Helicity-Resolved Vibrational Coupling in Twist WS2/WSe2 Heterostructures.

Helicity-resolved Raman spectra can provide an intricate view into lattice structural details. Through the analysis of peak positions, intensities, and circular polarized Raman signals, a wealth of information about chiral structure arrangement within the moiré superlattice, interlayer interaction strength, polarizability change in chemical bond, and beyond can be unveiled. However, the relationship between the circular polarization of high-frequency Raman and twist angle is still not clear. Here, we utilize helicity-resolved Raman spectroscopy to explore the interlayer interactions and the effect of the moiré superlattice in WS2/WSe2 heterostructures. For the out-of-plane Raman mode A1g of WS2 (A1g and 1E2g of WSe2), its intensity is significantly enhanced (suppressed) in WS2/WSe2 heterostructures when θ is less than 10° or greater than 50°. This observation could be attributed to the large polarizability changes in both W-S and W-Se covalent bonds. The circular polarization of 2LA(M) in WSe2 of the WS2/WSe2 heterostructure (θ < 10° or θ > 50°) is significantly enhanced compared to that of 2LA(M) in the monolayer WSe2. We deduce that the circular polarization of the Raman mode correlates with the proportion of high-symmetry area within a supercell of the moiré lattice. Our findings improve the understanding of twist-angle-modulated Raman modes in TMD heterostructures.

Synergetic interface engineering and space-confined effect in CoSe2@Ti3C2Tx heterostructure for high power and long life sodium ion capacitors.

The intriguing characteristics of two-dimensional (2D) heterostructures stem from their unique interfaces, which can improve ion storage capability and rate performance. However, there are still challenges in increasing the proportion of heterogeneous interfaces in materials and understanding the complex interaction mechanisms at these interfaces. Here, we have successfully synthesized confined CoSe2 within the interlayer space of Ti3C2Tx through a simple solvothermal method, resulting in the formation of a superlattice-like heterostructures of CoSe2@Ti3C2Tx. Both density functional theory (DFT) calculations and experimental results show that compared with CoSe2 and Ti3C2Tx, CoSe2@Ti3C2Tx can significantly improve adsorption of Na+ ions, while maintaining low volume expansion and high Na+ ions migration rate. The heterostructure formed by MXene and CoSe2 is a Schottky heterostructure, and its interfacial charge transfer induces a built-in electric field that promotes rapid ion transport. When CoSe2@Ti3C2Tx was used as an anode material, it exhibits a high specific capacity of up to 600.1 mAh/g and an excellent rate performance of 206.3 mAh/g at 20 A/g. By utilizing CoSe2@Ti3C2Tx as the anode and activated carbon (AC) as the cathode, the sodium-ion capacitor of CoSe2@Ti3C2Tx//AC exhibits excellent energy and power density (125.0 Wh kg-1 and 22.5 kW kg-1 at 300.0 W kg-1 and 37.5 Wh kg-1, respectively), as well as a long service life (86.3 % capacity retention over 15,300 cycles at 5 A/g), demonstrating its potential for practical applications.

Lithiation induced hetero-superlattice Zn/ZnLi as stable anode for aqueous zinc-ion batteries.

Three dimensional (3D) framework structure is one of the most effective ways to achieve uniform zinc deposition and thus inhibit the Zn dendrites growth in working Zn metallic anode. A major challenge facing for the most commonly used 3D zincophilic hosts is that the zincophilic layer tends to peel off during repeatedly cycling, making it less stable. Herein, for the first time, a hetero-superlattice Zn/ZnLi (HS-Zn/ZnLi) anode containing periodic arrangements of metallic Zn phase and zincophilic ZnLi phase at the nanoscale, is well designed and fabricated via electrochemical lithiation method. Based on binding energy and stripping energy calculation, and the operando optical observation of plating/stripping behaviors, the zincophilic ZnLi sites with a strong Zn adsorption ability in the interior of the 3D ZnLi framework structure can effectively guide uniform Zn nucleation and dendrite-free zinc deposition, which significantly improves the cycling stability of the HS-Zn/ZnLi alloy (over 2800 h without a short-circuit at 2 mA cm-2). More importantly, this strategy can be extended to HS-Zn/ZnNa and HS-Zn/ZnK anodes that are similar to the HS-Zn/ZnLi microstructure, also displaying significantly enhanced cycling performances in AZIBs. This study can provide a novel strategy to develop the dendrite-free metal anodes with stable cycling performance.

