Decrease In Band Gap Research Articles

Design and characterization of borosilicate glass modified with TiO2 for enhanced optical and radiation shielding applications

This work investigates the potential of borosilicate glass doped with titanium dioxide (TiO2) for radiation shielding applications. The study explored the impact of varying TiO2 concentrations on the glass structure, optical properties, and radiation shielding effectiveness. X-ray diffraction (XRD) and Raman spectroscopy confirmed the amorphous nature of the glasses. The addition of TiO2 affected the glass network structure, as evidenced by changes in the Raman spectra and density measurements. UV–Vis spectroscopy revealed a red shift in the absorption edge (416–481 nm) and a decrease in the indirect optical band gap (2.91–2.70 eV) with increasing TiO2 content. The refractive index also increased from 2.54 to 3.54 with TiO2 concentration. The mass attenuation coefficient (MAC) and linear attenuation coefficient (LAC) increased significantly with TiO2 addition, indicating enhanced radiation attenuation capability. The inclusion of TiO2 reduced the half-value layer (HVL), tenth-value layer (TVL), and mean free path (MFP), while increasing the effective atomic number (Zeff). The effective electron density (Neff) and effective conductivity (Ceff) showed a slight increase with TiO2 content. Energy build-up factors (EBF and EABF) indicated a higher rate of radiation intensity increase and energy absorption within the glass due to the presence of TiO2. Finally, the incorporation of TiO2 into borosilicate glass offered a promising approach to developing improved optical and radiation shielding glasses.

Green synthesis of calcium nanoferrites using leaf extract of Brassica oleracea for photocatalysis of malachite green dye

The calcium ferrite nanoparticles were made by the sol–gel process. X-ray diffraction, a scanning electron microscope, and UV–vis spectroscopy were used to analyze the material. There is an orthorhombic phase in the space group Pnma. There were four techniques used to calculate the average crystallite size. Using ImageJ software, the particles were aggregated and their size was ascertained. Using energy-dispersive X-ray (EDX) analysis, the composition of the material was ascertained. 2.29 eV was determined to be the band gap. Vibrating test magnetometer (VSM) provided an explanation for the materials’ magnetic property. A decreased band gap energy is responsible for the 90% degradation of malachite green dye at a concentration of 15 mg/L in 150 min, with a four-cycle reusability.

Structural, optical, and morphological properties of PVC-BaTiO3 nanocomposite films

This work aims to fabricate barium titanate (BaTiO3) nanoparticles and study the effect of adding different contents of BaTiO3 nanoparticles on the structural, optical, and electrical properties of PVC polymer matrices. The PVC/BaTiO3 nanocomposite films were characterized by X-ray diffraction, FT-IR spectroscopy, and SEM. In addition, dielectric properties were studied within the frequency range of 0.1 KHz–6 MHZ. The XRD analysis reveals an amorphous nature of pure PVC with two characteristic peaks at 2θ = 17.09° and 2θ = 23.25°, and it reveals that BaTiO3 has sharp and narrow peaks. In PVC/BaTiO3 nanocomposite films, all XRD peaks of BaTiO3 appeared in all the samples with an increase in the average particle size from ∼46 nm to 55 nm. There is no shift of IR position in PVC bands, but the decreased intensity of some bands suggests complexation between PVC and BaTiO3. The UV–visible absorption spectrum of pure PVC has a band at λ = 278 nm. This band was shifted to 252 nm after adding BaTiO3 content. UV–visible transmission spectra demonstrate a decrease in the transmittance as an increase of BaTiO3 content from 89.23 % for pure PVC to 5.23 % for 0.1 wt% of BaTiO3. The values of the optical bandgap decrease with increasing BaTiO3 contents due to defect formation in PVC matrices. The optical parameters of the prepared nanocomposite films were also enhanced. The AC conductivity shows an increase with both frequency and BaTiO3 concentration, leading to enhanced movement of charge carriers and relaxation of interface polarization.

