Large Band Gap Research Articles

Electronic, optical, elastic, piezoelectric and vibrational properties of P63 KLiSO4

Abstract KLiSO4 of the P63 symmetry is a well refined crystal at room temperature, which is a pyroelectric material with a large second harmonic generation response. However, its fundamental physical properties are still not well studied. In this work, first principles calculations are performed to study its electronic, optical, elastic, piezoelectric and vibrational properties. The results indicate that it is an ionic crystal with a large indirect band gap. Calculated optical properties imply that P63 KLiSO4 has little optical anisotropy at low frequencies. Obtained elastic constants reveal that it is mechanically stable but anisotropic, as illustrated by the directional bulk and shear moduli. Piezoelectric coefficients, dielectric constants, and Born effective charges (BECs) are computed using the density functional perturbation method. Studies disclose that it has a greater piezoelectric coefficient along the c axis. The ions have more contribution to the total dielectric constants than the electrons. The S atoms have the largest BECs. The phonon vibrational modes at the Brillouin zone center are analyzed by the factor group theory. Its infrared and Raman spectra are simulated. The causation for the vanishment of some infrared peaks in the computed infrared spectrum is uncovered. Additionally, elastic related moduli, hardness, melting point and electromechanical coupling coefficients of P63 KLiSO4 are also predicated.

Managing Edge States in Reduced-Dimensional Perovskites for Highly Efficient Deep-Blue LEDs.

Pure-halide reduced-dimensional perovskites, featuring large exciton binding energy and tunable bandgap, show great potential for high-efficiency deep-blue perovskite light-emitting diodes (PeLEDs). However, their efficiency, particularly in the low n-value phase domain ("n" represents the number of octahedral sheets), lags behind analogous perovskite emitters. Herein, it is demonstrated that the vibration of edge-dangling octahedra in the low n-value phase activates notorious exciton-phonon (EP) coupling, thereby deteriorating efficiency. To address this issue, an approach is reported to manage edge-state lattices by introducing tris(4-fluorophenyl) phosphine (TFP) ligands. Attributed to the large steric hindrance of TFP ligands and their strong binding affinity for edge-dangling octahedra, the edged-octahedral tilting reconstruction can effectively suppress lattice vibration and inhibit EP coupling. This strategy yields deep-blue emitting film with a spectral linewidth of 21nm and a photoluminescence quantum yield of 85% at low excitation densities. The resulting PeLEDs achieve deep-blue emission at 469nm, with a maximum luminance of 2,428cdm-2 and a maximum external quantum efficiency of 10.4%, marking them among the most efficient deep-blue PeLEDs reported. The strategy also showcases universality for higher n-value reduced-dimensional perovskites. It is believed that the observation, along with the edge-state management strategy, lays the groundwork for further advancements in reduced-dimensional perovskite optoelectronic devices.

Wave Function Localization Reduces the Bandgap of Disordered Double Perovskite Cs2AgBiBr6.

Double perovskite Cs2AgBiBr6 is a promising alternative to lead-based perovskites with excellent stability and attractive optoelectronic properties. However, a relatively large bandgap severely limits its performance in many applications such as solar cells and photodetectors. It has been reported that a random distribution of Ag and Bi atoms in Cs2AgBiBr6 effectively reduces its bandgap without introducing dopants or impurities, while the mechanism remains unclear. Here, using density functional theory calculations, we demonstrate that the Ag-Bi disorder in Cs2AgBiBr6 generates localized electronic states as band edges to regulate the bandgap. The disordered structures segregate Ag and Bi atoms in the lattice, and the formed homoatomic clusters lead to wave function localization. Moreover, the bandgap decrease exhibits a non-monotonic dependence on the degree of disorder. Our results are comparable with experimental observations and provide crucial insights into understanding the order-disorder transition in double perovskites.

