Large-Area Perovskite Nanocrystal Metasurfaces for Direction-Tunable Lasing.

Perovskite nanocrystals (PNCs) are attractive emissive materials for developing compact lasers. However, manipulation of PNC laser directionality has been difficult, which limits their usage in photonic devices that require on-demand tunability. Here we demonstrate PNC metasurface lasers with engineered emission angles. We fabricated millimeter-scale CsPbBr3 PNC metasurfaces using an all-solution-processing technique based on soft nanoimprinting lithography. By designing band-edge photonic modes at the high-symmetry X point of the reciprocal lattice, we achieved four linearly polarized lasing beams along a polar angle of ∼30° under optical pumping. The device architecture further allows tuning of the lasing emission angles to 0° and ∼50°, respectively, by adjusting the PNC thickness to shift other high-symmetry points (Γ and M) to the PNC emission wavelength range. Our laser design strategies offer prospects for applications in directional optical antennas and detectors, 3D laser projection displays, and multichannel visible light communication.

Customization of 2D Atomic-Molecular Heterojunction with Manipulatable Charge-Transfer and Band Structure.

Manipulating the properties of 2D materials through meticulously engineered artificial heterojunctions holds great promise for novel device applications. However, existing research on the crucial charge-transfer interactions and energy profile regulation is predominantly focused on 2D van der Waals structures formed via weak van der Waals forces, limiting regulatory efficiency at high costs. Herein, a refined atomic-molecular heterojunction strategy featuring strong covalent bonds between organic molecule and 2D violet phosphorus (VP) atomic crystal is developed, which enables enhanced charge-transfer dynamics and customizable band structure regulation at the molecular level. Both experimentally and theoretically, it is demonstrated that grafting efficiency, charge redistribution, and energy gap regulation critically depend on organic electronegativity, providing a low-cost yet high-efficiency regulatory effect on a large scale. As a proof of concept, the novel VP-molecular heterojunctions exhibit optimized performance in diverse application domains, presenting a general platform for future high-performance device applications.

Combined effect of strain and intrinsic spin-orbit coupling on band gap engineering of GNRs: a first-principles study.

By employing first-principles calculations, we theoretically investigate the impact of uniaxial strain and intrinsic spin-orbit coupling (SOC) on the electronic properties of zigzag and armchair edge hydrogen (H)-passivated graphene nanoribbons (GNRs). We find that band structure and density of states of 4-zigzag graphene nanoribbon (ZGNR) and 15-armchair graphene nanoribbon (AGNR) are highly sensitive to the combined effect of strain and intrinsic SOC. In the case of H-passivated 4-ZGNR, SOC with a strain>10% increases the energy band by increasing spin-polarized states at the opposite edges. In contrast to 4-ZGNR, the oscillatory behavior of band gap of H-passivated 15-AGNR is preserved in the presence of strain and SOC. Moreover, for both types of GNRs (zigzag and armchair), the presence of strain and intrinsic SOC preserve spin symmetry.

Electronic and Transport Engineering of A-Type Antiferromagnets with Ferroelectric Sandwich Structure: Toward Multistate Nonvolatile Memory Applications.

Achieving higher-order multistates with mutual interstate switching at the nanoscale is essential for high-density storage devices; yet, it remains a significant challenge. Here, we demonstrate that integrating A-type antiferromagnetic semiconductors sandwiched between ferroelectric layers is an effective strategy to achieve high-performance multistate data storage. Taking the Sc2CO2/VSi2P4 bilayer (bi-VSi2P4)/Sc2CO2 van der Waals multiferroic heterostructure as an example, our first-principles calculations show that by switching the polarization direction of the upper and bottom ferroelectric Sc2CO2 layers, antiferromagnetic bi-VSi2P4 can exhibit four distinct states with different band structures. The intriguing band structure engineering stems from the polarization-field-induced band shift and interface charge transfer. Accordingly, the proposed Sc2CO2/bi-VSi2P4/Sc2CO2-based multiferroic device can achieve four different resistance states, accompanied by fully spin-polarized currents and giant tunneling electroresistance ratios. Our results propose a viable strategy for realizing nonvolatile electrical control of antiferromagnets at the nanoscale and provide insights into the development of advanced memories.

