A Bandgap-Tuned Tetragonal Perovskite as Zero-Strain Anode for Potassium-Ion Batteries.

PIBs are emerging as a promising energy storage system due to high abundance of potassium resources and theoretical energy density, however, progress of PIBs is severely hindered by structural instability and poor cycling of anode material during continual insertion and extraction of larger-sized K+. Hence, developing anode material with structural stability and stable cycling remains a great challenge. Herein, bandgap-tuned Mo-doped and carbon-coated lead titanate (CMPTO) with zero-strain K+ storage is presented as ultra-stable PIBs anode. Mo doping introduces narrowed bandgap and optimized crystal lattice for enhanced intrinsic electron and ion transfer. Demonstrated by in situ XRD characterizations, the crystal structure stays stable with unchanged peak positions, fully revealing zero-strain characteristic of CMPTO anode during potassium storage for stable cyclic capability. Ultimately, CMPTO anode achieved ultra-stable cycling performance of 7000 cycles at 500 mA g-1 with high capacity retention of 90% and considerable specific capacity of 130.9 mAh g-1 after 600 cycles at 100 mA g-1; with relatively large density, CMPTO realized eminent volumetric capacity of 1111.09 mAh cm-3 and ultra-long cycling life of 10000 cycles at 7041 mA cm-3. This work introduces a promisingly new route into developing anode materials with ultra-stable performance for PIBs.

A Novel 3D-Printed Negative-Stiffness Lattice Structure with Internal Resonance Characteristics and Tunable Bandgap Properties.

The bandgap tuning potential offered by negative-stiffness lattice structures, characterized by their unique mechanical properties, represents a promising and burgeoning field. The potential of large deformations in lattice structures to transition between stable configurations is explored in this study. This transformation offers a novel method for modifying the frequency range of elastic wave attenuation, simultaneously absorbing energy and effectively generating diverse bandgap ranges. In this paper, an enhanced lattice structure is introduced, building upon the foundation of the normal negative-stiffness lattice structures. The research examined the behavior of the suggested negative-stiffness lattice structures when subjected to uniaxial compression. This included analyzing the dispersion spectra and bandgaps across different states of deformation. It also delved into the effects of geometric parameter changes on bandgap properties. Furthermore, the findings highlight that the normal negative-stiffness lattice structure demonstrates restricted capabilities in attenuating vibrations. In contrast, notable performance improvements are displayed by the improved negative-stiffness lattice structure, featuring distinct energy band structures and variable bandgap ranges in response to differing deformation states. This highlights the feasibility of bandgap tuning through the deformation of negatively stiffened structures. Finally, the overall metamaterial structure is simulated using a unit cell finite element dynamic model, and its vibration transmission properties and frequency response patterns are analyzed. A fresh perspective on the research and design of negative-stiffness lattice structures, particularly focusing on their bandgap tuning capabilities, is offered in this study.

One-Step Gas-Solid-Phase Diffusion-Induced Elemental Reaction for Bandgap-Tunable CuaAgm1Bim2In/CuI Thin Film Solar Cells.

Lead-free inorganic copper-silver-bismuth-halide materials have attracted more and more attention due to their environmental friendliness, high element abundance, and low cost. Here, we developed a strategy of one-step gas-solid-phase diffusion-induced reaction to fabricate a series of bandgap-tunable CuaAgm1Bim2In/CuI bilayer films due to the atomic diffusion effect for the first time. By designing and regulating the sputtered Cu/Ag/Bi metal film thickness, the bandgap of CuaAgm1Bim2In could be reduced from 2.06 to 1.78 eV. Solar cells with the structure of FTO/TiO2/CuaAgm1Bim2In/CuI/carbon were constructed, yielding a champion power conversion efficiency of 2.76%, which is the highest reported for this class of materials owing to the bandgap reduction and the peculiar bilayer structure. The current work provides a practical path for developing the next generation of efficient, stable, and environmentally friendly photovoltaic materials.

Linker-Based Bandgap Tuning in Conductive MOF Solid Solutions.