Unveiling the Pockels coefficient of ferroelectric nitride ScAlN

Nitride ferroelectrics have recently emerged as promising alternatives to oxide ferroelectrics due to their compatibility with mainstream semiconductor processing. ScAlN, in particular, has exhibited remarkable piezoelectric coupling strength (K2) comparable to that of lithium niobate, making it a valuable choice for RF filters in wireless communications. Recently, ScAlN has sparked interest in its use for nanophotonic devices, chiefly due to its large bandgap facilitating operation in blue wavelengths coupled with promises of enhanced nonlinear optical properties such as a large second-order susceptibility (χ(2)). It is still an open question whether ScAlN can outperform oxide ferroelectrics concerning the Pockels effect—an electro-optic coupling extensively utilized in optical communications devices. In this paper, we present a comprehensive theoretical analysis and experimental demonstration of ScAlN’s Pockels effect. Our findings reveal that the electro-optic coupling of ScAlN, despite being weak at low Sc concentration, may be significantly enhanced and exceed LiNbO3 at high levels of Sc doping, which points the direction of continued research efforts to unlock the full potential of ScAlN.

Cu2ZnSnS4 Nanoparticles as an Efficient Photocatalyst for the Degradation of Diclofenac in Water

Dangerous emerging water micropollutants like Diclofenac are harming ecosystems all over the planet, and immediate action is needed. The large bandgap photocatalysts conventionally used to degrade them need to be more efficient. Cu2ZnSnS4, a well-known light absorber in photovoltaics with a bandgap of 1.5 eV, can efficiently harvest an abundant portion of the solar spectrum. However, its photocatalytic activity has so far only been reported in relation to the degradation of organic dyes, and it is usually used as a benchmark to assess the activity of a photocatalyst without testing its actual potential on a hazardous water micropollutant conventionally encountered in primary and secondary waters. Here, we report the promising photocatalytic activity of Cu2ZnSnS4 nanoparticles in the degradation of Diclofenac, chosen as a benchmark for dangerous emerging water micropollutants.

Photodetectors performance of nanostructured materials in antimony III-V InGaAsSb/AlGaAsSb interband cascade structures

The aim of the study is to increase the performance of solar conversion by integrating nanostructured materials within conventional solar cells by employing multi-energy stages (i.e., interband and intersubband) in cascade systems to overcome the absorption length barrier and achieve large photo-generated carrier values. Specifically, InGaAsSb/Al GaAsSb MQWs are investigated with narrow well widths (2-20 nm) and transition energies of the structures are calculated for varied well/barrier widths and depths using numerical modelling. The results show that both interband and intersubband transitions are valuable for improving photovoltaic and photodetection applications, but their mechanisms and applications are distinct, so understanding and controlling these transitions within semiconductor materials is essential for optimising the performance of devices in both areas of optoelectronics, including strain as an important parameter of integrity. The data suggests that a single electron requires multiple photons to be transported, with the formation of a type-I broken-gap alignment between AlGa AsSb (barrier) and InGaAsSb (well). A wide range of wavelengths, from visible to medium infrared (MIR), will greatly enhance solar spectrum absorption. The long-term goal is to combine the thermal properties of antimonies (GaSbInSb) with a low band gap and the optical properties of arsenide (GaAsAlAs) with a large band gap.

A high-performance selenium nanoflake-based avalanche photodetector

Photodetectors are now indispensable in our daily lives, and there is a pressing need to explore new materials and mechanisms that can push the boundaries of device performance. Two-dimensional (2D) van der Waals (vdW) semiconductors have emerged recently as a promising material platform with exceptional optoelectronic properties, making them particularly suitable for high-performance photodetectors. However, photoinduced carrier generation in conventional 2D vdW photodetectors are usually limited, and new mechanisms need to be introduced to enhance device performance. Herein, we report a high-performance avalanche photodetector based on selenium (Se) nanoflakes. Our device achieves a high photoresponsivity (R) and specific detectivity (D*) of 361 A·W−1 and 2.4 × 1012 Jones, respectively. These figures of merit are two orders of magnitude higher than that in conventional Se photoconductive photodetectors. As a large bandgap vdW semiconductor, the Se channel allows the application of an extremely large bias voltage across it, and the resulting high electric field leads to the avalanche multiplication of carriers, which lays the groundwork for the improved device performance.