Topotactic Syntopogenous Sodium Vanadium Fluoride for High-Performance Sodium-Ion Batteries: Electron and Sodium-Ion Reservoirs in Perovskite/Diperovskite Superlattice.

In order to simultaneously accelerate ion and electron transfer in sodium-ion battery (SIB) cathodes, a topotactic superlattice was utilized, in which the atomically intrinsic lattice-matching effect from inner to external surface can boost the charge transfer due to the disappearance of the heterojunction interface. Herein, a topotactic syntopogenous Na3VF6/NaVF3 superlattice formulated as Na2.9V1.1F6 (NVF) was synthesized by a facile one-step low-temperature hydrothermal reaction. NVF nanoparticles show an excellent Na+ storage capacity (∼205 mAh g-1) in a high voltage window up to 4.2 V with ultralong cycling stability. That is associated with the mixed occupancy of V and Na in NVF. The multivalent V centers serve as electron reservoirs to inhibit phase transformation, and the Na-enriched Na3VF6 with better electron conductivity acts as a Na+ reservoir for effective electron transfer. Highly reversible (de)intercalation of Na+ is achieved in the channel of perovskite-type NaVF3 with structural integrity.

Spatial Filtering of Interlayer Exciton Ground State in WSe2/MoS2 Heterobilayer.

Long-life interlayer excitons (IXs) in transition metal dichalcogenide (TMD) heterostructure are promising for realizing excitonic condensates at high temperatures. Critical to this objective is to separate the IX ground state (the lowest energy of IX state) emission from other states' emissions. Filtering the IX ground state is also essential in uncovering the dynamics of correlated excitonic states, such as the excitonic Mott insulator. Here, we show that the IX ground state in the WSe2/MoS2 heterobilayer can be separated from other states by its spatial profile. The emissions from different moiré IX modes are identified by their different energies and spatial distributions, which fits well with the rate-diffusion model for cascading emission. Our results show spatial filtering of the ground state mode and enrich the toolbox to realize correlated states at elevated temperatures.

Predictive Modeling of Nanocrystal Orientation in Superlattices: Insights from Ligand Entropy.

The self-assembly of nanocrystals (NCs) into close-packed, ordered superlattices (SLs) is of broad, engineering interest. The coherent orientation of polyhedral nanocrystals within NC SLs enhances electronic, magnetic, and vibrational coupling, leading to a variety of emergent phenomena. Here, we show that coherent orientation of polyhedral NCs in many SLs can be understood simply by considering its effect on the conformational entropy of surface ligands. We report the predicted nanocrystal orientations and entropic driving force to orient for a broad range of nanocrystal shapes and superlattice unit cells, and we show that ligand entropy is sufficient to reproduce a host of reported experimental and computational observations. We additionally use this framework to predict the expected distribution of interstitial species such as solvent or unbound ligands in an oriented NC SL. This work offers intuition for understanding the orientation of NCs in superlattices and a future framework for analyzing multinary structures.

2D MXene/MBene Superlattice with Narrow Bandgap as Superior Electrocatalyst for High-Performance Lithium-Oxygen Battery.

