Tunable Band Gap Research Articles

Advancing Silver Bismuth Sulfide Quantum Dots for Practical Solar Cell Applications.

Colloidal quantum dots (CQDs) show unique properties that distinguish them from their bulk form, the so-called quantum confinement effects. This feature manifests in tunable size-dependent band gaps and discrete energy levels, resulting in distinct optical and electronic properties. The investigation direction of colloidal quantum dots (CQDs) materials has started switching from high-performing materials based on Pb and Cd, which raise concerns regarding their toxicity, to more environmentally friendly compounds, such as AgBiS2. After the first breakthrough in solar cell application in 2016, the development of AgBiS2 QDs has been relatively slow, and many of the fundamental physical and chemical properties of this material are still unknown. Investigating the growth of AgBiS2 QDs is essential to understanding the fundamental properties that can improve this material's performance. This review comprehensively summarizes the synthesis strategies, ligand choice, and solar cell fabrication of AgBiS2 QDs. The development of PbS QDs is also highlighted as the foundation for improving the quality and performance of AgBiS2 QD. Furthermore, we prospectively discuss the future direction of AgBiS2 QD and its use for solar cell applications.

Topology Optimization of Hard-Magnetic Soft Phononic Structures for Wide Magnetically Tunable Band Gaps

Abstract Hard-magnetic soft materials, which exhibit finite deformation under magnetic loading, have emerged as a promising class of soft active materials for the development of phononic structures with tunable elastic wave band gap characteristics. In this paper, we present a gradient-based topology optimization framework for designing the hard-magnetic soft materials-based two-phase phononic structures with wide and magnetically tunable anti-plane shear wave band gaps. The incompressible Gent hyperelastic material model, along with the ideal hard-magnetic soft material model, is used to characterize the constitutive behavior of the hard-magnetic soft phononic structure phases. To extract the dispersion curves, an in-house finite element model in conjunction with Bloch’s theorem is employed. The method of moving asymptotes is used to iteratively update the design variables and obtain the optimal distribution of the hard-magnetic soft phases within the phononic structure unit cell. Analytical sensitivity analysis is performed to evaluate the gradient of the band gap maximization function with respect to each one of the design variables. Numerical results show that the optimized phononic structures exhibit a wide band gap width in comparison to a standard hard-magnetic soft phononic structure with a central circular inclusion, demonstrating the effectiveness of the proposed numerical framework. The numerical framework presented in this study, along with the derived conclusions, can serve as a valuable guide for the design and development of futuristic tunable wave manipulators.

A Flexible MXene-Black Phosphorus/Zinc Oxide Hybrid Structure with Excellent UVA-Specific Photoelectric Sensing Properties for Human Skin Protection.

Ultraviolet A (UVA) radiation causes various irreversible damages to human skin, so the research about UVA-specific sensing device is urgent. 2D black phosphorus (BP) is used in many photosensors due to its advantages of high carrier mobility and tunable bandgap, but its application for UVA-specific photosensor is not reported. Here, a MXene-BP/Zinc oxide (ZnO) hybrid structure with lamellar-spherical interfaces like finger lime fruit is prepared by the layer-by-layer assembly (LLA) method, and p-n junctions are constructed between BP and ZnO with the Ti3C2Tx electrode, showing excellent photoelectric performance. Density functional theory (DFT) calculations demonstrate that the enhanced performance is attributed to the rapid separation of photogenerated carriers in the presence of a built-in electric field at interface. Furthermore, a flexible MXene-BP/ZnO based UVA-specific photosensor is prepared, which shows a specific response to UVA as high as 7 mAW-1 and excellent mechanical stability, maintaining 98.46% response after 100 bending cycles. In particular, the integrated anti-UVA skin protection device shows excellent UVA-specific identification and wireless transmission capability, which can provide timely UVA exposure information and skin protection warning for the visually impaired. This work demonstrates a new approach for further developments of advanced photoelectric sensing technology toward improving people's skin health protection.

