Direct Measurement of the Thermal Expansion Coefficient of Epitaxial WSe2 by Four-Dimensional Scanning Transmission Electron Microscopy.

Current reports of thermal expansion coefficients (TEC) of two-dimensional (2D) materials show large discrepancies that span orders of magnitude. Determining the TEC of any 2D material remains difficult due to approaches involving indirect measurement of samples that are atomically thin and optically transparent. We demonstrate a methodology to address this discrepancy and directly measure TEC of nominally monolayer epitaxial WSe2 using four-dimensional scanning transmission electron microscopy (4D-STEM). Experimentally, WSe2 from metal-organic chemical vapor deposition (MOCVD) was heated through a temperature range of 18-564 °C using a barrel-style heating sample holder to observe temperature-induced structural changes without additional alterations or destruction of the sample. By combining 4D-STEM measurements with quantitative structural analysis, the thermal expansion coefficient of nominally monolayer polycrystalline epitaxial 2D WSe2 was determined to be (3.5 ± 0.9) × 10-6 K-1 and (5.7 ± 2) × 10-5 K-1 for the in- and out-of-plane TEC, respectively, and (3.6 ± 0.2) × 10-5 K-1 for the unit cell volume TEC, in good agreement with historically determined values for bulk crystals.

Exceptional electronic transport and quantum oscillations in thin bismuth crystals grown inside van der Waals materials.

Confining materials to two-dimensional forms changes the behaviour of the electrons and enables the creation of new devices. However, most materials are challenging to produce as uniform, thin crystals. Here we present a synthesis approach where thin crystals are grown in a nanoscale mould defined by atomically flat van der Waals (vdW) materials. By heating and compressing bismuth in a vdW mould made of hexagonal boron nitride, we grow ultraflat bismuth crystals less than 10 nm thick. Due to quantum confinement, the bismuth bulk states are gapped, isolating intrinsic Rashba surface states for transport studies. The vdW-moulded bismuth shows exceptional electronic transport, enabling the observation of Shubnikov-de Haas quantum oscillations originating from the (111) surface state Landau levels. By measuring the gate-dependent magnetoresistance, we observe multi-carrier quantum oscillations and Landau level splitting, with features originating from both the top and bottom surfaces. Our vdW mould growth technique establishes a platform for electronic studies and control of bismuth's Rashba surface states and topological boundary modes1-3. Beyond bismuth, the vdW-moulding approach provides a low-cost way to synthesize ultrathin crystals and directly integrate them into a vdW heterostructure.

Structural alignment of ZnO columns across multiple monolayer MoS2 layers as compliant substrates.

Understanding the behavior of materials in multi-dimensional architectures composed of atomically thin two-dimensional (2D) materials and three-dimensional (3D) materials has become mandatory for progress in materials preparation via various epitaxy techniques, such as van der Waals and remote epitaxy methods. We investigated the growth behavior of ZnO on monolayer MoS2 as a model system to study the growth of a 3D material on a 2D material, which is beyond the scope of remote and van der Waals epitaxy. The study revealed column-to-column alignment and inversion of crystallinity, which can be explained by combinatorial epitaxy, grain alignment across an atomically sharp interface, and a compliant substrate. The growth study enabled the formation of a ZnO/MoS2 heterostructure with type-I band alignment. Our findings will have a scientific impact on realizing 2D/3D heterostructures for practical device applications.

Controllable strain-driven topological phase transition and dominant surface-state transport in HfTe5.

The fine-tuning of topologically protected states in quantum materials holds great promise for novel electronic devices. However, there are limited methods that allow for the controlled and efficient modulation of the crystal lattice while simultaneously monitoring the changes in the electronic structure within a single sample. Here, we apply significant and controllable strain to high-quality HfTe5 samples and perform electrical transport measurements to reveal the topological phase transition from a weak topological insulator phase to a strong topological insulator phase. After applying high strain to HfTe5 and converting it into a strong topological insulator, we found that the resistivity of the sample increased by 190,500% and that the electronic transport was dominated by the topological surface states at cryogenic temperatures. Our results demonstrate the suitability of HfTe5 as a material for engineering topological properties, with the potential to generalize this approach to study topological phase transitions in van der Waals materials and heterostructures.

Enabling Oxidation Protection and Carrier-Type Switching for Bismuth Telluride Nanoribbons via in Situ Organic Molecule Coating.