Solid-State High Harmonic Generation in Common Large Bandgap Substrate Materials.

Solid-state high harmonic generation (sHHG) spectroscopy is an emerging ultrafast technique for studying key material properties such as electronic structure at and away from equilibrium. sHHG anisotropy measurements, where sHHG spectra are recorded depending on the driving electric field relative to the crystal lattice, have become a powerful tool for studying crystal symmetries. Previous works on two-dimensional materials and other quantum materials have often used substrate-supported samples, assuming that all sHHG signals originate from the sample due to the relatively large bandgap of the substrate. While this assumption is generally reasonable, we show that some sHHG emissions from commonly used substrates can occur at moderate intensities of the sHHG driving field. In addition, we show that it is essential to consider not only the sHHG yield from a substrate but also its angular dependence relative to the material of interest. Specifically, in this work, the power-dependent and polarization angle-resolved sHHG emissions of fused silica, calcium fluoride, diamond, and sapphire of two different crystalline qualities and orientations are compared using a mid-infrared (MIR) driving field. This empirical characterization aims to guide the substrate selection for sHHG studies of novel materials to minimize the misattribution and interference of substrate-related sHHG emissions, which opens the possibility to study a wider array of materials.

Influence of non-metals doping on the structural, electronic, optical, and photocatalytic properties of rutile TiO2 based on density functional theory computations

This study investigates the influence of non-metal doping (C, F, N, and S) on the structural, electronic, and optical properties of rutile TiO2 using Hubbard-corrected density functional theory (DFT) within the Quantum ESPRESSO code. Rutile TiO2 is a promising material for environmental remediation and renewable energy applications. However, it has a large bandgap of 3.03 eV, which confines its use to UV light. By substituting oxygen atoms with a single dopant atom, we aim to shift the absorption edge toward the visible spectrum. Our findings reveal that doping with C, N, and S results in a redshift of the bandgap, while F doping does not exhibit this effect. The imaginary part of the dielectric function indicates shifted absorption edges for C, N, and S-doped TiO2, making them suitable for photocatalytic applications. Additionally, an increased refractive index after doping suggests the presence of excess charge carriers that affect light propagation. This work provides valuable insights for experimentalists exploring non-metal doping influences on rutile TiO2 for photocatalysis.

Evaluating Sulfur as a P‐Type Dopant in Cu3N Using Ab Initio Methods

Copper nitride (Cu3N) is an environmentally friendly semiconducting material with bipolar doping capability and is of interest to various applications. As deposited Cu3N films have inherent n‐type conductivity, further controllable n‐type doping is possible by introducing metal impurities. First‐principles methods based on density functional theory and beyond have been employed to study the p‐type doping behavior of sulfur atoms in Cu3N. The structural, electronic, optical, and thermal properties of pure Cu3N and sulfur‐doped Cu3N are computed for single and 3 × 3 × 3 supercells. Sulfur doping causes a shift from intrinsic n‐type to p‐type behavior. This study confirms that sulfur atoms in sulfur‐doped copper nitride preferentially occupy interstitial positions over nitrogen substitution, face‐centered, or copper substitution sites. Due to this change and an increased lattice constant, Cu3N becomes a softer material with a larger bandgap in the single‐cell alloy. Doped Cu3N supercell results show significant changes in optical properties appropriate for solar and other photoelectric applications. Cu3N:S exhibits remarkable enhancements in power factor and thermal and electrical conductivity, indicating potentially better performance in thermoelectric applications. The dielectric constant and absorption coefficient also significantly change with the incorporation of sulfur into Cu3N.

White Light Emission in Zero-Dimensional Indium Hybrid with Hydrogen Bond.