Enhanced thermoelectric properties in hybrid graphane/graphene nanoribbons

The thermoelectric properties of hybrid graphane and graphene nanoribbons (GGNRs) are studied by the Landauer formula within the atomistic non-equilibrium Green's function. It is shown that hybrid GGNRs present the tunable band gap depending upon the width ratio of their components. Modulation of hybrid GGNRs can give rise to the lower thermal conductance of phonons and the better thermoelectric properties compared to pure graphene nanoribbons and graphane nanoribbons. Introducing the hydrogen defects can enhance the maximum of ZT (ZTmax) in both armchair GGNRs (AGGNRs) and zigzag GGNRs (ZGGNRs). Such the enhancement of ZTmax sensitively depends upon the defect concentrations. Among different defect concentrations, ZTmax for the 20 % defect concentration has the highest value, which can be enhanced to 0.42 and 0.24 at T = 300 K in AGGNRs and ZGGNRs, respectively. A laconic analysis of these results is given.

Low-dimensional halide perovskites for advanced electronics

Halide perovskites are gaining prominence as promising materials for future electronic applications, primarily due to their unique properties including long carrier diffusion lengths, tunable bandgap, facile synthesis, and cost efficiency. However, polycrystalline halide perovskite thin films, which have been widely studied to date, have significant drawbacks including uncontrollable grain boundaries and instability issues. Recently, low-dimensional halide perovskites (LD HPs) offer enhanced stability and adaptable morphologies, making them attractive candidates for next-generation electronics beyond optoelectronics. This review comprehensively explores recent advancements in LD HP-based electronics, covering structural characteristics, synthesis methods tailored to different dimensions, and diverse applications. Furthermore, the impressive performance demonstrated by LD HPs in electronic applications including resistive random-access memory, advanced transistors, and neuromorphic computing hardware is discussed. Finally, the review outlines the challenges and perspectives required to scale up LD HP-based advanced electronics for commercial production, offering valuable insights for researchers venturing into the realm of new materials for advanced electronics.

Engineering Perovskite Bandgap for Control of Hot‐Electron Dynamics in Plasmonic Nanodiodes

Despite extensive research on utilizing plasmonic hot carriers to advance photovoltaics and photocatalysts, achieving high hot‐carrier flux remains challenging due to their rapid relaxation. Recent studies have shown that combining plasmonic metals with perovskites improves hot‐electron flow, due to the slow hot‐electron relaxation in perovskites. Additionally, perovskites offer the advantage of facile bandgap tuning through composition changes. Herein, the influence of tuning the perovskite bandgap on the lifetime and flow of hot electrons in a perovskite/plasmonic Au/TiO2 nanodiode is explored. The findings reveal that perovskites with wider bandgaps exhibit improved hot‐electron lifetime and flow, attributed to the modified hot‐electron energy favoring a slower energy loss rate, as verified by ultrafast transient absorption spectroscopic analysis. It is believed that the results successfully demonstrate the integration of engineered hot‐carrier physics into device functions, providing valuable guidance for the design of optimized hot‐carrier‐based devices in the future.

Halide tuning in derivative organic–inorganic perovskites, MAPb(Br1-xClx)3 (x = 0–1): exploring structural, optical and vibrational characteristics