Investigating the role of Ag-doped ZnO thin films in UV photodetectors produced via laser assisted chemical bath growth technique

This study introduces the innovative fabrication of Ag-doped ZnO thin films (AgxZnO(100−x) TFs) with varying silver (Ag) concentrations (x) of 0.5, 1.0, 1.5, and 2.0 at% on glass substrates using a simple and cost-effective method known as laser-assisted chemical bath growth (LACBG). This process aims to create metal-semiconductor-metal (MSM) ultraviolet (UV) photodetectors. A continuous wave semiconductor laser with a 444.5 nm wavelength, 5 W power, and 6 min irradiation time was employed to synthesize high-quality Ag-doped ZnO TFs on the glass substrate. Ag electrodes were utilized as Schottky contacts to form MSM UV photodetectors. Structural and morphological analyses conducted using XRD and SEM revealed vertically aligned nanorods and nanoflowers with a high c-axis orientation and hexagonal wurtzite facets, while EDX confirmed Ag incorporation into the ZnO lattice. The UV–Visible absorbance spectra indicated a decrease in bandgap from 3.28 to 2.84 eV with increased Ag content. The current-voltage (I–V) characteristics of the Ag-doped ZnO TFs UV photodetector showed significantly enhanced conductivity at a 2.0 at% concentration level, achieving a responsivity of 10.78 A/W, an external quantum efficiency of 34.67 % at −3 V bias voltage. Finally, the modified device exhibited a sensitivity of 14661.9 %, a gain of 147.62, and a detectivity of 2.25 ×107 Jones, demonstrating its suitability for optoelectronic applications.

Cerium oxide-reinforced Fe2O3–Na2O–SiO2–B2O3 glass matrix for protection against ionizing X and gamma rays

Radiation shielding glass is an interesting material in the field of radiation shielding due to its remarkable features. In the present paper, we investigated the physical properties of radiation-shielding glass materials that consist of sodium oxide (Na2O), cerium oxide (CeO2), and iron oxide (Fe2O3) incorporated into borosilicate glasses with the formula 90SiO2-(70-x)B2O3+ 20Na2O–1Fe2O3-xCeO2 (CeFeNaBS-glasses). One of the distinguishing characteristics of this glass system is its enhanced radiation shielding capabilities. The structural studies indicated a gradual rise in glass density from 1.954 to 2.658 g/cm with further CeO2 doping. Optical studies showed that the optical band gaps went down from 3.41 eV to 3.33 eV as the amount of CeO2 in the CeFeNaBS-glass matrix rose. The decrease in optical band gap has been correlated with the rising basicity. Also, the increased basicity behavior induces more conversion of Ce3+ to Ce4+ ions by losing a 4f electron. Moreover, with further CeO2 additions, the glass color changed from light brown to dark brown. The presence of Ce4+ ions with further CeO2 additions is responsible for this color transformation. The linear and non-linear refractive indices exhibit enhanced behaviors with higher CeO2 concentrations. We used declining basicity and polarizability behaviors to describe this behavior. The incorporation of larger CeO2 concentrations enhances the ability to improve radiation shielding properties, as demonstrated by the increased values of the mass attenuation coefficient and half-value layer, especially in the energy ranges of soft tissues X-ray and hard tissues X-ray. Hence, the investigated CeFeNaBS-glasses exhibit enhanced transparency and radiation shielding capabilities, rendering them highly suitable for implementation in this domain.