Lithium-oxygen (Li-O2) battery with large theoretical energy density (≈3500 Wh kg-1) is one of the most promising energy storage and conversion systems. However, the slow kinetics of oxygen electrode reactions inhibit the practical application of Li-O2 battery. Thus, designing efficient electrocatalysts is crucial to improve battery performance. Here, Ti3C2 MXene/Mo4/3B2-x MBene superlattice is fabricated its electrocatalytic activity toward oxygen redox reactions in Li-O2 battery is studied. It is found that the built-in electric field formed by a large work function difference between Ti3C2 and Mo4/3B2-x will power the charge transfer at the interface from titanium (Ti) site in Ti3C2 to molybdenum (Mo) site in Mo4/3B2-x. This charge transfer increases the electron density in 4d orbital of Mo site and decreases the d-band center of Mo site, thus optimizing the adsorption of intermediate product LiO2 at Mo site and accelerating the kinetics of oxygen electrode reactions. Meanwhile, the formed film-like discharge products (Li2O2) improve the contact with electrode and facilitate the decomposition of Li2O2. Based on the above advantages, the Ti3C2 MXene/Mo4/3B2-x MBene superlattice-based Li-O2 battery exhibits large discharge specific capacity (17 167 mAh g-1), low overpotential (1.16 V), and superior cycling performance (475 cycles).

Homo-Site Nucleation Growth of Twisted Bilayer MoS2 with Commensurate Angles.

Moiré superlattices, composed of two layers of transition metal dichalcogenides with a relative twist angle, provide a novel platform for exploring the correlated electronic phases and excitonic physics. Here, a gas-flow perturbation chemical vapor deposition (CVD) approach is demonstrated to directly grow MoS2 bilayer with versatile twist angles. It is found that the formation of twisted bilayer MoS2 homostructures sensitively depends on the gas-flow perturbation modes, correspondingly featuring the nucleation sites of the second layer at the same (homo-site) as or at the different (hetero-site) from that of the first layer. The commensurate twist angle of ≈22° in homo-site nucleation strategy accounts for ≈16% among the broad range of twist angles due to its low formation energy, which is in consistence with the theoretical calculation. More importantly, moiré interlayer excitons with the enhanced photoluminescence (PL) intensity and the prolonged lifetime are evidenced in the twisted bilayer MoS2 with a commensurate angle of 22°, which is owing to the reason that the strong moiré potential facilitates the interlayer excitons to be trapped in the moiré superlattices. The work provides a feasible route to controllably built twisted MoS2 homostructures with strong moiré potential to investigate the correlated physics in twistronics systems.

Emergence of Optical Anisotropy in Moiré Superlattice via Heterointerface Engineering.

The interaction between light and moiré superlattices presents a platform for exploring unique light-matter phenomena. Tailoring these optical properties holds immense potential for advancing the utilization of moiré superlattices in photonics, optoelectronics, and valleytronics. However, the control of the optical polarization state in moiré superlattices, particularly in the presence of moiré effects, remains elusive. Here, we unveil the emergence of optical anisotropy in moiré superlattices by constructing twisted WSe2/WSe2/SiP heterostructures. We report a linear polarization degree of ∼70% for moiré excitons, attributed to the spatially nonuniform charge distribution, corroborated by first-principles calculations. Furthermore, we demonstrate the modulation of this linear polarization state via the application of a magnetic field, resulting in polarization angle rotation and a magnetic-field-dependent linear polarization degree, influenced by valley coherence and moiré potential effects. Our findings demonstrate an efficient strategy for tuning the optical polarization state of moiré superlattices using heterointerface engineering.

Emergent Inhomogeneity and Nonlocality in a Graphene Field-Effect Transistor on a Near-Parallel Moiré Superlattice of Transition Metal Dichalcogenides.

At near-parallel orientation, twisted bilayers of transition metal dichalcogenides exhibit interlayer charge transfer-driven out-of-plane ferroelectricity. Here, we report detailed electrical transport in a dual-gated graphene field-effect transistor placed on a 2.1° twisted bilayer WSe2. We observe hysteretic transfer characteristics and an emergent charge inhomogeneity with multiple local Dirac points evolving with an increasing electric displacement field (D). Concomitantly, we also observe a strong nonlocal voltage signal at D ∼ 0 V/nm that decreases rapidly with increasing D. A linear scaling of the nonlocal signal with longitudinal resistance suggests edge mode transport, which we attribute to the breaking of valley symmetry of graphene due to the spatially fluctuating electric field from the underlying polarized moiré domains. A quantitative analysis suggests the emergence of finite-size domains in graphene that modulate the charge and the valley currents simultaneously. This work underlines the impact of interfacial ferroelectricity that can trigger a new generation of devices.