Herein, the synthesis of Cu3 (HAB)x (TATHB)2-x (HAB: hexaaminobenzene, TATHB: triaminotrihydroxybenzene) is reported. Synthetic improvement of Cu3 (TATHB)2 leads to a more crystalline framework with higher electrical conductivity value than previously reported. The improved crystallinity and analogous structure between TATHB and HAB enable the synthesis of Cu3 (HAB)x (TATHB)2-x with ligand compositions precisely controlled by precursor ratios. The electrical conductivity is tuned from 4.2 × 10-8 to 2.9 × 10-5  S cm-1 by simply increasing the nitrogen content in the crystal lattice. Furthermore, computational calculation supports that the solid solution facilitates the band structure tuning. It is envisioned that the findings not only shed light on the ligand-dependent structure-property relationship but create new prospects in synthesizing multicomponent electrically conductive metal-organic frameworks (MOFs) for tailoring optoelectronic device applications.

One-pot ultrasonicated synthesized lead-less hybrid perovskite nanocrystals: structural, morphological and optical analysis.

In contemporary years, hybrid lead halide perovskites nanocrystals (HPNCs) have emerged as core materials for low-cost solution-processable photovoltaic, light-emitting devices as well as in other optoelectronic fields, such as high-efficiency perovskite fluorescent quantum dots (quantum dot, QD). Although the high efficiency makes them an attractive active material, reducing the Pb-toxicity and enhancing the stability while sustaining the efficiency of the HPNCs devices is important for their successful commercialization in future. Here, we report for the first time the fabrication of excellent quality Pb-less, MAPb1-xSnxBr3(x = 0 to 0.50) perovskite NCs by one-pot ultrasonication method. Interestingly, an outstanding photoluminescence quantum yield (PLQY) of 94% and better lifetime performance than 100% Pb-based HPNCs is obtained for Pb-less HPNCs. The successful incorporation of Sn MAPb1-xSnxBr3HPNCs is confirmed by energy-dispersive x-ray (EDX) and x-ray photoelectron spectroscopy (XPS) analysis. Although the particle size for Pb-less HPNCs was different, the change in morphology and structure was minimal as confirmed by transmission electron microscopy (TEM) analysis. The optical analysis indicated bandgap tuning, which is evident by the blue shift of the band edge in absorbance spectra and photoluminescence peak after incorporating Sn2+. To the best of our knowledge, this is the highest achieved PLQY for Sn-substituted hybrid Pb-based HPNCs. The synthesis by using one pot ultrasonication method might be helpful for large-scale HPNCs production and can pave the way for future research on less-toxic and stable alternatives to Pb-based HPNCs.

Magnetic, Electronic, and Optical Studies of Gd-Doped WO3: A First Principle Study.

Tungsten trioxide (WO3) is mainly studied as an electrochromic material and received attention due to N-type oxide-based semiconductors. The magnetic, structural, and optical behavior of pristine WO3 and gadolinium (Gd)-doped WO3 are being investigated using density functional theory. For exchange-correlation potential energy, generalized gradient approximation (GGA+U) is used in our calculations, where U is the Hubbard potential. The estimated bandgap of pure WO3 is 2.5 eV. After the doping of Gd, some states cross the Fermi level, and WO3 acts as a degenerate semiconductor with a 2 eV bandgap. Spin-polarized calculations show that the system is antiferromagnetic in its ground state. The WO3 material is a semiconductor, as there is a bandgap of 2.5 eV between the valence and conduction bands. The Gd-doped WO3's band structure shows few states across the Fermi level, which means that the material is metal or semimetal. After the doping of Gd, WO3 becomes the degenerate semiconductor with a bandgap of 2 eV. The energy difference between ferromagnetic (FM) and antiferromagnetic (AFM) configurations is negative, so the Gd-doped WO3 system is AFM. The pure WO3 is nonmagnetic, where the magnetic moment in the system after doping Gd is 9.5599575 µB.