Band Structure Engineering in 2D Metal-Organic Frameworks.

The design of 2D metal-organic frameworks (2D MOFs) takes advantage of the combination of the diverse electronic properties of simple organic ligands with different transition metal (TM) centers. The strong directional nature of the coordinative bonds is the basis for the structural stability and the periodic arrangement of the TM cores in these architectures. Here, direct and clear evidence that 2D MOFs exhibit intriguing energy-dispersive electronic bands with a hybrid character and distinct magnetic properties in the metal cores, resulting from the interactions between the TM electronic levels and the organic ligand π-molecular orbitals, is reported. Importantly, a method to effectively tune both the electronic structure of 2D MOFs and the magnetic properties of the metal cores by exploiting the electronic structure of distinct TMs is presented. Consequently, the ionization potential characteristic of selected TMs, particularly the relative energy position and symmetry of the 3d states, can be used to strategically engineer bands within specific metal-organic frameworks. These findings not only provide a rationale for band structure engineering in 2D MOFs but also offer promising opportunities for advanced material design.

Bandgap Calculation and Experimental Analysis of Piezoelectric Phononic Crystals Based on Partial Differential Equations.

Focusing on the bending wave characteristic of plate-shell structures, this paper derives the complex band curve of piezoelectric phononic crystal based on the equilibrium differential equation in the plane stress state using COMSOL PDE 6.2. To ascertain the computational model's accuracy, the computed complex band curve is then cross-validated against real band curves obtained through coupling simulations. Utilizing this model, this paper investigates the impact of structural and electrical parameters on the bandgap range and the attenuation coefficient in the bandgap. Results indicate that the larger surface areas of the piezoelectric sheet correspond to lower center bands in the bandgap, while increased thickness widens the attenuation coefficient range with increased peak values. Furthermore, the influence of inductance on the bandgap conforms to the variation law of the electrical LC resonance frequency, and increased resistance widens the attenuation coefficient range albeit with decreased peak values. The incorporation of negative capacitance significantly expands the low-frequency bandgap range. Visualized through vibration transfer simulations, the vibration-damping ability of the piezoelectric phononic crystal is demonstrated. Experimentally, this paper finds that two propagation modes of bending waves (symmetric and anti-symmetric) result in variable voltage amplitudes, and the average vibration of the system decreases by 4-5 dB within the range of 1710-1990 Hz. The comparison between experimental and model-generated data confirms the accuracy of the attenuation coefficient calculation model. This convergence between experimental and computational results emphasizes the validity and usefulness of the proposed model, and this paper provides theoretical support for the application of piezoelectric phononic crystals in the field of plate-shell vibration reduction.

High dynamic range scanning tunneling microscopy.

We increase the dynamical range of a scanning tunneling microscope (STM) by actively subtracting dominant current-harmonics generated by nonlinearities in the current-voltage characteristics that could saturate the current preamplifier at low junction impedances or high gains. The strict phase relationship between a cosinusoidal excitation voltage and the current-harmonics allows excellent cancellation using the displacement-current of a driven compensating capacitor placed at the input of the preamplifier. Removal of DC currents has no effect on, and removal of the first harmonic only leads to a rigid shift in differential conductance that can be numerically reversed by adding the known removal current. Our method requires no permanent change of the hardware but only two phase synchronized voltage sources and a multi-frequency lock-in amplifier to enable high dynamic range spectroscopy and imaging. • Active power filter • Dynamic range compression • High gain preamplifier.

Slow sound mode prediction and band structure calculation in 1D phononic crystal nanobeams using an artificial neural network.