Construction of scheelite CaWO4 with natural diatomite for boosted photocatalytic degradation of tetracycline and doxycycline antibiotics under natural conditions

Fabrication of efficient and recyclable catalysts with natural supporting materials is still a challenge in the field of photocatalysis. In the present work, scheelite type calcium tungstate was successfully constructed with natural diatomite via in-situ co-precipitation method for effective photocatalytic degradation of tetracycline (TC) and doxycycline (DC) antibiotics. The as-synthesized photocatalysts were characterized by SEM-EDX, TEM, BET, XRD, XRF, XPS, FTIR, UV–vis DRS, PL and EIS techniques. The morphological and physiochemical analyses confirmed the successful hybridization of CaWO4 with natural diatomite. The optical, photoluminescence and electrochemical tests confirmed that the composite material displayed narrower band gap energy, lower recombination rate and facilitated separation of photogenerated carriers. After construction of CaWO4 with the diatomite structure, the TC and DC decomposition efficiencies were found 4.70 and 2.54 times higher than that of the pristine sample, respectively. Furthermore, the composite catalyst showed superior degradation performances (91.8 % for TC and 90.7 % for DC) in the presence of hydrogen peroxide as a Fenton-agent. The enhanced photocatalytic performance was assigned to the increased specific surface area and pore volume, decreased band gap energy, limited recombination rate of photoinduced carriers, decreased charge transfer resistance as well as the abundant of hydroxyl radicals. The degradation reaction was found to be mainly driven by photogenerated holes and superoxide radicals. The CWO@DT/Vis/Fenton catalytic system exhibited good performance at near-neutral pH, also the composite catalyst was sufficiently utilized in the presence of co-existing anions. Furthermore, the photocatalytic efficiency was also tested under natural sunlight irradiation and the TC degradation remained 71.4 % after four cycles, indicating the outstanding feature of the composite catalyst in outdoor process conditions. Under these circumstances, the present work demonstrated the utilization potential of natural diatomite for effective photocatalytic remediation of antibiotic molecules under natural sunlight irradiation.

(Ce, Nd) co-doped TiO2 NPs via hydrothermal route:Structural, optical, photocatalytic and thermal behavior

Rare earth (Ce, Nd) doped/co-doped titania (TiO2) nanoparticles were successfully produced by hydrothermal route. Titanium isopropoxide (IV), cerium nitrate hexahydrate and neodymium nitrate hexahydrate were utilized as raw/starting materials. The effect of Ce and Nd doping/co-doping in TiO2 were studied through different complementary tools such as XRD, FTIR, FE-SEM, EDX, XPS, UV–Visible, PL, photocatalytic and thermal analysis. XRD spectra revealed anatase tetragonal phase and cubic phase due to titania and ceria nanoparticles respectively. The crystallite size, lattice constants, volume and no. of unit cell were determined through XRD data. Optical studies revealed the band gap, urbach energy, extinction coefficient, refractive index, optical conductivity and photoluminescence emission wavelength. FTIR spectra investigated the chemical bondings and functional groups present in prepared samples. Optical absorption spectra confirmed that absorption edge is red shifted, indicating a decrease in band gap from 3.5 to 3.0 eV with the incorporation of rare earth ions (Ce, Nd) in TiO2 matrix. The rate of electron-hole pair recombination was reduced through co-doping of (Ce, Nd) in TiO2 lattice as exhibited by reduction in intensity of photo luminescence spectra. The photocatalytic efficiency was enhanced with the integration of rare earth metal ions in TiO2 matrix for different dyes such as rhodamine B (RhB) and malachite green (MG) with visible light irradiation. The degradation efficiency of (Ce, Nd) co-doped TiO2 NPs against RhB and MG dyes was found to be 89 and 95 % respectively. TGA analysis was carried out to find weight loss during different thermodynamic phases such as dehydration, decomposition and combustion, and crystallization. Various thermodynamic parameters such as activation energy, entropy and enthalpy were estimated by thermal analysis.