Transition metal-doped SnO2 and graphene oxide (GO) supported nanocomposites as efficient photocatalysts and antibacterial agents.

In the present work, pristine and transition metal (TM) (W, Ag, Zn)-doped SnO2 nanocrystals using a facile sol-gel approach were synthesized. The grown products were anchored on graphene oxide (GO) sheets via a simple ultrasonication technique to fabricate binary nanocomposites. The structural, optical, and morphological properties of as-synthesized samples were studied by XRD, FTIR, Raman, EDX, UV-Visible, PL, and FE-SEM. The charge transferability of graphene oxide-based samples was investigated by EIS. The XRD exhibited the TM doping in SnO2 and the development of GO-based nanocomposite. FTIR data evidenced the existence of the metal-oxygen bonds. Raman spectra presented the optical phonon modes of SnO2 and the existence of oxygen vacancy defects. FE-SEM images demonstrated the anchoring of particles on the GO sheet, and EDX further approved the existence of desired dopants. The integration of SnO2 with TM doping remarkably reduced optical bandgap (3.65-3.10 eV), which was further decreased (3.10-2.99 eV) by making composite with GO. The photodegradation results exhibited that GO-based nanocomposites have the higher potential to degrade synthetic dyes (methyl red (MR), and methyl orange (MO) and SnZnO2/GO have shown superb photocatalytic performance after 80-min sunlight illumination (99.9% MR and 95.0% MO dyes) with the higher rate constant and superior stability up to 6th cycle against MR dye. The grown samples were tested for bacterial disinfection, and SnZnO2/GO sample showed a higher zone of inhibition towards S. aureus and K. pneumoniae bacteria strains. The greater charge transfer rate and lower recombination of charge carriers in GO-based composites were also observed by EIS and PL analysis. Moreover, the present article ascribed that the photocatalytic and antibacterial properties of bare SnO2 could be improved by TM doping and fabricating their composite with GO.

A Sequenced Study of Improved Dielectric Properties of Carbon Nanotubes and Metal Oxide-Reinforced Polymer Composites.

Polymers have gained attraction at the industrial level owing to their elastic and lightweight nature, as well as their astonishing mechanical and electrical applications. Their scope is limited due to their organic nature, which eventually leads to the degradation of their properties. The aim of this work was to produce polymer composites with finely dispersed metal oxide nanofillers and carbon nanotubes (CNTs) for the investigation of their charge-storage applications. This work reports the preparation of different polymeric composites with varying concentrations of metal oxide (MO) nanofillers and single-walled carbon nanotubes (SWCNTs). The successful synthesis of nanofillers (i.e., NiO and CuO) was carried out via the sonication and precipitation methods, respectively. After, the smooth and uniform polymeric composite thin films were prepared via the solution-casting methodology. Spectroscopy and diffraction techniques were used for the preliminary characterization. Scanning electron microscopy was used to check the dispersion of carbon nanotubes (CNTs) and MOs in the polymer matrix. The addition of nanofillers and carbon nanotubes (CNTs) tuned the bandgap, reduced the strain, and enhanced the elastic limit of the polymer. The addition of CNT enhanced the mechanical strength of the composite; however, it increased the conductivity, which was tuned by using metal oxides. By increasing the concentration of NiO and CuO from 2% to 6% bandgap of PVA, which is 5-6 eV reduced to 4.41 and 4.34 eV, Young's moduli of up to 59 and 57.7 MPa, respectively, were achieved. Moreover, improved dielectric properties were achieved, which shows that the addition of metal oxide enhances the dielectric behavior of the material.

Azetidinium Lead Halide Ruddlesden-Popper Phases.

A family of Ruddlesden-Popper (n = 1) layered perovskite-related phases, Az2PbClxBr4-x with composition 0 ≤ x ≤ 4 were obtained using mechanosynthesis. These compounds are isostructural with K2NiF4 and therefore adopt the idealised n = 1 Ruddlesden-Popper structure. A linear variation in unit cell volume as a function of anion average radius is observed. A tunable bandgap is achieved, ranging from 2.81 to 3.43 eV, and the bandgap varies in a second-order polynomial relationship with the halide composition.

