 10−2 min−1 which was approximately 4.35 and 2.27 times greater than that of WO3 (0.34 × 10−2 min−1) and g-C3N4/WO3 (0.65 × 10−2 min−1) respectively. Furthermore, RhB degradation in the presence of scavengers validated the participation of superoxide and hydroxyl radicals in the degradation mechanisms. This was possible only when the conduction band electrons of WO3 recombined with the valence band holes of Gd-modified g-C3N4. The present work helps to understand the S-scheme heterojunction formation between surface-modified g-C3N4 and metal oxides and retain the involvement of energetic charge carriers in the desired redox reactions.

Sunlight-Driven Nitrate-to-Ammonia Reduction with Water by Iron Oxyhydroxide Photocatalysts.

The photocatalytic reduction of harmful nitrates (NO3-) in strongly acidic wastewater to ammonia (NH3) under sunlight is crucial for the recycling of limited nitrogen resources. This study reports that a naturally occurring Cl--containing iron oxyhydroxide (akaganeite) powder with surface oxygen vacancies (β-FeOOH(Cl)-OVs) facilitates this transformation. Ultraviolet light irradiation of the catalyst suspended in a Cl--containing solution promoted quantitative NO3--to-NH3 reduction with water under ambient conditions. The photogenerated conduction band electrons promoted the reduction of NO3--to-NH3 over the OVs. The valence band holes promoted self-oxidation of Cl- as the direct electron donor and eliminated Cl- was compensated from the solution. Photodecomposition of the generated hypochlorous acid (HClO) produced O2, facilitating catalytic reduction of NO3--to-NH3 with water as the electron donor in the entire system. Simulated sunlight irradiation of the catalyst in a strongly acidic nitric acid (HNO3) solution (pH ∼ 1) containing Cl- stably generated NH3 with a solar-to-chemical conversion efficiency of ∼0.025%. This strategy paves the way for sustainable NH3 production from wastewater.

On the specific behavior of the work function and surface potential of an asymmetric metal-dielectric nanosandwich

We examine thin film on a dielectric substrate (vacuum/Al/SiO2) in the stabilized jellium model and the Kohn–Sham method. We investigate surface and size effects on the effective potential and the electron work function, and analyze the spatial distributions of electrons and potentials. It is found that a dielectric environment generally leads to a decrease in the work function. The effect of dielectric confinement for the electron work function of the asymmetric metal-dielectric nanosandwiches is reduced only by the surface area weighted average value of the dielectric constants. This conclusion follows from the application of the Gauss theorem for a conducting sphere with an inhomogeneous dielectric coating. The flow of electrons from the dielectric face to the vacuum one due to the contact potential difference manifests itself in the appearance of an additional dipole between the left and right face within the spatial distributions of ions. This leads to the fact that in a vacuum the electrostatic and effective potentials change sign twice, as a result of which a potential barrier appears above the vacuum level. We introduced the position of an electron conduction band in the dielectric as the input parameter in the self-consistency procedure for one of the sandwich approximations. As it turned out, the barrier height depends only on the used local or non-local approximation of the exchange-correlation energy. The nontrivial origin and behavior of the calculated effective potential on the vacuum side of the film, as well as the reasons for it, are discussed.

Why Is the Bandgap of GaP Indirect While That of GaAs and GaN Are Direct?

Many III–V semiconductors possess direct bandgaps and are thus widely applied in optoelectronics. Although GaN (either in wurtzite phase or zinc blende phase), GaAs, and GaSb are well‐known direct‐gap semiconductors, GaP exhibits an indirect bandgap nevertheless. In this work, the generic rule of energy gaps in GaN, GaP, and GaAs of the zinc blende phase is analyzed, and the trends of gap variation are studied concerning the lattice constant and anion electronegativity. It turns out that GaP actually manifests a normal behavior, the reason why GaN surprisingly has a direct gap is analyzed through examining and perturbing its valence band as well as conduction band (CB). The CB electron shows a non‐negligible probability to emerge near the N cores. The attractive nucleus potential pulls down the CB more strongly at Γ, which is in principle further supported through an analysis of the Kronig–Penney model. The difference between GaP and GaN in this respect is also analyzed in detail.