Organic–inorganic metal halide perovskites (OIMHP’s), particularly CH3NH3PbX3 (X = I, Br, Cl) and their derivatives shows favorable properties for energy harvesting such as high absorption coefficients, adjustable band gaps, and low charge recombination rate. The structure and hence nature of bonding between different atoms of these perovskites is known to affect their properties significantly. Tuning of band gap can be achieved in these systems with the help of compositional variation. These systems are studied extensively in the single halide compositions (MAPbI3, MAPbBr3 and MAPbCl3); while, their derivatives seem to have gained less attention though being important for various applications. So, in this work, halide tuning is achieved in derivative perovskite, MAPb(Br1-xClx)3 (x = 0 to 1) and further studied for structural and optical properties along with vibrational properties using X-ray diffraction (XRD), diffuse reflectance spectroscopy, and Raman spectroscopy techniques, respectively. A decrease in the lattice parameter is observed as the Chlorine content increases in the MAPb(Br1-xClx)3 (x = 0 to 1) perovskite. The substitution of Chlorine with Bromine also results in significant increase in the band gap value. In contrast to previous reports, it was clearly observed that the Urbach energy strongly depends on the composition. For the first time, appearance of two features for torsional mode of methylammonium (MA) is discussed even at room temperature, indicative of disorder. It is observed that although the band gap tuning is achieved with the help of halide mixing (Br and Cl), it is also found to introduce disorder in the intermediate compositions; while, the stability increases toward Chlorine compositions. Interestingly, the information of disorder is found to be contained in both the global as well as local measurements which opens up new pathways for studying these materials. This study will lay down a pathway for better understanding of key properties of these hybrid mix halide perovskites which are promising material for futuristic energy applications.

Tunable bandgaps of guided waves by periodic shunting circuits in multilayered piezoelectric plates

The multi-mode and dispersion characteristics of guided waves in plate bring great challenges to the manipulation of guided waves and controlling vibration and noise. In this study, the Stroh formalism is developed to establish a theoretical model for deriving the dispersion relations of guided waves in a multilayered piezoelectric plate. The dispersion characteristics under different electrical boundary conditions introduced by periodic shunting circuits are discussed to reveal the influences of external circuits on guided wave propagation. The proper shunting circuit is not only the key point to obtain the specific frequency of bandgap, but also the effective method to control the bandwidth. Furthermore, for the separation of symmetric and anti-symmetric modes of guided waves, the multilayered piezoelectric plate with a mirror plane is studied by using an equivalent model. Results indicate that the propagation behaviors of guided waves in multilayered piezoelectric plates can be interpreted by developed Stroh formalism, and their bandgaps can be effectively manipulated by periodically external circuits. The tunable bandgaps in this work could be helpful for designing smart devices of wave isolation based on multilayered piezoelectric plate.

Synthesis and Processing Strategy for High-Bandgap PbS Quantum Dots: A Promising Candidate for Harvesting High-Energy Photons in Solar Cells.

The wide tunability of the energy bandgap of colloidal lead sulfide (PbS) quantum dots (QDs) has uniquely positioned them for the development of single junction and tandem solar cells. While there have been substantial advancements in moderate and narrow bandgap PbS QDs-ideal for single junction solar cells and the bottom cell in tandem solar cells, respectively; progress has been limited in high-bandgap PbS QDs that are ideally suited for the formation of the top cell in tandem solar cells. The development of appropriate high bandgap PbS QDs would be a major advancement toward realizing efficient all-QD tandem solar cells utilizing different sizes of PbS QDs. Here, we report a comprehensive approach encompassing synthetic strategy, ligand engineering, and hole transport layer (HTL) modification to implement high-bandgap PbS QDs into solar cell devices. We achieved a greater degree of size homogeneity in high-bandgap PbS QDs through the use of a growth retarding agent and a partial passivation strategy. By adjusting the ligand polarity, we successfully grow HTL over the QD film to fabricate solar cells. With the aid of an interface modifying layer, we incorporated an organic HTL for the realization of high-performance solar cells. These solar cells exhibited an impressive open-circuit voltage of 0.824 V and a power conversion efficiency of 10.7%, marking a 360% improvement over previous results.

Tuning of Band Gap of Cathode Li2NiPO4F by Replacing P to Nb and Forming Li2NiNbO4F for Application as 5 V Cathode in Lithium Ion Battery: A Density Functional Theory Study