Low-dimensional organic-inorganic metal halides (OIMHs) have been explored as single-component white light emitters for applications in solid-state lighting. Herein, we report a zero-dimensional (0D) In-based OIMH (TMPDA)[InCl5(H2O)] (TMPDA = N,N,N',N'-tetramethyl-1,4-phenylenediamine), which crystallizes in the noncentrosymmetric P212121 space group and contains hydrogen bonds between the adjacent [InCl5(H2O)]2- octahedra in structure. It exhibits a large optical band gap (4.10 eV) and dual-band emission under UV light. Spectroscopic analysis and theoretical calculation indicate that the high (404 nm)- and low (513 nm)-energy emissions are attributed to the bound excitons in organic ligands and self-trapped excitons in [InCl5(H2O)]2- units, respectively. It is found that Sb doping in this 0D hybrid provides additional orange (590 nm) emission assigned to the 3P1 → 1S0 triplet radiative recombination. By adjusting the doping level, the emission color can be turned from turquoise to orange, and interestingly, a single-component white-light emission is realized by balancing the high-energy emission from organic ligand, the turquoise emission from [InCl5(H2O)]2-, and the orange one from [SbCl5(H2O)]2-. This work not only provides a new OIMH showing the single-component white light emission but also demonstrates the potential of In-based hybrids with hydrogen bonds for solid-state luminescence.

Flexible Single Microwire X-Ray Detector with Ultrahigh Sensitivity for Portable Radiation Detection System.

Sensitive, flexible, and low false alarm rate X-ray detector is crucial for medical diagnosis, industrial inspection, and scientific research. However, most semiconductors for X-ray detectors are susceptible to interference from ambient light, and their high thickness hinders their application in wearable electronics. Herein, a flexible visible-blind and ultraviolet-blind X-ray detector based on Indium-doped Gallium oxide (Ga2O3:In) single microwire is prepared. Joint experiment-theory characterizations reveal that the Ga2O3:In microwire possess a high crystal quality, large band gap, and satisfactory stability, and reliability. On this basis, an extraordinary sensitivity of 5.9×105µCGyair -1cm-2 and a low detection limit of 67.4nGyairs-1 are achieved based on the prepared Ag/Ga2O3:In/Ag device, which has outstanding operation stability and excellent high temperature stability. Taking advantage of the flexible properties of the single microwire, a portable X-ray detection system is demonstrated that shows the potential to adapt to flexible and lightweight formats. The proposed X-ray detection system enables real-time monitor for X-rays, which can be displayed on the user interface. More importantly, it has excellent resistance to natural light interference, showing a low false alarm rate. This work provides a feasible method for exploring high-performance flexible integrated micro/nano X-ray detection devices.

Advanced spectroscopic methods for probing in-gap defect states in amorphous SiNx for charge trap memory applications

Silicon nitride (SiNx) serves as the charge trap layer in current 3D NAND flash memory devices. The precise formation mechanism and electronic structure of localized defect trap states in SiNx remain elusive. Here, we present a refined experimental methodology to elucidate the in-gap defect states and the band gaps in amorphous SiNx thin films. Our approach integrates high-resolution reflection electron energy loss spectroscopy (REELS) and spectroscopic ellipsometry (SE) for comprehensive analysis. By systematical analysis, we aim to provide a robust method for determining in-gap electronic states in SiNx. We investigated two different SiNx films prepared by plasma-enhanced chemical vapor deposition and sputtering. Our analysis revealed several distinct in-gap states and determined band gap energies. This approach not only provide advanced spectroscopic methods to characterize the defect electronic states in SiNx, but also applicable to other large band gap semiconductors or dielectrics to predict device-level characteristics for future devices.

Study Effect of rGO Addition on Photocatalytic Activity of TiO2 in Reducing Carbon Dioxide Using Electrochemical Method

Abstract Increasing the carbon dioxide (CO2) concentration every year can cause various environmental problems. One of the technologies to reduce CO2 is carbon capture. The semiconductor of TiO2 is widely used as a photocatalyst to reduce CO2. However, TiO2 has limitations in absorbing light in the visible region because it has a large band gap value. Besides, TiO2 has a fast recombination of electron-hole pairs so it can reduce photocatalytic activity. An addition of rGO is expected to cover the shortcomings of TiO2 because rGO has good conductivity and a small band gap. We synthesized rGO-TiO2 photocatalyst and measured its activity in capturing and converting CO2 using an electrochemical method. By using voltage difference as an electron driver in reacting with CO2 we observe the reaction between electrons and CO2. The measurements were carried out under irradiated and unirradiated conditions. The CV measurements show that the rGO-TiO2 electrode with 60% rGO content has reduction and oxidation peaks. Based on the electrochemical half-reaction table, the reduction peaks in unirradiated conditions indicate the conversion of CO2 to CH4 and (COOH)2, while under irradiated the reduction peak indicates the formation of HCOO− and CH2CH2. The results show that by using the rGO-TiO2 composite as an electrode not only reduces CO2 but also converts the CO2 into hydrocarbon.