Phononic crystals, which are artificial crystals formed by the periodic arrangement of materials with different elastic coefficients in space, can display modulated sound waves propagating within them. Similar to the natural crystals used in semiconductor research with electronic bandgaps, phononic crystals exhibit the characteristics of phononic bandgaps. A gap design can be utilized to create various resonant cavities, confining specific resonance modes within the defects of the structure. In studies on phononic crystals, phononic band structure diagrams are often used to investigate the variations in phononic bandgaps and elastic resonance modes. As the phononic band frequencies vary nonlinearly with the structural parameters, numerous calculations are required to analyze the gap or mode frequency shifts in phononic band structure diagrams. However, traditional calculation methods are time-consuming. Therefore, this study proposes the use of neural networks to replace the time-consuming calculation processes of traditional methods. Numerous band structure diagrams are initially obtained through the finite-element method and serve as the raw dataset, and a certain proportion of the data is randomly extracted from the dataset for neural network training. By treating each mode point in the band structure diagram as an independent data point, the training dataset for neural networks can be expanded from a small number to a large number of band structure diagrams. This study also introduces another network that effectively improves mode prediction accuracy by training neural networks to focus on specific modes. The proposed method effectively reduces the cost of repetitive calculations.

Room-Temperature Magneto-Photoresponse in All-2D Optoelectronic Devices for In-Sensor Vision Systems.

Interplay between magnetism and photoelectric properties introduces the effective control of photoresponse in optoelectronic devices via magnetic field, termed as magneto-photoresponse. It enriches the application scenarios and shows potential to construct in-sensor vision systems for artificial intelligence with gate-free architecture. However, achieving a simultaneous existence of room-temperature magnetism and notable photoelectric properties in semiconductors is a great challenge. Here, the room-temperature magneto-photoresponse is accomplished in all-2D optoelectronic devices, employing 2D ferromagnet Fe3GaTe2 as the source and drain, with WSe2 forming the channel. The interplay between room-temperature magnetism and photoelectric properties is realized by introducing the unique magneto-band structure effect from 2D interface, resulting in magneto-tunable charge transfer between Fe3GaTe2 and WSe2. The photocurrent in this 2D optoelectronic device exhibits robust response to both the direction and amplitude of external magnetic fields. Utilizing constructed 2D optoelectronic devices with magneto-photoresponse, traditional gate-controlled phototransistors are replaced and a prototype in-sensor vision system with visual adaptation, significantly improving the recognition accuracy to over four times in low-contrast environments is established. These findings pave a way for achieving high-temperature magneto-photoresponse, thereby guiding the construction of robust in-sensor vision systems toward high performance and broad applications.

The visible magneto-optical response of RE1-xAxMnO3manganites: relationship with the charge component of the material.

Magnetic circular dichroism (MCD) spectroscopy for manganite films of various compositions and morphologies has been studied in the range of 1.2-3.7 eV. The primary focus was on the temperature behavior of the MCD spectra, as well as the magnetization and resistivity of the films. The data obtained were analyzed in comparison with magneto-optical spectroscopy of the Kerr rotation (KR) on both single crystal and thin film of manganites. It has been established that the MCD response at 2.3 eV is typical for manganites transitioning into a conducting state. Consequently, it reflects a change in the band structure of the material. This response is also observed in the KR spectrum of manganites in the range 2.3-2.6 eV below the metal-insulator transition temperature. These findings complement the understanding of the electronic structure of manganites in general. Moreover, they also provide a basis for the search for new functional materials.

Topological phases of tight-binding trimer lattice in the BDI symmetry class.

In this work, we theoretically study a modified Su-Schrieffer-Heeger (SSH) model in which each unit cell consists of three sites. Unlike existing extensions of the SSH model which are made by enlarging the periodicity of the (nearest-neighbor) hopping amplitudes, our modification is obtained by replacing the Pauli matrices in the system's Hamiltonian by their higher dimensional counterparts. This, in turn, leads to the presence of next-nearest neighbor hopping terms and the emergence of different symmetries than those of other extended SSH models. Moreover, the system supports a number of edge states that are protected by a combination of particle-hole, time-reversal, and chiral symmetry. Finally, our system could be potentially realized in various experimental platforms including superconducting circuits as well as acoustic/optical waveguide arrays.