Structural Complexities in Sodium Ion Conductive Antiperovskite Revealed by Cryogenic Transmission Electron Microscopy.

We use low-dose cryogenic transmission electron microscopy (cryo-TEM) to investigate the atomic-scale structure of antiperovskite Na2NH2BH4 crystals by preserving the room-temperature cubic phase and carefully monitoring the electron dose. Via quantitative analysis of electron beam damage using selected area electron diffraction, we find cryogenic imaging provides 6-fold improvement in beam stability for this solid electrolyte. Cryo-TEM images obtained from flat crystals revealed the presence of a new, long-range-ordered supercell with a cubic phase. The supercell exhibits doubled unit cell dimensions of 9.4 Å × 9.4 Å as compared to the cubic lattice structure revealed by X-ray crystallography of 4.7 Å × 4.7 Å. The comparison between the experimental image and simulated potential map indicates the origin of the supercell is a vacancy ordering of sodium atoms. This work demonstrates the potential of using cryo-TEM imaging to study the atomic-scale structure of air- and electron-beam-sensitive antiperovskite-type solid electrolytes.

PbI2 Passivation of Three Dimensional PbS Quantum Dot Superlattices Toward Optoelectronic Metamaterials.

Lead chalcogenide colloidal quantum dots are one of the most promising materials to revolutionize the field of short-wavelength infrared optoelectronics due to their bandgap tunability and strong absorption. By self-assembling these quantum dots into ordered superlattices, mobilities approaching those of the bulk counterparts can be achieved while still retaining their original optical properties. The recent literature focused mostly on PbSe-based superlattices, but PbS quantum dots have several advantages, including higher stability. In this work, we demonstrate highly ordered 3D superlattices of PbS quantum dots with tunable thickness up to 200 nm and high coherent ordering, both in-plane and along the thickness. We show that we can successfully exchange the ligands throughout the film without compromising the ordering. The superlattices as the active material of an ion gel-gated field-effect transistor achieve electron mobilities up to 220 cm2 V-1 s-1. To further improve the device performance, we performed a postdeposition passivation with PbI2, which noticeably reduced the subthreshold swing making it reach the Boltzmann limit. We believe this is an important proof of concept showing that it is possible to overcome the problem of high trap densities in quantum dot superlattices enabling their application in optoelectronic devices.

Simultaneous enhancement of strength and ductility via microband formation and nanotwinning in an L12-strengthened alloy.

Metallic alloys with high strength and large ductility are required for extreme structural applications. However, the achievement of ultrahigh strength often results in a substantially decreased ductility. Here, we report a strategy to achieve the strength-ductility synergy by tailoring the alloy composition to control the local stacking fault energy (SFE) of the face-centered-cubic (fcc) matrix in an L12-strengthened superlattice alloy. As a proof of concept, based on the thermodynamic calculations, we developed a non-equiatomic CoCrNi2(Al0.2Nb0.2) alloy using phase separation to create a near-equiatomic low SFE disordered CoCrNi medium-entropy alloy matrix with in situ formed high-content coherent Ni3(Al, Nb)-type ordered nanoprecipitates (∼ 12 nm). The alloy achieves a high tensile strength up to 1.6 GPa and a uniform ductility of 33%. The low SFE of the fcc matrix promotes the formation of nanotwins and parallel microbands during plastic deformation which could remarkably enhance the strain hardening capacity. This work provides a strategy for developing ultrahigh-strength alloys with large uniform ductility.

How Depletion Layers Govern the Dynamic Plasmonic Response of In-Doped CdO Nanocrystals.