Roll-to-Roll Manufactured Polyetherimide Nanocomposite With Different Diameters of SiO2 Nanoparticles Exhibiting Improved High-Temperature Dielectric Energy Storage Performance.

To enhance the high-temperature energy storage performance of the polymer-based dielectric film, inorganic nanofillers with large band gaps are much more effective and have been widely adopted. However, the impact of nanoparticle diameters on the dielectric properties of polymer nanocomposites has been less studied. Herein, silicon dioxide nanoparticles (SiO2-NPs)with varying diameters (20, 60, 120, 200nm) prepared by the sol-gel method are incorporated in the PEI matrix to form PEI/SiO2 nanocomposites. The characterization results reveal a distinct correlation between the dielectric properties of polyetherimide (PEI) composites and the diameters of SiO2-NPs. Leakage current density analysis and breakdown strength simulations indicate that SiO2-NPs with smaller diameters generate more deep traps that impede the transport of charge carriers, especially under high temperatures. Notably, PEI/20nm-SiO2 exhibits a high discharged energy density of 4.4 J cm-3 with an efficiency of 90% at 150°C. Furthermore, PEI/SiO2 films with 10µm in thickness are manufactured by a large-scale solution casting process. The continuously prepared PEI/20nm-SiO2 film exhibits a discharged energy density of 3.2 J cm-3 with an efficiency of 90% at 150°C. This study not only provides a strategy for the design of high-performance dielectric polymer composites but also offers a large-scale high-temperature dielectric film for practical use.

Photocatalytic overall water splitting Z-schemes for hydrogen production with the X@CTF-0/β-Sb (X = S, Se) heterostructures

The covalent triazine framework (CTF-0) is believed to possess the potential to serve as a photocatalyst for overall water splitting, but its large bandgap constrains the solar-to-hydrogen (STH) efficiency. Here, we demonstrate that the STH efficiency can be boosted by constructing the CTF-0/β-Sb heterostructure and manipulating the band gap by the doped S or Se atoms in the CTF-0 monolayer. The electronic, optical, and thermodynamic properties are calculated to justify the photocatalytic Z-scheme for overall water splitting, and the interlayer transfers of the photogenerated carriers are investigated using non-adiabatic molecular dynamics simulations to understand the photocatalytic activity of the carriers. The electronic properties indicate that the band alignments hold a staggered character and there is a built-in electric field from the β-Sb to the CTF-0 monolayers in the heterostructures, which supports the photogenerated carriers to perform photocatalytic overall water splitting with Z-scheme and STH efficiencies of 13.28 % and 12.17 % can be achieved for the S@CTF-0/β-Sb and Se@CTF-0/β-Sb heterostructures. Moreover, the STH efficiencies remain increasing within 4 % biaxial strains, regardless of the tensile and compressive ones, implying that no need to worry about the effect of the smaller deformations on the photocatalytic performance in the preparation. Nonadiabatic molecular dynamics simulations show that the photocatalytic activities of the photogenerated carriers in the S@CTF-0/β-Sb are better protected in comparison with those in the Se@CTF-0/β-Sb heterostructures. However, the recombination times indicate that the latter can exert a better photocatalytic performance. Therefore, both the S@CTF-0/β-Sb and Se@CTF-0/β-Sb heterostructures are promising candidates for overall water-splitting for hydrogen production.

K0.9Rb2.1B8PO16: Design and Synthesis of a Deep-Ultraviolet Nonlinear Optical Crystal with Balanced Performance Derived from π-Conjugated and Non-π-Conjugated Groups.