Thermoelectric materials with high electrical conductivity and low thermal conductivity (e.g., Bi2Te3) can efficiently convert waste heat into electricity; however, in spite of favorable theoretical predictions, individual Bi2Te3 nanostructures tend to perform less efficiently than bulk Bi2Te3. We report a greater-than-order-of-magnitude enhancement in the thermoelectric properties of suspended Bi2Te3 nanoribbons, coated in situ to form a Bi2Te3/F4-TCNQ core-shell nanoribbon without oxidizing the core-shell interface. The shell serves as an oxidation barrier but also directly functions as a strong electron acceptor and p-type carrier donor, switching the majority carriers from a dominant n-type carrier concentration (∼1021 cm-3) to a dominant p-type carrier concentration (∼1020 cm-3). Compared to uncoated Bi2Te3 nanoribbons, our Bi2Te3/F4-TCNQ core-shell nanoribbon demonstrates an effective chemical potential dramatically shifted toward the valence band (by 300-640 meV), robustly increased Seebeck coefficient (∼6× at 250 K), and improved thermoelectric performance (10-20× at 250 K).

Manipulating Interlayer Excitons for Near-Infrared Quantum Light Generation.

Interlayer excitons (IXs) formed at the interface of van der Waals materials possess various novel properties. In parallel development, strain engineering has emerged as an effective means for creating 2D quantum emitters. Exploring the intersection of these two exciting areas, we use MoS2/WSe2 heterostructure as a model system and demonstrate how strain, defects, and layering can be utilized to create defect-bound IXs capable of bright, robust, and tunable quantum light emission in the technologically important near-infrared spectral range. Our work presents defect-bound IXs as a promising platform for pushing the performance of 2D quantum emitters beyond their current limitations.

Proximity-induced chiral quantum light generation in strain-engineered WSe2/NiPS3 heterostructures.

Quantum light emitters capable of generating single photons with circular polarization and non-classical statistics could enable non-reciprocal single-photon devices and deterministic spin-photon interfaces for quantum networks. To date, the emission of such chiral quantum light relies on the application of intense external magnetic fields, electrical/optical injection of spin-polarized carriers/excitons or coupling with complex photonic metastructures. Here we report the creation of free-space chiral quantum light emitters via the nanoindentation of monolayer WSe2/NiPS3 heterostructures at zero external magnetic field. These quantum light emitters emit with a high degree of circular polarization (0.89) and single-photon purity (95%), independent of pump laser polarization. Scanning diamond nitrogen-vacancy microscopy and temperature-dependent magneto-photoluminescence studies reveal that the chiral quantum light emission arises from magnetic proximity interactions between localized excitons in the WSe2 monolayer and the out-of-plane magnetization of defects in the antiferromagnetic order of NiPS3, both of which are co-localized by strain fields associated with the nanoscale indentations.

Enhanced Exciton-to-Trion Conversion by Proton Irradiation of Atomically Thin WS2.

Defect engineering of van der Waals semiconductors has been demonstrated as an effective approach to manipulate the structural and functional characteristics toward dynamic device controls, yet correlations between physical properties with defect evolution remain underexplored. Using proton irradiation, we observe an enhanced exciton-to-trion conversion of the atomically thin WS2. The altered excitonic states are closely correlated with nanopore induced atomic displacement, W nanoclusters, and zigzag edge terminations, verified by scanning transmission electron microscopy, photoluminescence, and Raman spectroscopy. Density functional theory calculation suggests that nanopores facilitate formation of in-gap states that act as sinks for free electrons to couple with excitons. The ion energy loss simulation predicts a dominating electron ionization effect upon proton irradiation, providing further evidence on band perturbations and nanopore formation without destroying the overall crystallinity. This study provides a route in tuning the excitonic properties of van der Waals semiconductors using an irradiation-based defect engineering approach.

Tuning of the electronic and vibrational properties of epitaxial MoS2through He-ion beam modification.

Atomically thin transition metal dichalcogenides (TMDs), like MoS2with high carrier mobilities and tunable electron dispersions, are unique active material candidates for next generation opto-electronic devices. Previous studies on ion irradiation show great potential applications when applied to two-dimensional (2D) materials, yet have been limited to micron size exfoliated flakes or smaller. To demonstrate the scalability of this method for industrial applications, we report the application of relatively low power (50 keV)4He+ion irradiation towards tuning the optoelectronic properties of an epitaxially grown continuous film of MoS2at the wafer scale, and demonstrate that precise manipulation of atomistic defects can be achieved in TMD films using ion implanters. The effect of4He+ion fluence on the PL and Raman signatures of the irradiated film provides new insights into the type and concentration of defects formed in the MoS2lattice, which are quantified through ion beam analysis. PL and Raman spectroscopy indicate that point defects are generated without causing disruption to the underlying lattice structure of the 2D films and hence, this technique can prove to be an effective way to achieve defect-mediated control over the opto-electronic properties of MoS2and other 2D materials.