Anodization of cast and sintered Fe40Al alloy in etidronic acid: Morphological and semiconductive properties of the oxide films

Fe40Al alloys produced by casting and sintering were anodized to form nanostructured oxide layers. Microstructural characterization revealed a lower grain size for the sintered alloy compared to the cast alloy. Anodizing was performed in four electrolytes with a constant etidronic acid concentration (0.3 M) and different ethylene glycol-water ratios. Different voltages (5–400 V) and treatment times (1–4 hours) were evaluated for cast and sintered Fe40Al alloys. Among the studied anodization regimes, only four anodic films formed on sintered Fe40Al were homogeneous. These films were annealed at 900°C and analyzed by conventional characterization techniques (SEM/EDS and XRD). Results indicated a non-self-ordered morphology and different content of P, Fe, and Al species as a function of the electrolyte composition. Annealing post-treatment led to the formation of Fe/Al oxides and spinels in selected anodic films. An additional peak of FePO4 was detected only in the anodic film formed in pure ethylene glycol. The band gap values (UV-Vis reflectance spectroscopy) of the anodic film formed in ethylene glycol decreased from 2.87 eV to 2.45 eV after annealing. This band gap decrease was associated with the preferential formation of conductive phases (Fe2O3 and FeAlO3) over insulating phases (γ-Al2O3 and FeAl2O4) after annealing.

Synthesis and Characterization of Polycarbonate/Polystyren/Polyethylene Oxide/Zinc Sulfide Nanocomposites: Gamma Ray Induced Changes in their Optical and Color Properties

Amorphous polycarbonate (PC), amorphous polystyrene (PS), semicrystalline polyethylene oxide (PEO) and zinc sulfide (ZnS) nanoparticles (NP) were used to fabricate PC/PS/PEO/ZnS nanocomposite (NC) films. We believe that this study is novel in the area of the effect of γ ray radiation on such NC. The synthesized ZnS NP had an average particle size of 18 nm, as indicated from the Rietveld refinement of the X-ray diffraction (XRD) scans. Samples of the PC/PS/PEO/ZnS NC films were irradiated with γ ray doses ranging from 20 to 180 kGy. UV-vis spectroscopy and the International Commission on Illumination (CIE) color changes technique were used to investigate the resulting effects of the γ ray irradiation on the optical and color properties of the prepared films. The light absorbance of the NC films increased as it was irradiated with the γ ray doses up to 180 kGy, the maximum dose used. The increase in absorbance was associated with a decrease in the direct bandgap from 5.88 to 4.92 eV, and an increase of Urbach energy from 0.43 to 0.81 eV. This was attributed to the dominance of chain crosslinks. The γ ray effects on the absorbance, extinction coefficient, refractive index and optical conductivity of the NC films were studied. The modifications in the optical properties indicated that the γ radiation is a useful tool that allows the application of the resulting PC/PS/PEO/ZnS NC films in optoelectronic devices. Furthermore, the color differences between the pristine and irradiated films were evaluated using the CIE color differences technique. The pristine film was uncolored but showed significant color changes when irradiated with γ radiation up to 180 kGy, the maximum dose used.

Influence of pressure on the different physical features of lead-free double perovskite materials K2SnX6 (X = Cl, and Br): DFT replication

The influence of pressure (0–12 GPa) on several physical features of perovskite materials K2SnX6 (X = Cl, and Br) has been executed through DFT replication coded with CASTEP. Very close relation is noticed concerning the studied and synthesized lattice parameters. The studied compounds are mechanically stable under pressure according to Born's stability criteria. The Pugh's and Poisson's ratios indicate the brittle nature K2SnCl6 at 0 GPa and ductile nature at above 2 GPa. On the other hand, the phase K2SnBr6 exhibits ductile in nature at 0 GPa to high pressure. The increasing behaviors of machinable index with increasing pressure making these materials effectively useable in industrial applications. The determined Vickers hardness (Hv) values at several pressures of both the phases did not exceed 8 GPa which enables them to be more machinable and damage-tolerant. The decrease of band gap with increasing pressure ensures the probable application of these materials in optoelectronic devices. The bond length decreases with increasing pressure and consequently materials become harder. As the static dielectric constant of K2SnBr6 is higher than K2SnCl6, hence K2SnBr6 is more suitable for optoelectronic device applications. In the ultraviolet region, both the materials show their intense peak of absorption and conductivity. Both the studied compounds processes very low thermal conductivity in the entire pressure ranges comparing to the well-known thermal barrier coating (TBC) materials ABO3 which confirming their better uses in industry as TBC materials. Having very high melting temperature at high pressure these compounds are suitable for high-temperature application purposes.