ZnS-coated Yb3+-doped perovskite quantum dots: A stable and efficient quantum cutting photon energy converter for silicon-based electronics

Yb3+ doped lead halide perovskite quantum dots (PeQDs) with efficient quantum cutting emission are thought to be the most promising photon energy converter for improving the performance of silicon-based electronics. Nevertheless, the low external quantum efficiency (EQE) and instability make it unfeasible for industrial use. Here, we present a unique PeQDs@ ZnS core–shell device that achieves outstanding stability and up to 39 % EQE by effectively controlling energy transfer from the PeQDs to the Yb3+ through ZnS coating. These advances are attributed to the large UV absorption and the strong localized effect of the ZnS shells on the conduction band electrons of the PeQDs. Density functional theory (DFT) first-principles simulations indicate that ZnS coating can facilitate the energy transfer of PeQDs to Yb3+. Power conversion efficiency (PCE) of silicon solar cells was significantly enhanced by ZnS-coated Yb3+ doped PeQDs, yielding a noteworthy 13.5 % relative PCE improvement over 30 measurement sets. Significantly, the stability of SSCs with ZnS-coated PeQDs films is considerably improved, resulting in a capped device T80 lifespan of up to 11,224 h. Moreover, ZnS-coated PeQDs films can significantly boost the EQE of silicon photodiodes (Si-PDs) and extend their response to deep ultraviolet light. This paper presents an efficient and consistently stable photon energy converter with great commercialization potential.

Towards achieving an ideal convergence of light and heavy electron conduction bands in SnTe: Insights into copper doping

In recent years, tin telluride has garnered significant attention in the field of thermoelectrics, offering a promising avenue for sustainable ecofriendly conversion of waste heat into electricity. The unique electronic structure of this material makes it a compelling candidate for exploring innovative strategies to enhance its transport properties by employing substitutional doping. Among myriad elements doped, copper has been considered an intriguing candidate due to its ability to lower the thermal conductivity. However, its impact on the electronic structure has not been thoroughly explored till date. Herein, we investigate a nuanced aspect of copper doping, specifically focusing on its impact on tuning the electronic structure of SnTe. Significantly, our findings reveal a novel dimension to copper doping, showcasing its potential to enhance n-type performance in SnTe through the near-perfect convergence of its conduction bands - a feature not observed when doped in GeTe. We also shed the light on improvement of the p-type performance by means of valence band convergence and increased band gap. Furthermore, we reveal that copper doping allows the contribution of low-lying bands in SnTe to participate in transport, ensuring a higher Seebeck coefficient across the entire temperature range. Overall, this work provides a panoramic view of role of copper in improving the Seebeck co-efficient of SnTe making it a potential lead-free material for several thermoelectric applications.

Giant amplification of Berezinskii-Kosterlitz-Thouless transition temperature in superconducting systems characterized by cooperative interplay of small-gapped valence and conduction bands

Two-dimensional superconductors and electron-hole superfluids in van der Waals heterostructures having tunable valence and conduction bands in the electronic spectrum are emerging as rich platforms to investigate novel quantum phases and topological phase transitions. In this work, by adopting a mean-field approach considering multiple-channel pairings and the Kosterlitz-Nelson criterion, we demonstrate giant amplifications of the Berezinskii-Kosterlitz-Thouless (BKT) transition temperature and a shrinking of the pseudogap for small energy separations between the conduction and valence bands and small density of carriers in the conduction band. The presence of the holes in the valence band, generated by intra-band and pair-exchange couplings, contributes constructively to the phase stiffness of the total system, adding up to the phase stiffness of the conduction band electrons that is boosted as well, due to the presence of the valence band electrons. This strong cooperative effect avoids the suppression of the BKT transition temperature for low density of carriers, that occurs in single-band superconductors where only the conduction band is present. Thus, we predict that in this regime, multi-band superconducting and superfluid systems with valence and conduction bands can exhibit much larger BKT critical temperatures with respect to single-band and single-condensate systems.