Spatially Resolved Band Gap and Dielectric Function in Two-Dimensional Materials from Electron Energy Loss Spectroscopy.

The electronic properties of two-dimensional (2D) materials depend sensitively on the underlying atomic arrangement down to the monolayer level. Here we present a novel strategy for the determination of the band gap and complex dielectric function in 2D materials achieving a spatial resolution down to a few nanometers. This approach is based on machine learning techniques developed in particle physics and makes possible the automated processing and interpretation of spectral images from electron energy loss spectroscopy (EELS). Individual spectra are classified as a function of the thickness with K-means clustering, and then used to train a deep-learning model of the zero-loss peak background. As a proof of concept we assess the band gap and dielectric function of InSe flakes and polytypic WS2 nanoflowers and correlate these electrical properties with the local thickness. Our flexible approach is generalizable to other nanostructured materials and to higher-dimensional spectroscopies and is made available as a new release of the open-source EELSfitter framework.

Mobility Extraction in 2D Transition Metal Dichalcogenide Devices-Avoiding Contact Resistance Implicated Overestimation.

Schottky barrier (SB) transistors operate distinctly different from conventional metal-oxide semiconductor field-effect transistors, in a unique way that the gate impacts the carrier injection from the metal source/drain contacts into the channel region. While it has been long recognized that this can have severe implications for device characteristics in the subthreshold region, impacts of contact gating of SB in the on-state of the devices, which affects evaluation of intrinsic channel properties, have been yet comprehensively studied. Due to the fact that contact resistance (RC ) is always gate-dependent in a typical back-gated device structure, the traditional approach of deriving field-effect mobility from the maximum transconductance (gm ) is in principle not correct and can even overestimate the mobility. In addition, an exhibition of two different threshold voltages for the channel and the contact region leads to another layer of complexity in determining the true carrier concentration calculated from Q = COX * (VG -VTH ). Through a detailed experimental analysis, the effect of different effective oxide thicknesses, distinct SB heights, and doping-induced reductions in the SB width are carefully evaluated to gain a better understanding of their impact on important device metrics.

Electric-field induced structural transition in vertical MoTe2- and Mo1-xWxTe2-based resistive memories.

Transition metal dichalcogenides have attracted attention as potential building blocks for various electronic applications due to their atomically thin nature and polymorphism. Here, we report an electric-field-induced structural transition from a 2H semiconducting to a distorted transient structure (2Hd) and orthorhombic Td conducting phase in vertical 2H-MoTe2- and Mo1-xWxTe2-based resistive random access memory (RRAM) devices. RRAM programming voltages are tunable by the transition metal dichalcogenide thickness and show a distinctive trend of requiring lower electric fields for Mo1-xWxTe2 alloys versus MoTe2 compounds. Devices showed reproducible resistive switching within 10 ns between a high resistive state and a low resistive state. Moreover, using an Al2O3/MoTe2 stack, On/off current ratios of 106 with programming currents lower than 1 µA were achieved in a selectorless RRAM architecture. The sum of these findings demonstrates that controlled electrical state switching in two-dimensional materials is achievable and highlights the potential of transition metal dichalcogenides for memory applications.

Effect of oblique versus normal deposition orientation on the properties of perpendicularly magnetized L10 FePd thin films.

Materials such as L10 Fe-based alloys with perpendicular magnetic anisotropy derived from crystal structure have the potential to deliver higher thermal stability of magnetic memory elements compared to materials whose anisotropy is derived from surfaces and interfaces. A number of processing parameters enable control of the quality and texture of L10 FePd among them, including substrate, deposition temperature, pressure and seed and buffer layer. The angle of inclination between the substrate and the sputtering target can also impact the texture of L10 crystallization of sputtered Fe-Pd and magnetic properties of the derived thin films. This study examines the difference between FePd layers that have been magnetron sputter deposited on Cr(15 nm)/Pt, Ir, or Ru(4 nm)/FePd (8 nm)/Ru(2 nm)/Ta(3 nm) substrate layers at an oblique angle (30° tilt from the sputtering target) versus normal incidence (target facing the substrate). X-ray diffraction, ferromagnetic resonance spectroscopy and vibrating sample magnetometry were used to compare the degree of L10 order and static and dynamic properties of films deposited under both conditions. The films grown using the oblique orientation exhibit a stronger degree of L10 orientation, a larger magnetic anisotropy energy and a lower Gilbert damping, on all three buffer layers.

Automated Mechanical Exfoliation of MoS2 and MoTe2 Layers for 2D Materials Applications.

An automated technique is presented for mechanically exfoliating single-layer and few-layer transition metal dichalcogenides using controlled shear and normal forces imposed by a parallel plate rheometer. A thin sample that is removed from bulk MoS2 or MoTe2 is initially attached to the movable upper fixture of the rheometer using blue dicing tape while the lower base plate also has the same tape to capture and exfoliate samples when the two plates are brought into contact then separated. A step-and-repeat exfoliation process is initiated using a preprogrammed contact force and liftoff speed. It was determined that atomically thin films of these materials could be obtained reproducibly using this technique, achieving single-layer and few-layer thicknesses for engineering novel 2D transistor devices for future electronic technologies. We show that varying the parameters of the rheometer program can improve the mechanical exfoliation process.