Electronic structure transition of cubic CsSnCl3 under pressure: effect of rPBE and PBEsol functionals and GW method.

The antiperovskites based on metal halides have emerged as potential materials for advanced photovoltaic and electronic device applications. But the wide bandgap of non-toxic CsSnCl3 reduces its photovoltaic efficiency. Here, we report the change of electronic structure of CsSnCl3 at different pressure by using GGA-rPBE and GGA-PBEsol functionals and the GW method. We have shown that the prediction of electronic structure transition (semiconducting to metallic state) strongly depends on the exchange-correlation and the GW method gives the most reasonable values of the bandgap under pressure. The pressure increases the electronic density of states close to the Fermi level by pushing the valence electrons upward and thus, reduces the bandgap linearly. Afterward, we have also investigated the influence of pressure on absorption coefficient, and mechanical properties meticulously. Although the pressure shifts the absorption peak to lower photon energies, the absorption coefficient is slightly improved.

Bandgap-tuned ultra-small SnO2-nanoparticle-decorated 2D-Bi2WO6 nanoplates for visible-light-driven photocatalytic applications.

With the rapid rate of industrialization, the emission of effluents represents a serious threat to aquatic living organisms and the environment. Semiconductor-mediated photocatalysis has been highlighted as the most attractive technology for the elimination of pollutants. In this connection, bandgap-tuned ultra-small SnO2-nanoparticle-decorated 2D-Bi2WO6 nanoplates were prepared via the hydrothermal method. The tuning of the bandgap was altered by the thermal annealing procedure. Moreover, we investigated the influence of different bandgaps of SnO2 on the anchoring of the 2D-Bi2WO6 nanoplates and studied their photocatalytic activity through the degradation of Rhodamine B under visible light irradiation. The ultra-small SnO2 nanoparticles were highly anchored on the surface of the 2D-Bi2WO6 plates, which resulted in more photon harvesting, improved charge separation, the transfer of photoinduced charge carriers, and the alteration of band positions towards the visible region of light. Furthermore, the anchored SnO2 nanoparticles improved the performance of the photocatalytic activity of 2D-Bi2WO6 nanoplates by more than 2.7 times.

Continuously Tuning Electronic Properties of Few-Layer Molybdenum Ditelluride with in Situ Aluminum Modification toward Ultrahigh Gain Complementary Inverters.

Semiconducting molybdenum ditelluride (2H-MoTe2), a two-dimensional (2D) transition metal dichalcogenide, has attracted extensive research attention due to its favorable physical properties for future electronic devices, such as appropriate bandgap, ambipolar transport characteristic, and good chemical stability. The rational tuning of its electronic properties is a key point to achieve MoTe2-based complementary electronic and optoelectronic devices. Herein, we demonstrate the dynamic and effective control of the electronic properties of few-layer MoTe2, through the in situ surface modification with aluminum (Al) adatoms, with a view toward high-performance complementary inverter devices. MoTe2 is found to be significantly electron doped by Al, exhibiting a continuous transport transition from p-dominated ambipolar to n-type unipolar with enhanced electron mobility. Using a spatially controlled Al doping technique, both p- and n-channels are established on a single MoTe2 nanosheet, which gives complementary inverters with a record-high gain of ∼195, which stands out in the 2D family of materials due to the balanced p- and n-transport in Al-modified MoTe2. Our studies coupled with the tunable nature of in situ modification enable MoTe2 to be a promising candidate for high-performance complementary electronics.

Anomalous and Polarization-Sensitive Photoresponse of Td -WTe2 from Visible to Infrared Light.