Tailoring the Optical Properties of Gamma Ray Irradiated Polyvinyl Alcohol/Carboxymethyl Cellulose/Sodium Lignosulfonate Blend Films for their Application in Optoelectronic Devices

Polyvinyl alcohol, carboxymethyl cellulose and sodium lignosulfonate (PVA/CMC/LS) blends were fabricated using a casting technique. Samples from the prepared PVA/CMC/LS films were irradiated with γ ray doses ranging from 5 to 110 kGy. To explore the resulting effects of the γ ray irradiation on the optical properties of the prepared films UV-vis spectroscopy was used. The effects of the γ ray irradiation on the light absorbance, transmission, extinction coefficient, refractive index, dielectric loss and optical conductivity of the PVA/CMC/LS films were investigated. The absorbance of the blend films increased as it was irradiated with the γ ray doses up to 110 kGy, the maximum dose used. The increase in absorbance was associated with a decrease in the direct bandgap from 5.60 to 4.55 eV, and an increase of Urbach energy from 0.31 to 0.84 eV. We attribute this behavior to the domination of crosslinking that destroyed the ordered structure and thus increased the amorphous regions. Additionally, we used the optical dielectric loss (ε”) to detect the type of microelectronic transition for the PVA/CMC/LS films, which was found to be a direct allowed transition. Moreover, the optical color changes between the pristine and the irradiated films were evaluated using the International Commission on Illumination (CIE) color differences technique. The pristine PVA/CMC/LS film was uncolored. It showed significant color changes when irradiated with γ radiation up to 110 kGy. The changes in the optical properties of PVA/CMC/LS film suggested its usage as a promising candidate for future optoelectronics characterization techniques.

Structures and properties of LiBaF3 microwave dielectric ceramics for ULTCC applications

Perovskite structural LiBaF3 ceramics with excellent microwave dielectric properties were synthesized using traditional solid-state method. By regulating the sintering temperatures from 600 °C to 675 °C, LiBaF3 ceramics exhibit tunable dielectric constant (εr) from 12.42 to 13.72, adjustable Q × f value from 55000 GHz to 73000 GHz, and regulable temperature coefficient of resonance frequency (τf) from −36.78 ppm/°C to −34.68 ppm/°C. The properties are strongly associated with the density, and can be further optimized by 0.5 wt%TiO2 addition (εr = 14.43, Q × f = 56000 GHz, τf = -1.26 ppm/°C). The LiBaF3 ceramics also exhibit excellent compatibility with Ag and Al electrodes. Furthermore, relationships between multiscale structures and microwave dielectric properties of the ceramics were revealed. Oxidation behaviors between LiBaF3 and O2 would result in the lattice shrinkage, the introduction of defect level, the decrease of bandgap and density, and then deteriorating the microwave dielectric properties. All the findings make the LiBaF3 ceramic a promising candidate for ULTCC application, and may facilitate the development of other novel microwave dielectric materials.

Threefold enhanced photodegradation of methylene blue using MgO composite with minimum Nd2O3: finding the sweet spot.