Electrochemical properties of Li2NiPO4F were studied using density functional theory. The obtained voltage, electronic band gap, capacity (∼ for 2 Li+ extraction) and energy density are achieved as 5.33 V, 4.0 eV, 287.3 mAh g−1 and 1531.31 Wh kg−1, respectively. Although, the electrochemical properties of Li2NiPO4F are promising, large electronic band gap would certainly pose a limitation for its commercial application. Nb is a transition metal and its electronegativity is 1.6 which is less than the electronegativity of 2.19 for P. This implies, less operating voltage would be obtained if we replace P in Li2NiPO4F by Nb to form Li2NiNbO4F. However, electronic configuration of Nb is [Kr] 4d45 s1 and the valance state of Nb in Li2NiNbO4F is +5, which in turn specify that, localized Nb d states will reside in conduction band of Li2NiNbO4F and hence the electronic band-gap would be less owing to this localized Nb-d states. Our speculation gets verified by the calculated properties of Li2NiNbO4F obtained through DFT as follows; Voltage, electronic band gap, capacity (∼ for 2 Li+ extraction) and energy density achieved, respectively, are 5.01 V, 3.64 eV (less than LiFePO4), 215.71 mAh g−1, 1080.71 Wh kg−1. Lower electronic band gap of Li2NiNbO4F makes it an alternative to Li2NiPO4F.

Structural and photoelectric properties of hybrid halide perovskites CsxMA1-xMgyPb1-yI3 from first-principles

Lead toxicity and stability are important issues to be addressed in organic/inorganic hybrid perovskite solar cell materials. In this study, the electronic, structural, and optical properties of Cs and Mg co-doped organic/inorganic hybrid perovskites were investigated through first-principles calculations. The synergistic effect of (Cs, Mg) doping improves the lattice stability, reduces the content of elemental lead, thereby reducing environmental pollution, and induces a tunable band gap of 0.96–2.58 eV. Perovskite with a bandgap of 1.5–1.6 eV is an ideal adsorbent for solar cells, while that with a bandgap greater than 1.70 eV can be used for perovskite-silicon tandem solar cells. Co-doping of Cs and Mg compresses the neighboring Pb–I and Mg–I bond and distorts the [PbI6] octahedra. The organic/inorganic hybrid perovskites co-doped with cesium and magnesium significantly increase the light absorption coefficients in the near-ultraviolet and visible regions. The predicted Cs and Mg co-doped halide perovskites with intriguing properties would become a promising candidate for applications in solar cells and optoelectronic devices.

Photo-Driven Ion Directional Transport across Artificial Ion Channels: Band Engineering of WS2 via Peptide Modification.

Biological photo-responsive ion channels play important roles in the important metabolic processes of living beings. To mimic the unique functions of biological prototypes, the transition metal dichalcogenides, owing to their excellent mechanical, electrical, and optical properties, are already used for artificial intelligent channel constructions. However, there remain challenges to building artificial bio-semiconductor nanochannels with finely tuned band gaps for accurately simulating or regulating ion transport. Here, two well-designed peptides are employed for the WS2 nanosheets functionalization with the sequences of PFPFPFPFC and DFDFDFDFC (PFC and DFC; P: proline, D: aspartate, and F: phenylalanine) through cysteine (Cys, C) linker, and an asymmetric peptide-WS2 membrane (AP-WS2M) could be obtained via self-assembly of peptide-WS2 nanosheets. The AP-WS2M could realize the photo-driven anti-gradient ion transport and vis-light enhanced osmotic energy conversion by well-designed working patterns. The photo-driven ion transport mechanism stems from a built-in photovoltaic motive force with the help of formed type II band alignment between the PFC-WS2 and DFC-WS2. As a result, the ions would be driven across the channels of the membrane for different applications. The proposed system provides an effective solution for building photo-driven biomimetic 2D bio-semiconductor ion channels, which could be extensively applied in the fields of drug delivery, desalination, and energy conversion.