3D Lead-Organoselenide-Halide Perovskites and their Mixed-Chalcogenide and Mixed-Halide Alloys.

We incorporate Se into the 3D halide perovskite framework using the zwitterionic ligand: SeCYS (+NH3(CH2)2Se-), which occupies both the X- and A+ sites in the prototypical ABX3 perovskite. The new organoselenide-halide perovskites: (SeCYS)PbX2 (X=Cl, Br) expand upon the recently discovered organosulfide-halide perovskites. Single-crystal X-ray diffraction and pair distribution function analysis reveal the average structures of the organoselenide-halide perovskites, whereas the local lead coordination environments and their distributions were probed through solid-state 77Se and 207Pb NMR, complemented by theoretical simulations. Density functional theory calculations illustrate that the band structures of (SeCYS)PbX2 largely resemble those of their S analogs, with similar band dispersion patterns, yet with a considerable band gap decrease. Optical absorbance measurements indeed show band gaps of 2.07 and 1.86 eV for (SeCYS)PbX2 with X=Cl and Br, respectively. We further demonstrate routes to alloying the halides (Cl, Br) and chalcogenides (S, Se) continuously tuning the band gap from 1.86 to 2.31 eV-straddling the ideal range for tandem solar cells or visible-light photocatalysis. The comprehensive description of the average and local structures, and how they can fine-tune the band gap and potential trap states, respectively, establishes the foundation for understanding this new perovskite family, which combines solid-state and organo-main-group chemistry.

Regulating band structure, charge transfer and separation, oxygen adsorption and activation by surface ion modification.

As a most promising environmental technology, the substantial enhancement of photocatalytic efficiency is still a big challenge for practical applications. In this work, the surface of Bi2O2CO3 (BOC) nanotubes are modified by Cl and I. The as-obtained samples at different hydrothermal temperatures (T) are designated as T-X-BOC (X = Cl, I). X-ray diffraction (XRD), energy dispersive X-ray (EDX) spectroscopy and X-ray photoelectron spectroscopy (XPS) prove that Cl and I merely chemically adsorb on the BOC surface, rather than dope into the crystal lattice. The surface modification of Cl and I slightly increases light absorption range, while significantly promotes the photoelectron migration from bulk to the surface that greatly enhances the carrier separation efficiency. Density functional theory (DFT) calculations further prove that surface Cl and I have adjusted band structure and surface charge distribution. Besides, the surface Cl and I favor the O2 adsorption and trap the surface photoelectrons, thus promoting the formation of •O2-; while the surface Cl and I impede the surface adsorption of H2O, thus refraining the generation of •OH. In the degradation of rhodamine B (RhB), holes and •O2- radicals play the crucial role. Under ultraviolet light irradiation (λ < 420 nm) for 45 min, the RhB degradation ratios over 150-Cl-BOC (94%) and 150-I-BOC (85%) are 4.2 and 3.7 times higher than that of original BOC (18%), respectively. This work demonstrates that the simple surface halogenation modification greatly improves the photocatalytic activity.

Efficient integration of covalent triazine frameworks (CTFs) for augmented photocatalytic efficacy: A review of synthesis, strategies, and applications.