Removal of organic dyes like methylene blue (MB) from industrial effluents serves as potential source of potable water. Photocatalytic degradation using sustainable catalyst is deemed to be an affordable solution. In this work, Nd2O3/MgO nanocomposite with different compositions (1, 3, and 5wt% Nd2O3 with MgO) have been achieved using hydrothermal synthesis and characterized extensively. Interestingly, increasing Nd2O3 proportion (1-5%) enhances light absorption, and decreases band gap and electron-hole recombination. The efficacy of the photocatalysts is tested with the degradation of MB dye, through optimizing Nd2O3/MgO proportion, contact time, catalyst dose, and pH. Interestingly, control experiments reveal that 5wt% Nd2O3/MgO achieve 99.6% degradation of MB in 90min at pH 7, compared to 88.8% with bare MgO under same condition. Kinetic data show that 5wt% Nd2O3/MgO exhibits ca. 3 times higher degradation rate compared to MgO. For the first time, our work enable MgO-based sustainable photocatalyst development with minimum (5wt%) rare-earth combination to achieve excellent photocatalytic degradation performance.

Synthesis of new synthetic hybrid glasses using metallic nano-particles and rare-earth: Effect of plasmonic diluents

Borophosphate-based glass materials have the potential to revolutionize optical technology because of their outstanding optical properties, long-lasting nature, and cost-effectiveness. The present research addresses the intricate functions of rare earth and metallic nanoparticles (NPs) in borophosphate glass, which have significant potential for optical photonic and medical applications by incorporating Dy3+ ions and Cu NPs. We developed novel hybrid glasses through the melt-quenching technique, which includes the creation of functional groups and the establishment of bonds between P2O5 and B2O3, as confirmed by FTIR and Raman spectroscopy. UV–visible absorption spectra were used to identify the presence of Cu⁺ and Cu (Saeed et al., 2021) [2]⁺ ions and Cu nanoparticles, with the absorption peaks indicating their respective states. Furthermore, the underlying mechanisms of energy transfer in a glass matrix that is co-doped with dysprosium ions (Dy3+) have been studied. The experimental findings of this research not only provide valuable information about the physical properties of borophosphate glass but also emphasize the collaborative relationship between the rare-earth ion and copper nano-powders. The Tauc plot analysis demonstrated a correlation between the concentration of Cu and Dy dopants and a decrease in the energy band gap of the glass. This suggests that these dopants influence the electronic structure of the glass. This study opens up possibilities for creating innovative photonic materials with customized optical attributes.

Multi-Doping Exploration of (Sb, Bi and Ba) by First Principles on Ordered Zn–Si–P Compounds as High-Performance Anodes for Next-Generation Li-Ion Batteries

Chalcopyrite ZnSiP2 has emerged as a promising anode material for next generation Li-ion-based batteries due to its high theoretical capacity. First principles multiple-dopant effect computations were made on the structural, electronic, magnetic, and thermodynamic responses for chalcopyrite ZnSiP2(1−x)Sbx, ZnSiP2(1−x)Bix, Zn(1−x)BaxSiP2, and Zn1−xBaxSiP2(1−x)Sbx, using both the norm conserving, ultra-soft pseudopotentials with generalized gradient approximation (GGA+PBE) and the main frame of density functional theory. Lattice coefficient volume, bulk modulus, formation energy, and total energy of host materials were computed and compared with experimental and theoretical results. Energy band gap for the pure chalcopyrite ZnSiP2 system (1.4 eV) matches previous data and validates the accuracy of current calculations as doping concentration (x = 0.6, 0.9, and 0.12) of (Sb, Bi, and Ba) at Zn and P sites increases. The corresponding band gap decreases, resulting in greater enhancement in electronic conductivity. Finally, the phonon dispersion relation, phonon density of states, vibration frequencies of phonon, Gibbs free energy, enthalpy, entropy effect, and Debye temperature (θ D) were estimated to confirm the thermodynamic stability of both pure and doped systems. These investigations are predicted to contribute a deeper sympathy of the doping effects on ZnSiP2, facilitating further advancements in anode materials design for Li-ion batteries.