Doped metal oxide nanocrystals exhibit a localized surface plasmon resonance that is widely tunable across the mid- to near-infrared region, making them useful for applications in optoelectronics, sensing, and photocatalysis. Surface states pin the Fermi level and induce a surface depletion layer that hinders conductivity and refractive index sensing but can be advantageous for optical modulation. Several strategies have been developed to both synthetically and postsynthetically tailor the depletion layer toward particular applications; however, this understanding has primarily been advanced in Sn-doped In2O3 (ITO) nanocrystals, leaving open questions about generalizing to other doped metal oxides. Here, we quantitatively analyze the depletion layer in In-doped CdO (ICO) nanocrystals, which is shown to have an intrinsically wide depletion layer that leads to broad plasmonic modulation via postsynthetic chemical reduction and ligand exchange. Leveraging these insights, we applied depletion layer tuning to enhance the inherently weak plasmonic coupling in ICO nanocrystal superlattices. Our results demonstrate how an electronic band structure dictates the radial distribution of electrons and governs the response to postsynthetic modulation, enabling the design of tunable and responsive plasmonic materials.

Tuning Displacement Fields in a Two-Dimensional Topological Insulator Using Nanopatterned Gates.

Epitaxial heterostructures with topological insulators enable novel quantum phases and practical device applications. Their topological electronic states are sensitive to the microscopic parameters, including structural inversion asymmetry (SIA), which is an inherent feature of many real heterostructures. Controlling SIA is challenging, because it requires the ability to tune the displacement field across the topological film. Here, using nanopatterned gates, we demonstrate a tunable displacement field in a heterostructure of the two-dimensional topological insulator cadmium arsenide. Transport studies in magnetic fields reveal an extreme sensitivity of the band inversion to SIA. We show that a relatively small displacement field (∼50 mV/nm) converts the crossing of the two zeroth Landau levels in magnetic field to an avoided crossing, signaling a change to trivial band order. This work demonstrates a universal methodology for tuning electronic states in topological thin films.

Dimensionality Engineering of Magnetic Anisotropy from the Anomalous Hall Effect in Synthetic SrRuO3 Crystals.

Magnetic anisotropy in atomically thin correlated heterostructures is essential for exploring quantum magnetic phases for next-generation spintronics. Whereas previous studies have mostly focused on van der Waals systems, here we investigate the impact of dimensionality of epitaxially grown correlated oxides down to the monolayer limit on structural, magnetic, and orbital anisotropies. By designing oxide superlattices with a correlated ferromagnetic SrRuO3 and nonmagnetic SrTiO3 layers, we observed modulated ferromagnetic behavior with the change of the SrRuO3 thickness. Especially, for three-unit-cell-thick layers, we observe a significant 1500% improvement of the coercive field in the anomalous Hall effect, which cannot be solely attributed to the dimensional crossover in ferromagnetism. The atomic-scale heterostructures further reveal the systematic modulation of anisotropy for the lattice structure and orbital hybridization, explaining the enhanced magnetic anisotropy. Our findings provide valuable insights into engineering the anisotropic hybridization of synthetic magnetic crystals, offering a tunable spin order for various applications.

The Effect of Sputtering Sequence Engineering in Superlattice-like Sb-Rich-Based Phase Change Materials.

This paper presents a comprehensive investigation into the thermal stability of superlattice-like (SLL) thin films fabricated by varying the sputtering sequences of the SLL [Ge8Sb92(25nm)/GeTe(25nm)]1 and SLL [GeTe(25nm)/Ge8Sb92(25nm)]1 configurations. Our results reveal significantly enhanced ten-year data retention (Tten) for both thin films measured at 124.3 °C and 151.9 °C, respectively. These values surpass the Tten of Ge2Sb2Te5 (85 °C), clearly demonstrating the superior thermal stability of the studied SLL configurations. Interestingly, we also observe a distinct difference in the thermal stability between the two SLL configurations. The superior thermal stability of SLL [GeTe(25nm)/Ge8Sb92(25nm)]1 is attributed to the diffusion of the Sb precipitated phase from Ge8Sb92 to GeTe. This diffusion process effectively reduces the impact of the Sb phase on the thermal stability of the thin film. In contrast, in the case of SLL [Ge8Sb92(25nm)/GeTe(25nm)]1, the presence of the Sb precipitated phase in Ge8Sb92 facilitates the crystallization of GeTe, leading to reduced thermal stability. These findings underscore the significant influence of the sputtering sequence on the atomic behavior and thermal properties of superlattice-like phase change materials. Such insights provide a robust foundation for the design and exploration of novel phase change materials with improved thermal performance.