Heterogeneous photocatalysis emerges as an exceptionally appealing technological avenue for the direct capture, conversion, and storage of renewable solar energy, facilitating the generation of sustainable and ecologically benign solar fuels and a spectrum of other pertinent applications. Heterogeneous nanocomposites, incorporating Covalent Triazine Frameworks (CTFs), exhibit a wide-ranging spectrum of light absorption, well-suited electronic band structures, rapid charge carrier mobility, ample resource availability, commendable chemical robustness, and straightforward synthetic routes. These attributes collectively position them as highly promising photocatalysts with applicability in diverse fields, including but not limited to the production of photocatalytic solar fuels and the decomposition of environmental contaminants. As the field of photocatalysis through the hybridization of CTFs undergoes rapid expansion, there is a pressing and substantive need for a systematic retrospective analysis and forward-looking evaluation to elucidate pathways for enhancing performance. This comprehensive review commences by directing attention to diverse synthetic methodologies for the creation of composite materials. And then it delves into a thorough exploration of strategies geared towards augmenting performance, encompassing the introduction of electron donor-acceptor (D-A) units, heteroatom doping, defect Engineering, architecture of Heterojunction and optimization of morphology. Following this, it systematically elucidates applications primarily centered around the efficient generation of photocatalytic hydrogen, reduction of carbon dioxide through photocatalysis, and the degradation of organic pollutants. Ultimately, the discourse turns towards unresolved challenges and the prospects for further advancement, offering valuable guidance for the potent harnessing of CTFs in high-efficiency photocatalytic processes.

Insights into Antisite Defect Complex Induced High Ferro-Piezoelectric Properties in KNbO3 Perovskite: First-Principles Study.

Improving ferro-piezoelectric properties of niobate-based perovskites is highly desirable for developing eco-friendly high-performance sensors and actuators. Although electro-strain coupling is usually obtained by constructing multiphase boundaries via complex chemical compositions, defect engineering can also create opportunities for novel property and functionality advancements. In this work, a representative tetragonal niobate-based perovskite, i.e., KNbO3, is studied by using first-principles calculations. Two intrinsic types of Nb antisite defect complexes are selected to mimic alkali-deficiency induced excess Nb antisites in experiments. The formation energy, electronic profiles, polarization, and piezoelectric constants are systematically analyzed. It is shown that the structural distortion and chemical heterogeneity around the energetically favorable antisite pair defects, i.e., (NbK4·+KNb4'), lower the crystal symmetry of KNbO3 from tetragonal to triclinic phase, and facilitate polarization emergence and reorientation to substantially enhance intrinsic ferro-piezoelectricity (i.e., spontaneous polarization Ps of 68.2 µC/cm2 and piezoelectric strain constant d33 of 228.3 pC/N) without complicated doping and alloying.

Unconventional Spectral Gaps Induced by Charge Density Waves in the Weyl Semimetal (TaSe4)2I.

Coupling Weyl quasiparticles and charge density waves (CDWs) can lead to fascinating band renormalization and many-body effects beyond band folding and Peierls gaps. For the quasi-one-dimensional chiral compound (TaSe4)2I with an incommensurate CDW transition at TC = 263 K, photoemission mappings thus far are intriguing due to suppressed emission near the Fermi level. Models for this unconventional behavior include axion insulator phases, correlation pseudogaps, polaron subbands, bipolaron bound states, etc. Our photoemission measurements show sharp quasiparticle bands crossing the Fermi level at T > TC, but for T < TC, these bands retain their dispersions with no Peierls or axion gaps at the Weyl points. Instead, occupied band edges recede from the Fermi level, opening a spectral gap. Our results confirm localization of quasiparticles (holes created by photoemission) is the key physics, which suppresses spectral weights over an energy window governed by incommensurate modulation and inherent phase defects of CDW.

Emergence of Band Structure in a Two-Dimensional Metal-Organic Framework upon Hierarchical Self-Assembly.