Induced Ferromagnetism in Epitaxial Uranium Dioxide Thin Films.

Actinide materials have various applications that range from nuclear energy to quantum computing. Most current efforts have focused on bulk actinide materials. Tuning functional properties by using strain engineering in epitaxial thin films is largely lacking. Using uranium dioxide (UO2 ) as a model system, in this work, the authors explore strain engineering in actinide epitaxial thin films and investigate the origin of induced ferromagnetism in an antiferromagnet UO2 . It is found that UO2+ x thin films are hypostoichiometric (x<0) with in-plane tensile strain, while they are hyperstoichiometric (x>0) with in-plane compressive strain. Different from strain engineering in non-actinide oxide thin films, the epitaxial strain in UO2 is accommodated by point defects such as vacancies and interstitials due to the low formation energy. Both epitaxial strain and strain relaxation induced point defects such as oxygen/uranium vacancies and oxygen/uranium interstitials can distort magnetic structure and result in magnetic moments. This work reveals the correlation among strain, point defects and ferromagnetism in strain engineered UO2+ x thin films and the results offer new opportunities to understand the influence of coupled order parameters on the emergent properties of many other actinide thin films.

Manufacturing of Complex Silicon-Carbon Structures: Exploring SixCy Materials.

This paper reports on the manufacturing of complex three-dimensional Si/C structures via a chemical vapor deposition method. The structure and properties of the grown materials were characterized using various techniques including scanning electron microscopy, aberration-corrected transmission electron microscopy, confocal Raman spectroscopy, and X-ray photoelectron spectroscopy. The spectroscopy results revealed that the grown materials were composed of micro/nanostructures with various compositions and dimensions. These included two-dimensional silicon carbide (SiC), cubic silicon, and various SiC polytypes. The coexistence of these phases at the nano-level and their interfaces can benefit several Si/C-based applications ranging from ceramics and structural applications to power electronics, aerospace, and high-temperature applications. With an average density of 7 mg/cm3, the grown materials can be considered ultralightweight, as they are three orders of magnitude lighter than bulk Si/C materials. This study aims to impact how ceramic materials are manufactured, which may lead to the design of new carbide materials or Si/C-based lightweight structures with additional functionalities and desired properties.

Visualizing Grain Statistics in MOCVD WSe2 through Four-Dimensional Scanning Transmission Electron Microscopy.

Using four-dimensional scanning transmission electron microscopy, we demonstrate a method to visualize grains and grain boundaries in WSe2 grown by metal organic chemical vapor deposition (MOCVD) directly onto silicon dioxide. Despite the chemical purity and uniform thickness and texture of the MOCVD-grown WSe2, we observe a high density of small grains that corresponds with the overall selenium deficiency we measure through ion beam analysis. Moreover, reconstruction of grain information permits the creation of orientation maps that demonstrate the nucleation mechanism for new layers-triangular domains with the same orientation as the layer underneath induces a tensile strain increasing the lattice parameter at these sites.

Site-controlled telecom-wavelength single-photon emitters in atomically-thin MoTe2.

Quantum emitters (QEs) in two-dimensional transition metal dichalcogenides (2D TMDCs) have advanced to the forefront of quantum communication and transduction research. To date, QEs capable of operating in O-C telecommunication bands have not been demonstrated in TMDCs. Here we report site-controlled creation of telecom QEs emitting over the 1080 to 1550 nm telecommunication wavelength range via coupling of 2D molybdenum ditelluride (MoTe2) to strain inducing nano-pillar arrays. Hanbury Brown and Twiss experiments conducted at 10 K reveal clear photon antibunching with 90% single-photon purity. The photon antibunching can be observed up to liquid nitrogen temperature (77 K). Polarization analysis further reveals that while some QEs display cross-linearly polarized doublets with ~1 meV splitting resulting from the strain induced anisotropic exchange interaction, valley degeneracy is preserved in other QEs. Valley Zeeman splitting as well as restoring of valley symmetry in cross-polarized doublets are observed under 8 T magnetic field.

Intrinsic helical twist and chirality in ultrathin tellurium nanowires.

Robust atomic-to-meso-scale chirality is now observed in the one-dimensional form of tellurium. This enables a large and counter-intuitive circular-polarization dependent second harmonic generation response above 0.2 which is not present in two-dimensional tellurium. Orientation variations in 1D tellurium nanowires obtained by four-dimensional scanning transmission electron microscopy (4D-STEM) and their correlation with unconventional non-linear optical properties by second harmonic generation circular dichroism (SHG-CD) uncovers an unexpected circular-polarization dependent SHG response from 1D nanowire bundles - an order-of-magnitude higher than in single-crystal two-dimensional tellurium structures - suggesting the atomic- and meso-scale crystalline structure of the 1D material possesses an inherent chirality not present in its 2D form; and which is strong enough to manifest even in the aggregate non-linear optical (NLO) properties of aggregates.