Research on Improved Crystallization Properties and Underlying Mechanism of the Sb2Te3 Phase-Change Thin Film by Inserting Sn15Sb85 Layers.

As a non-volatile semiconductor memory technology, phase-change memory has a wide range of application prospects as a result of the excellent comprehensive performance. In this paper, multilayer thin films based on Sb2Te3 material were designed and prepared by inserting the Sn15Sb85 layer. The thermal and electrical properties of superlattice-like Sb2Te3/Sn15Sb85 phase-change films can be adjusted by controlling the thickness ratio of Sb2Te3/Sn15Sb85. In comparison to the monolayer Sb2Te3 film, the multilayer layer Sb2Te3/Sn15Sb85 materials have a higher crystallization temperature, larger crystallization activation energy, and longer data lifetime, indicating the great improvement of thermal stability. The changes in the phase structure and vibrational modes of multilayer Sb2Te3/Sn15Sb85 films were characterized by X-ray diffraction and Raman spectroscopy, respectively. The presence of Sn15Sb85 layers restrains grain growth and refines the grain size. The multilayer Sb2Te3/Sn15Sb85 films exhibit better surface flatness, smaller surface potential undulation, and lower thickness variations than single-layer Sb2Te3. Phase-change memory cells based on the [Sb2Te3 (1 nm)/Sn15Sb85 (9 nm)]5 thin film has a lower threshold voltage (1.9 V) and threshold current (3.1 µA) compared to the Ge2Sb2Te5 film. Meanwhile, the electrical heating model of a phase-change memory cell based on a [Sb2Te3 (1 nm)/Sn15Sb85 (9 nm)]5 multilayer structure was established by multiphysics coupling analysis, proving the great improvement in heat transfer performance and efficiency. The experimental and theoretical studies confirm that the insertion of the Sn15Sb85 layer can significantly improve the crystallization properties of Sb2Te3 films, paving the way for optimizing the phase-change materials by regulating the microstructural parameters.

Chern Insulator States with Tunable Chern Numbers in a Graphene Moiré Superlattice.

Moiré superlattices, constituted by two-dimensional materials, demonstrate a variety of strongly correlated and topological phenomena including correlated insulators, superconductivity, and integer/fractional Chern insulators. In the realm of topological nontrivial Chern insulators within specific moiré superlattices, previous studies usually observe a single Chern number at a given filling factor in a device. Here we present the observation of gate-tunable Chern numbers within the Chern insulator state of an ABC-stacked trilayer graphene/hexagonal boron nitride moiré superlattice device. Near quarter filling, the moiré superlattice exhibits spontaneous valley polarization and distinct ferromagnetism associated with the Chern insulator states over a range of the displacement field. Surprisingly we find a transition of the Chern number from C = 3 to 4 as the displacement field is increased. Our observation of gate-tunable correlated Chern insulators suggests new ways to control and manipulate topological states in a moiré superlattice device.

Ultralow-Noise MoS2/Type II Superlattice Mixed-Dimensional van der Waals Barrier Long-Wave Infrared Detector.

Low-noise, high-performance long-wave infrared detectors play a crucial role in diverse applications, including in the industrial, security, and medical fields. However, the current performance of long-wave detectors is constrained by the noise associated with narrow bandgaps. Therefore, exploring novel heterostructures for long-wavelength infrared detection is advantageous for the development of compact and high-performance infrared sensing. In this investigation, we present a MoS2/type II superlattice mixed-dimensional van der Waals barrier long-wave infrared detector (Mixed-vdWH). Through the design of the valence band barrier, substantial suppression of device dark noise is achieved, resulting in 2 orders of magnitude reduction in dark current. The device exhibits outstanding performance, with D* reaching 4 × 1010 Jones. This integration approach synergizes the distinctive properties of two-dimensional layered materials (2DLM) with the well-established processing techniques of traditional three-dimensional semiconductor materials, offering a compelling avenue for the large-scale integration of 2DLM.