Recently, an emergent layered material Td -WTe2 was explored for its novel electron-hole overlapping band structure and anisotropic inplane crystal structure. Here, the photoresponse of mechanically exfoliated WTe2 flakes is investigated. A large anomalous current decrease for visible (514.5 nm), and mid- and far-infrared (3.8 and 10.6 µm) laser irradiation is observed, which can be attributed to light-induced surface bandgap opening from the first-principles calculations. The photocurrent and responsivity can be as large as 40 µA and 250 A W-1 for a 3.8 µm laser at 77 K. Furthermore, the WTe2 anomalous photocurrent matches its in-plane crystal structure and exhibits light polarization dependence, maximal for linear laser polarization along the W atom chain a direction and minimal for the perpendicular b direction, with the anisotropic ratio of 4.9. Consistently, first-principles calculations confirm the angle-dependent bandgap opening of WTe2 under polarized light irradiation. The anomalous and polarization-sensitive photoresponses suggest that linearly polarized light can significantly tune the WTe2 surface electronic structure, providing a potential approach to detect polarized and broadband lights up to far infrared range.

Nanoscale Bandgap Tuning across an Inhomogeneous Ferroelectric Interface.

We report nanoscale bandgap engineering via a local strain across the inhomogeneous ferroelectric interface, which is controlled by the visible-light-excited probe voltage. Switchable photovoltaic effects and the spectral response of the photocurrent were explored to illustrate the reversible bandgap variation (∼0.3 eV). This local-strain-engineered bandgap has been further revealed by in situ probe-voltage-assisted valence electron energy-loss spectroscopy (EELS). Phase-field simulations and first-principle calculations were also employed for illustration of the large local strain and the bandgap variation in ferroelectric perovskite oxides. This reversible bandgap tuning in complex oxides demonstrates a framework for the understanding of the optically related behaviors (photovoltaic, photoemission, and photocatalyst effects) affected by order parameters such as charge, orbital, and lattice parameters.

Bandgap-Tuning in Triple-Chalcogenophene Polymer Films by Thermal Annealing.

The authors study adjustable bandgap properties of the novel triple chalcogenophene-based polymer poly-(3-hexyl-2(3-(4-hexylthiophene-2-yl)-4,5-butylselenophene-1-yl)-5-(4,5-butyltellurophene-1-yl)thiophene) through a combination of morphological, spectroscopic, and computational techniques. The bandgap can be tuned after polymerization by means of mild temperature annealing, which will allow for a partnership with a broader range of donor/acceptor molecules, a property that makes it potentially suitable for organic photovoltaic implementation. The bandgap is modified by selection of the annealing temperatures, and the process is arguably related to the aggregation of tellurophene units, as similar effects are observed in polytellurophenes. Moreover, adequate chemistry engineering ensures easy solution processability and attainment of homogeneous films, which is also essential for applications.

Near Full-Composition-Range High-Quality GaAs1-xSbx Nanowires Grown by Molecular-Beam Epitaxy.

Here we report on the Ga self-catalyzed growth of near full-composition-range energy-gap-tunable GaAs1-xSbx nanowires by molecular-beam epitaxy. GaAs1-xSbx nanowires with different Sb content are systematically grown by tuning the Sb and As fluxes, and the As background. We find that GaAs1-xSbx nanowires with low Sb content can be grown directly on Si(111) substrates (0 ≤ x ≤ 0.60) and GaAs nanowire stems (0 ≤ x ≤ 0.50) by tuning the Sb and As fluxes. To obtain GaAs1-xSbx nanowires with x ranging from 0.60 to 0.93, we grow the GaAs1-xSbx nanowires on GaAs nanowire stems by tuning the As background. Photoluminescence measurements confirm that the emission wavelength of the GaAs1-xSbx nanowires is tunable from 844 nm (GaAs) to 1760 nm (GaAs0.07Sb0.93). High-resolution transmission electron microscopy images show that the grown GaAs1-xSbx nanowires have pure zinc-blende crystal structure. Room-temperature Raman spectra reveal a redshift of the optical phonons in the GaAs1-xSbx nanowires with x increasing from 0 to 0.93. Field-effect transistors based on individual GaAs1-xSbx nanowires are fabricated, and rectifying behavior is observed in devices with low Sb content, which disappears in devices with high Sb content. The successful growth of high-quality GaAs1-xSbx nanowires with near full-range bandgap tuning may speed up the development of high-performance nanowire devices based on such ternaries.