A new deep-ultraviolet (DUV) nonlinear optical (NLO) material K0.9Rb2.1B8PO16 (KRBPO) has been designed and synthesized by adjusting the B/P molar ratio to 8:1. The KRBPO crystals were synthesized by a flux method and crystallized in noncentrosymmetric (NCS) and polar space group Cc. This compound exhibits a double-layer structure in which the A layer is composed of [B2O5] and [BO4] units and the B layer is formed by interconnected [B3O7] and [BO3] groups, and the two layers are connected by [PO4] tetrahedron. The theoretical calculations and experiments show that the synergistic interaction of π-conjugated and non-π-conjugated units leads to relatively well-balanced NLO properties of the title compound, including moderated SHG (0.7 × KDP), short UV cutoff edge (λcutoff < 190 nm), and a large band gap of 6.16 eV. Specifically, the coplanar arrangement of B-O groups in double-layer makes the KRBPO display a large birefringence (0.075@532 nm) and enables the shortest phase-matched wavelength to reach an important laser output wavelength of 266 nm.

First-principles prediction of a novel superhard orthorhombic carbon allotrope with large bandgap

First-principles prediction of a novel superhard orthorhombic carbon allotrope with large bandgap

Biochar-Supported Titanium Oxide for the Photocatalytic Treatment of Orange II Sodium Salt

Recent improvements in advanced technology for toxic chemical remediation have involved the application of titanium oxide nanoparticles as a photocatalyst. However, the large energy bandgap associated with titanium oxide nanoparticles (3.0–3.20 eV) is a limitation for their application as a photocatalyst within the solar spectrum. Various structural modification methods have led to significant reductions in the energy bandgap but not without their disadvantages, such as electron recombination. In the current investigation, biochar was made from the leaves of an invasive plant (Acacia saligna) and subsequently applied as a support in the synthesis of titanium oxide nanoparticles. The characterization of biochar-supported titanium oxide nanoparticles was performed using scanning electron microscopy, Fourier transformer infrared, X-ray diffraction, and Brunauer–Emmett–Teller analyses. The results showed that the titanium oxide was successfully immobilized on the biochar’s external surface. The synthesized biochar-supported titanium oxide nanoparticles exhibited the phenomenon of small hysteresis, which represents the typical type IV isotherm attributed to mesoporous materials with low porosity. Meanwhile, X-ray diffraction analysis revealed the presence of a mixture of rutile and anatase crystalline phase titanium oxide. The synthesis of biochar-supported titanium oxide nanoparticles was highly efficient in the degradation of Orange II Sodium dye under solar irradiation. Moreover, 83.5% degradation was achieved when the biochar-supported titanium oxide nanoparticles were used as photocatalysts in comparison with the reference titanium oxide, which only achieved 20% degradation.

Realizing n-type carbon nanotubes via halide perovskite nanowires Cs4MX5 inner filling

N-type carbon nanotubes (CNTs)-based field-effect transistors (FETs) have huge potential applications in low-power consumption tunnel FETs. However, the low-work function metal electrodes can achieve n-type CNTs, but they are easily oxidized due to poor environmental stability. Therefore, based on first-principles calculations, we proposed halide perovskite nanowires Cs4MX5 (M = Pb, Sn; X = Cl, Br, I) inner filling to achieve n-type single-walled CNTs (SWCNTs). The results indicated that all the perovskite nanowires located at the center of the SWCNTs possess high stability. Moreover, the diameter of SWCNTs is a crucial factor affecting the inner filling of perovskite nanowires with an optimal diameter of about 1.4 nm. Furthermore, all the perovskite nanowires Cs4MX5 are excellent electron donors, and the largest charge transfer is up to 1.72 e/nm for Cs4SnI5. Their interaction mechanism reveals that the low work function and the large internal bandgap are two important factors for cubic-phase nanowires to realize the n-type CNTs. Our findings provide some candidate materials and a feasible way to achieve n-type CNTs for applying CNTs-based FETs.