Development and characterization of PVA-based nanocomposites with graphene and natural quartz nanoparticles for energy storage applications

This study presents the development and characterization of polymer nanocomposites (PNCs) using polyvinyl alcohol (PVA) as a matrix, incorporating graphene (Gr) and natural quartz nanoparticles (NQNs) as nanofillers. The graphene content was fixed at 1 wt%, while the quartz content was varied at 3 wt%, 7 wt%, and 11 wt%. The NQNs were derived from natural quartz rocks, which were ground and milled to nanosize, emphasizing the utilization of natural materials. Comprehensive characterization was performed using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier-transform infrared spectroscopy (FTIR), UV–visible spectroscopy (UV–Vis), and extensive electrical and dielectric measurements. SEM and EDS analyses revealed the nearly spherical shape of the NQNs, with sizes ranging from 25 to 88 nm and an average size of 61.2 ± 13.1 nm. XRD patterns indicated a decrease in crystallinity of the polymer matrix with increasing NQNs content, with the PVA/Gr-11 wt% NQNs showing nearly amorphous characteristics. FTIR spectra demonstrated the incorporation of NQNs within the PVA matrix, affecting the chemical bonding and reducing the intensity of characteristic peaks. UV–Vis spectra indicated a significant decrease in the optical bandgap with the addition of NQNs, suggesting enhanced electronic properties. The electrical conductivity measurements, at a frequency range of 50 Hz to 8 MHz and temperature range from 20 °C to 80 °C, showed that the incorporation of Gr, a two-dimensional (2D) material, and NQNs significantly enhanced the conductivity of the nanocomposites, with the optimal performance observed at 7 wt% NQNs. Dielectric measurements revealed that the PVA/Gr-7 wt% NQNs nanocomposite exhibited superior dielectric properties, with higher dielectric constant and lower dielectric loss compared to pure PVA. Nyquist plots indicated reduced bulk resistance and enhanced thermal stability for the PVA/Gr-7 wt% NQNs composite. Capacitance-frequency and conductance-frequency analyses of the fabricated capacitor confirmed this composite's superior performance for dielectric capacitors. The optimized PVA/Gr-7 wt% NQNs nanocomposite, leveraging the unique properties of natural quartz and 2D graphene, demonstrated significant improvements in electrical and dielectric properties, making it a promising candidate for advanced dielectric capacitors in energy storage applications. The study confirms the innovative use of natural and 2D materials to develop energy storage devices.

Substantial Energy Band Modulation of Semiconducting Hexagonal GaTe Quantum Wells by Layer Thickness and Mirror Twin Boundaries.

Exploring emerging two-dimensional (2D) van der Waals (vdW) semiconducting materials and precisely tuning their electronic properties at the atomic level have long been recognized as crucial issues for developing their high-end electronic and optoelectronic applications. As a III-VI semiconductor, ultrathin layered hexagonal GaTe (h-GaTe) remains unexplored in terms of its intrinsic electronic properties and band engineering strategies. Herein, we report the successful synthesis of ultrathin h-GaTe layers on a selected graphene/SiC(0001) substrate, via molecular beam epitaxy (MBE). The widely tunable quasiparticle band gaps (∼2.60-1.55 eV), as well as the vdW quantum well states (QWSs) that can be strictly counted by the layer numbers, are well characterized by onsite scanning tunneling microscopy/spectroscopy (STM/STS), and their origins are clearly addressed by density functional theory (DFT) calculations. More intriguingly, distinctive 8|8E and 4|4P (Ga) mirror twin boundaries (MTBs) are identified in the ultrathin h-GaTe flakes, which can induce decreased band gaps and prominent p-doping effects. This work should deepen our understanding on the electronic tunability of 2D III-VI semiconductors by thickness control and line defect engineering, which may hold promise for fabricating atomic-scale vertical and lateral homojunctions toward ultrascaled electronics and optoelectronics.

Sulfur-Vacancy-Engineered Two-Dimensional Cu@SnS2-x Nanosheets Constructed via Heterovalent Substitution for High-Efficiency Piezocatalytic Tumor Therapy.