New Insights into the Origins of Sb-Induced Effects on Self-Catalyzed GaAsSb Nanowire Arrays.

Ternary semiconductor nanowire arrays enable scalable fabrication of nano-optoelectronic devices with tunable bandgap. However, the lack of insight into the effects of the incorporation of Vy element results in lack of control on the growth of ternary III-V(1-y)Vy nanowires and hinders the development of high-performance nanowire devices based on such ternaries. Here, we report on the origins of Sb-induced effects affecting the morphology and crystal structure of self-catalyzed GaAsSb nanowire arrays. The nanowire growth by molecular beam epitaxy is changed both kinetically and thermodynamically by the introduction of Sb. An anomalous decrease of the axial growth rate with increased Sb2 flux is found to be due to both the indirect kinetic influence via the Ga adatom diffusion induced catalyst geometry evolution and the direct composition modulation. From the fundamental growth analyses and the crystal phase evolution mechanism proposed in this Letter, the phase transition/stability in catalyst-assisted ternary III-V-V nanowire growth can be well explained. Wavelength tunability with good homogeneity of the optical emission from the self-catalyzed GaAsSb nanowire arrays with high crystal phase purity is demonstrated by only adjusting the Sb2 flux.

Hybrid Perovskite Quantum Nanostructures Synthesized by Electrospray Antisolvent-Solvent Extraction and Intercalation.

Perovskites based on organometal lead halides have attracted great deal of scientific attention recently in the context of solar cells and optoelectronic devices due to their unique and tunable electronic and optical properties. Herein, we show that the use of electrospray technique in conjunction with the antisolvent-solvent extraction leads to novel low-dimensional quantum structures (especially 2-D nanosheets) of CH3NH3PbI3- and CH3NH3PbBr3-based layered perovskites with unusual luminescence properties. We also show that the optical bandgaps and emission characteristics of these colloidal nanomaterials can be tuned over a broad range of visible spectral region by compositional tailoring of mixed-halide (I- and Br-based) perovskites.

Blue-Green Color Tunable Solution Processable Organolead Chloride-Bromide Mixed Halide Perovskites for Optoelectronic Applications.

Solution-processed organo-lead halide perovskites are produced with sharp, color-pure electroluminescence that can be tuned from blue to green region of visible spectrum (425-570 nm). This was accomplished by controlling the halide composition of CH3NH3Pb(BrxCl1-x)3 [0 ≤ x ≤ 1] perovskites. The bandgap and lattice parameters change monotonically with composition. The films possess remarkably sharp band edges and a clean bandgap, with a single optically active phase. These chloride-bromide perovskites can potentially be used in optoelectronic devices like solar cells and light emitting diodes (LEDs). Here we demonstrate high color-purity, tunable LEDs with narrow emission full width at half maxima (FWHM) and low turn on voltages using thin-films of these perovskite materials, including a blue CH3NH3PbCl3 perovskite LED with a narrow emission FWHM of 5 nm.

Band Gap Tuning of CH3NH3Pb(Br(1-x)Clx)3 Hybrid Perovskite for Blue Electroluminescence.

We report on the structural, morphological and optical properties of AB(Br(1-x)Cl(x))3 (where, A = CH3NH3(+), B = Pb(2+) and x = 0 to 1) perovskite semiconductor and their successful demonstration in green and blue emissive perovskite light emitting diodes at room temperature. The bandgap of perovskite thin film is tuned from 2.42 to 3.16 eV. The onset of optical absorption is dominated by excitonic effects. The coulomb field of the exciton influences the absorption at the band edge. Hence, it is necessary to explicitly account for the enhancement of the absorption through the Sommerfield factor. This enables us to correctly extract the exciton binding energy and the electronic bandgap. We also show that the lattice constant varies linearly with the fractional chlorine content satisfying Vegards law.