Thermoelectric properties of antimony selenide hexagonal nanotubes.

Antimony selenide (Sb2Se3) is a material widely used in photodetectors and relatively new as a possible material for thermoelectric applications. Taking advantage of the new properties after nanoscale fabrication, this material shows great potential for the development of efficient low temperature thermoelectric devices. Here we study the synthesis, the crystal properties and the thermal and thermoelectric transport response of Sb2Se3 hexagonal nanotubes (HNT) in the temperature range between 120 and 370 K. HNT have a moderate electrical conductivity ∼102 S m-1 while maintaining a reasonable Seebeck coefficient ∼430 µV K-1 at 370 K. The electrical conductivity in Sb2Se3 HNT is about 5 orders of magnitude larger and its thermal conductivity one half of what is found in bulk. Moreover, the calculated figure of merit (ZT) at room temperature is the largest value reported in antimony selenide 1D structures.

1D to 2D Transition in Tellurium Observed by 4D Electron Microscopy.

A new microwave-enhanced synthesis method for the production of tellurium nanostructures is reported-with control over products from the 1D regime (sub-5 nm diameter nanowires), to nanoribbons, to the 2D tellurene regime-along with a new methodology for local statistical quantification of the crystallographic parameters of these materials at the nanometer scale. Using a direct electron detector and image-corrected microscope, large and robust 4D scanning transmission electron microscopy datasets for accurate structural analysis are obtained. These datasets allow the adaptation of quantitative techniques originally developed for X-ray diffraction (XRD) refinement analyses to transmission electron microscopy, enabling the first demonstration of sub-picometer accuracy lattice parameter extraction while also obtaining both the size of the coherent crystallite domains and the nanostrain, which is observed to decrease as nanowires transition to tellurene. This new local analysis is commensurate with global powder XRD results, indicating the robustness of both the new synthesis approach and new structural analysis methodology for future scalable production of 2D tellurene and characterization of nanomaterials.

Isotope Effect in Bilayer WSe2.

Isotopes of an element have the same electron number but differ in neutron number and atomic mass. However, due to the thickness-dependent properties in MX2 (M = Mo, W; X = S, Se, Te) transition metal dichalcogenides (TMDs), the isotopic effect in atomically thin TMDs still remains unclear especially for phonon-assisted indirect excitonic transitions. Here, we report the first observation of the isotope effect on the electronic and vibrational properties of a TMD material, using naturally abundant NAWNASe2 and isotopically pure 186W80Se2 bilayer single crystals over a temperature range of 4.4-300 K. We demonstrate a higher optical band gap energy in 186W80Se2 than in NAWNASe2 (3.9 ± 0.7 meV from 4.41 to 300 K), which is surprising as isotopes are neutral impurities. Phonon energies decrease in the isotopically pure crystal due to the atomic mass dependence of harmonic oscillations, with correspondingly longer E2g and A21g phonon lifetimes than in the naturally abundant sample. The change in electronic band gap renormalization energy is postulated as being the dominant mechanism responsible for the change in optical emission spectra.

Uncertainty analysis of axial temperature and Seebeck coefficient measurements.

Experimental investigations of solid materials at elevated temperatures rely on the optimized thermal design of the measurement system, as radiation becomes a predominant source of heat loss which can lead to large uncertainty in measured temperature and related physical properties of a test sample. Advancements in surface temperature measurements have reduced thermal losses arising from the cold-finger effect using axially inserted thermocouples and from radiation using shields or other thermal guards. The leading technology for temperature sensing at temperatures up to ∼900 °C makes use of these design features for measuring thermopower, yet uncertainty analysis estimation of this technique is not known. This work makes use of finite element modeling to determine spatial temperature distributions to obtain the upper limit of confidence expected for the axially inserted thermocouple approach when a heated radiation shield is incorporated into the design. Using an axially inserted thermocouple to measure the sample surface temperature, the temperature variations across the sample hot and cold surfaces at 900 °C for a temperature drop of 0, 5, and 10 °C are calculated to be as low as 0.02, 0.21, and 0.41 °C, respectively, when a heated radiation shield is employed. Uniform temperature distribution on the thermocouple cross-wire geometry indicates that the axial thermocouple measurement design is indeed effective for suppressing the cold-finger effect. Using a heated radiation shield is found to significantly reduce the temperature gradient across the thermocouples.