The nonlinear optical property of bandgap-tunable TMDs-PdSe2: Toward a generation mode for near-infrared ultrashort laser pulses

Two-dimensional (2D) transition metal chalcogenides (TMDs) materials have been more and more important in various research fields such as nanoelectronics, spintronics, ultrafast photonics, etc. Optical materials with compositive functions have always been desired. This work successfully verified that 2D PdSe2 nanosheets have adjustable layers and tunable bandgaps. Besides, by using the 2D PdSe2 nanosheets as saturable absorption devices in a 2 μm solid-state laser, it is discovered that the 2D PdSe2 shows obvious nonlinear saturable absorption characteristics. Moreover, in the 2 μm Q-switched mode-locked laser, an ultrashort pulse laser output of 486.5 ps was achieved, proving the excellent ultrafast modulation characteristics of PdSe2. To insight into the relationship between the structure and its optical performances, theoretical modeling and calculations were implemented based on the layered structure of PdSe2. All the above indicates that the 2D PdSe2 could be promising saturable absorption devices and ultrafast photonic devices, which may promote the development of ultrashort lasers.

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.

Mechanical Design Guidelines to Inhibit Fracture in Perovskite Solar Cells

Perovskite (PVSK) solar cells offer significant benefits over conventional silicon cells including low‐cost solution processibility, minimal materials usage related to strong photon absorption in thin‐film cell architectures, and a tunable bandgap. However, PVSK films are mechanically fragile, and fracture of PVSK layers and adjacent interfaces are a significant concern during fabrication, encapsulation, and operation. Herein, a thin‐film mechanics fracture analysis tailored for p–i–n and n–i–p PVSK solar cells on both soda lime glass and polyimide substrates fabricated with three PVSK crystallization methods is presented. The role of thermal processing of each cell layer is explored to determine the maximum allowable temperature below which fracture is inhibited. In the analysis, the mechanics basis for processing and materials selection guidelines for preventing fracture in PVSK solar cells is provided.

All-solution preparation of perovskite light-emitting diodes in ambient air through film-forming regulation of light-emitting layers based on dual-additive doping and oxygen plasma treatment

Organic-inorganic hybrid perovskites are promising for optoelectronics owing to their high color purity, tunable bandgaps, and low nonradiative recombination rates. However, challenges such as rough surfaces and poor film-forming properties constrain the optoelectronic performance of light-emitting devices. Herein, the PEDOT:PSS film treated by oxygen plasma serves as the hole transport layer, while the formation of perovskite films is optimized by dual-additive doping of PEO and TPBi in ambient air. The results show that the PEDOT:PSS films with PSSH-rich after oxygen plasma treatment provide more nucleation sites, favoring the formation of the perovskite film. Meanwhile, the dual-additive prompts to form a dense and uniform film as well. The intrinsic mechanisms involve PEO as a binder to fill grain gaps and improve water-oxygen stability in the perovskite film, while TPBi acts as a passivator to stimulate uniform nucleation and dense crystallization, improving the grain coverage of the light-emitting layer. Under atmospheric conditions, all-solution processed perovskite devices reach a maximum luminance of 810.4 cd m−2 and a maximum current efficiency of 0.437 cd A−1. This work highlights the significance of using oxygen plasma treatment and additives to improve the performance of perovskite films and achieve superior PeLEDs.

Self-aware active metamaterial cell 3D-printed in a single process

Metamaterials are capable of attenuating undesired mechanical vibrations within a narrow band-gap frequency range; however, real-world applications often require adjustments due to varying loads and frequency content. This study introduces a self-aware, thermo-active metamaterial, 3D-printed in a single process using thermoplastic material extrusion. The adjustment of the natural frequency and band-gap region is achieved through resistive heating of conductive paths, which alters the stiffness of the base cell’s resonator. Additionally, these conductive paths facilitate the detection of the resonator’s excitation frequency and temperature, thereby eliminating the need for external sensors. This dynamic adaptability, experimentally demonstrated by achieving a band-gap tuning range from 505 Hz to 445 Hz with a 17 °C temperature difference, highlights the potential of these metamaterials for applications in smart structures across the aerospace, civil, and automotive industries.

Influence of Edges and Interlayer Electron-phonon Coupling in WS2/h-BN Heterostructure.