Ultrasound (US)-mediated piezocatalytic tumor therapy has attracted much attention due to its notable tissue-penetration capabilities, noninvasiveness, and low oxygen dependency. Nevertheless, the efficiency of piezocatalytic therapy is limited due to an inadequate piezoelectric response, low separation of electron-hole (e--h+) pairs, and complex tumor microenvironment (TME). Herein, an ultrathin two-dimensional (2D) sulfur-vacancy-engineered (Sv-engineered) Cu@SnS2-x nanosheet (NS) with an enhanced piezoelectric effect was constructed via the heterovalent substitution strategy of Sn4+ by Cu2+. The introduction of Cu2+ ion not only causes changes in the crystal structure to increase polarization but also generates rich Sv to decrease band gap from 2.16 to 1.62 eV and inhibit e--h+ pairs recombination, collectively leading to the highly efficient generation of reactive oxygen species under US irradiation. Moreover, Cu@SnS2-x shows US-enhanced TME-responsive Fenton-like catalytic activity and glutathione depletion ability, further aggravating the oxidative stress. Both in vitro and in vivo results prove that the Sv-engineered Cu@SnS2-x NSs can significantly kill tumor cells and achieve high-efficiency piezocatalytic tumor therapy in a biocompatible manner. Overall, this study provides a new avenue for sonocatalytic therapy and broadens the application of 2D piezoelectric materials.

The electronic, magnetic, and optical behaviors of graphyne modulated by metal atoms adsorption: a first-principles study

The electronic, magnetic, and optical behaviors of graphyne modulated by various adsorbed metal atoms (Li, Na, K, Mg, Ca, Al, and Zn) from typical metal-ion batteries are studied by first-principles calculation. Notably, Mg and Zn adsorption systems are deemed unstable. In contrast, Li, Na, K, Ca, and Al systems exhibit two preferential adsorption sites, with the optimal position being the hollow center site within the large acetylenic ring. Upon the adsorption of these metal atoms, except for Ca adsorption systems exhibit semi-metallic behavior, while the other metal adsorption systems induced a transition from p-type to n-type semiconductors with decreased band gaps. Intriguingly, the inherent magnetism of the metal atoms vanished, resulting in a total magnetic moment of 0 μ B for the adsorption systems. Furthermore, the optical absorption and reflectivity peak positions for Ca adsorption systems show a significant redshift from violet to green and blue light regions. Conversely, other adsorption systems exhibit new absorption and reflection peaks in the infrared range, accompanied by an increase in both absorption coefficient and reflectivity across various spectral regions. These findings are conducive to the application in the field of novel optoelectronics and optical films.

Exploring the multifaceted properties of zinc-doped nanocrystalline calcium chromite: A comprehensive investigation into structural, morphological, optical, and magnetic behavior

The production of CaCr1−xZnxO3 a calcium chromite doped with zinc (0 ≤ x ≤ 0.4). The samples were prepared using the sol-gel auto-combustion process, and then we analysed their optical and dielectric characteristics, microstructure, and morphology to determine how doping with Zn affected them. The microstructural investigation verified that the samples were composed of a single phase through the use of X-ray diffraction and Fourier transform infrared spectroscopy. The crystallite size was determined using the Scherrer equation and Williamson-Hall analysis, while the lattice parameters, density, unit cell volume, bond lengths, and bond angles were all clarified from Xrd data. Both the size of crystallites and the volume of unit cells increased as the Zn level grew. The creation of uniform and regular samples was confirmed by surface morphology examination using SEM-EDX. Furthermore, optical properties revealed a decrease in the optical energy bandgap (Eg) and an increase in Urbach energy with rising Zn doping. Magnetic saturation exhibited an initial increase from x = 0.1 to 0.4 (35.4–55.7 emu/g) followed by a decrease from x = 0.3 to 0.4 (41.6–40.7 emu/g) as Zn progressively occupied A and B sites. VSM results also indicated a decrease in remanence (Mr) and coercivity (Hc) with increasing Zn concentration.