Two-dimensional metal-organic frameworks (2D-MOFs) represent a category of atomically thin materials that combine the structural tunability of molecular systems with the crystalline structure characteristic of solids. The strong bonding between the organic linkers and transition metal centers is expected to result in delocalized electronic states. However, it remains largely unknown how the band structure in 2D-MOFs emerges through the coupling of electronic states in the building blocks. Here, we demonstrate the on-surface synthesis of a 2D-MOF exhibiting prominent π-conjugation. Through a combined experimental and theoretical approach, we provide direct evidence of band structure formation upon hierarchical self-assembly, going from metal-organic complexes to a conjugated two-dimensional framework. Additionally, we identify the robustly dispersive nature of the emerging hybrid states, irrespective of the metallic support type, highlighting the tunability of the band structure through charge transfer from the substrate. Our findings encourage the exploration of band-structure engineering in 2D-MOFs for potential applications in electronics and photonics.

Tailoring structural and optical properties of ZnO system through elemental Mn Doping through First-principles calculations.

In this study, band structure and optical properties of Manganese (Mn) doped ZnO are investigated adopting first-principles study calculations. It is observed that, by addition of Mn in ZnO crystal, the electrical properties like conductivity and dielectric function of material have been improved. The elastic constants for the elements are also calculated which shows that the element is stable after addition of dopant. The computational study is done on CASTEP and Material Studio. The ZnO system is simulated and atoms of Mn has been added replacing Zn atoms. The properties that studied are band structure and optics including conductivity, reflectivity, dielectric function, absorption and refractive index. Furthermore, this study also includes calculation of Elastic constants, XRD Spectra, Phonon dispersion and Temperature profile of doped ZnO systems. The computational study produced promising results and experimental approach can be adopted to reinforce the outcomes of this study.

Hydrostatic pressure-induced transformations and multifunctional properties of Francium-based halide perovskite FrCaCl3: Insights from first-principles calculations.

Under varying hydrostatic pressures ranging from 0 to 150 GPa, first-principles calculations were conducted to investigate the structural, electronic, bonding, optical, elastic, and mechanical characteristics of the Lead (Pb)-free halide perovskite FrCaCl3 using both the GGA and hybrid HSE06 parameterized density functional theory (DFT). Since the FrCaCl3 cubic perovskite has not yet been synthesized experimentally, its structural and thermodynamic stabilities are confirmed by the Goldschmidt tolerance factor, the octahedral factor, and the formation energy. The induction of pressure has caused a simultaneous decrease in both the lattice parameters and the electronic band gap. Applying the hybrid HSE06 potential refines the accuracy of the band gap, with values decreasing from 5.705 to 2.618 eV from 0 to 150 GPa pressure, suggesting improved optoelectronic attributes. Employing pressure facilitates the formation of stronger chemical bonds characterized by reduced bond lengths. The investigation of optical functions demonstrates that with increased pressure ranging to 150 GPa, the optical conductivity along with the absorption coefficient is oriented towards the low-energy region. The FrCaCl3 perovskite has the prospect to be used in X-ray imaging and other fields of nuclear medicine and diagnostics as it contains the radioactive element Francium (Fr). Additionally, it is found via the study of mechanical characteristics that FrCaCl3 is mechanically stable under various applied pressure, and adding pressure makes it more ductile as well as more anisotropic.

Advancing Nanoelectronics Applications: Progress in Non-van der Waals 2D Materials.

Extending the inventory of two-dimensional (2D) materials remains highly desirable, given their excellent properties and wide applications. Current studies on 2D materials mainly focus on the van der Waals (vdW) materials since the discovery of graphene, where properties of atomically thin layers have been found to be distinct from their bulk counterparts. Beyond vdW materials, there are abundant non-vdW materials that can also be thinned down to 2D forms, which are still in their early stage of exploration. In this review, we focus on the downscaling of non-vdW materials into 2D forms to enrich the 2D materials family. This underexplored group of 2D materials could show potential promise in many areas such as electronics, optics, and magnetics, as has happened in the vdW 2D materials. Hereby, we will focus our discussion on their electronic properties and applications of them. We aim to motivate and inspire fellow researchers in the 2D materials community to contribute to the development of 2D materials beyond the widely studied vdW layered materials for electronic device applications. We also give our insights into the challenges and opportunities to guide researchers who are desirous of working in this promising research area.