The semiconducting layered transition metal dichalcogenides (e.g., WS2) are excellent candidates for the realization of optoelectronic and nanophotonic applications on account of their band gap tunability, high binding energy and oscillator strength of the excitons, strong light-matter interaction, appreciable charge carrier mobility, and valleytronic properties. However, the photoluminescence (PL) emissions are reported to show a nonuniform spatial distribution, with the edges emitting features like defect-bound excitons and biexcitons at low temperatures in addition to the typical excitons and trions. The appearance of these additional PL features has been shown in the literature to have a strong dependence on the presence of S-vacancies and excess charge carriers. We demonstrate an enhancement of the defect-bound excitons and biexcitons by creating a heterostructure of WS2 with h-BN where the coupling between the charge carriers in WS2 with the polar phonons in h-BN governs the enhancement. Furthermore, we have performed a comprehensive resonant Raman study with varying polarization and magnetic field which not only confirms the presence of electron-phonon coupling in WS2/h-BN heterostructure, it further demonstrates a thermally induced differential resonance behavior with the excitonic level and the defect-induced midgap states (due to S-vacancies at the edge of WS2) exhibited by a dome-shaped behavior of the Raman intensities with temperature for the normal and defect-induced phonon modes. The defect-bound Raman modes exhibit maximum resonance at ∼240 K while normal Raman modes show at ∼280 K owing to a thermal variation of the electronic states.

Non-linear dynamics and bandgap control in magneto-rheological elastomers metamaterials with inertial amplification

Sandwich plate structures are extensively utilized in engineering due to their favorable stiffness-to-weight ratio. Nonetheless, these lightweight thin-walled structures frequently encounter challenges related to inadequate low-frequency vibration performance, which significantly restricts their applications, particularly in the realm of precision instruments which is sensitive to vibration. This study introduces an innovative design of an active nonlinear metamaterial, to achieve tunable broadband low-frequency bandgaps for sandwich plates. The nonlinear oscillator incorporates an inertia amplification mechanism (IAM), Euler-buckled beams, mass elements, and magneto-rheological elastomers (MREs), which are modulated via external magnetic fields to adjust the material's stiffness dynamically. Employing Hamilton's principles and the plate wave expansion method (PWE), the dispersion relations for the metamaterial plate are derived, elucidating the dispersion surfaces and the band structures within its sandwich-like plates.The dynamical equations of the metamaterial plate are formulated and validated through numerical simulations using the Galerkin method, confirming the theoretical predictions. The results demonstrate effective control over low-frequency and broadband bandgaps under low mass ratio conditions through strategic manipulation of the inertia amplification factor and magnetic flux. The study extensively explores the nonlinear dynamic responses of the metamaterial, highlighting the significant impact of excitation amplitudes on the amplitude-dependent bandgaps.

Water-Soluble Lead Sulfide Nanoparticles: Direct Synthesis and Ligand Exchange Routes.

Colloidal semiconductor nanoparticles (NPs) represent an emergent state of matter with unique properties, bridging bulk materials and molecular structures. Their distinct physical attributes, such as bandgap and photoluminescence, are intricately tied to their size and morphology. Ligand passivation plays a crucial role in shaping NPs and determining their physical properties. Ligand exchange (LE) offers a versatile approach to tailoring NP properties, often guided by Pearson's Hard-Soft Acid-Base theory. Lead sulfide (PbS), a semiconductor of considerable interest, exhibits size-dependent tunable bandgaps from the infrared to the visible range. Here, we present two methods for synthesizing water-soluble, polyvinylpyrrolidone (PVP)-coated PbS NPs. The first involves direct synthesis in an aqueous solution while utilizing PVP as the surfactant for the formation of nano-cubes with a crystal coherence length of ~30 nm, while the second involves LE from octadecylamine-coated PbS truncated nano-cubes to PVP-coated PbS NPs with a crystal coherence length of ~15 nm. Multiple characterization techniques, including X-ray diffraction, transmission electron microscopy, Fourier-transform infrared spectroscopy, and thermal gravimetric analysis, confirmed the results of the synthesis and allowed us to monitor the ligand exchange process. Our findings demonstrate efficient and environmentally friendly approaches for synthesizing PVP-coated PbS NPs.