Dielectric Properties of NbxW1-xSe2 Alloys.

The growth of transition metal dichalcogenide (TMDC) alloys provides an opportunity to experimentally access information elucidating how optical properties change with gradual substitutions in the lattice compared with their pure compositions. In this work, we performed growths of alloyed crystals with stoichiometric compositions between pure forms of NbSe2 and WSe2, followed by an optical analysis of those alloys by utilizing Raman spectroscopy and spectroscopic ellipsometry.

Probing the Optical Properties and Strain-Tuning of Ultrathin Mo1- xW xTe2.

Ultrathin transition metal dichalcogenides (TMDCs) have recently been extensively investigated to understand their electronic and optical properties. Here we study ultrathin Mo0.91W0.09Te2, a semiconducting alloy of MoTe2, using Raman, photoluminescence (PL), and optical absorption spectroscopy. Mo0.91W0.09Te2 transitions from an indirect to a direct optical band gap in the limit of monolayer thickness, exhibiting an optical gap of 1.10 eV, very close to its MoTe2 counterpart. We apply tensile strain, for the first time, to monolayer MoTe2 and Mo0.91W0.09Te2 to tune the band structure of these materials; we observe that their optical band gaps decrease by 70 meV at 2.3% uniaxial strain. The spectral widths of the PL peaks decrease with increasing strain, which we attribute to weaker exciton-phonon intervalley scattering. Strained MoTe2 and Mo0.91W0.09Te2 extend the range of band gaps of TMDC monolayers further into the near-infrared, an important attribute for potential applications in optoelectronics.

Electronic Characteristics of MoSe2 and MoTe2 for Nanoelectronic Applications.

Single-crystalline MoSe2 and MoTe2 platelets were grown by Chemical Vapor Transport (CVT), followed by exfoliation, device fabrication, optical and electrical characterization. We observed that for the field-effect-transistor (FET) channel thickness in range of 5.5 nm to 8.5 nm, MoTe2 shows p-type, whereas MoSe2 with channel thickness range of 1.6 nm to 10.5 nm, shows n-type conductivity behavior. At room temperature, both MoSe2 and MoTe2 FETs have high ON/OFF current ratio and low contact resistance. Controlling charge carrier type and mobility in MoSe2 and MoTe2 layers can pave a way for utilizing these materials for heterojunction nanoelctronic devices with superior performance.

Novel nanofluidic chemical cells based on self-assembled solid-state SiO2 nanotubes.

Novel nanofluidic chemical cells based on self-assembled solid-state SiO2 nanotubes on silicon-on-insulator (SOI) substrate have been successfully fabricated and characterized. The vertical SiO2 nanotubes with a smooth cavity are built from Si nanowires which were epitaxially grown on the SOI substrate. The nanotubes have rigid, dry-oxidized SiO2 walls with precisely controlled nanotube inner diameter, which is very attractive for chemical-/bio-sensing applications. No dispersion/aligning procedures were involved in the nanotube fabrication and integration by using this technology, enabling a clean and smooth chemical cell. Such a robust and well-controlled nanotube is an excellent case of developing functional nanomaterials by leveraging the strength of top-down lithography and the unique advantage of bottom-up growth. These solid, smooth, clean SiO2 nanotubes and nanofluidic devices are very encouraging and attractive in future bio-medical applications, such as single molecule sensing and DNA sequencing.

Near-theoretical fracture strengths in native and oxidized silicon nanowires.

In this letter, fracture strengths σ f of native and oxidized silicon nanowires (SiNWs) were determined via atomic force microscopy bending experiments and nonlinear finite element analysis. In the native SiNWs, σ f in the Si was comparable to the theoretical strength of Si〈111〉, ≈22 GPa. In the oxidized SiNWs, σ f in the SiO2 was comparable to the theoretical strength of SiO2, ≈6 to 12 GPa. The results indicate a change in the failure mechanism between native SiNWs, in which fracture originated via inter-atomic bond breaking or atomic-scale defects in the Si, and oxidized SiNWs, in which fracture initiated from surface roughness or nano-scale defects in the SiO2.

Electron microscopy observation of TiO2 nanocrystal evolution in high-temperature atomic layer deposition.

Understanding the evolution of amorphous and crystalline phases during atomic layer deposition (ALD) is essential for creating high quality dielectrics, multifunctional films/coatings, and predictable surface functionalization. Through comprehensive atomistic electron microscopy study of ALD TiO2 nanostructures at designed growth cycles, we revealed the transformation process and sequence of atom arrangement during TiO2 ALD growth. Evolution of TiO2 nanostructures in ALD was found following a path from amorphous layers to amorphous particles to metastable crystallites and ultimately to stable crystalline forms. Such a phase evolution is a manifestation of the Ostwald-Lussac Law, which governs the advent sequence and amount ratio of different phases in high-temperature TiO2 ALD nanostructures. The amorphous-crystalline mixture also enables a unique anisotropic crystal growth behavior at high temperature forming TiO2 nanorods via the principle of vapor-phase oriented attachment.

Single-Phase L10-Ordered High Entropy Thin Films with High Magnetic Anisotropy.

The vast high entropy alloy (HEA) composition space is promising for discovery of new material phases with unique properties. This study explores the potential to achieve rare-earth-free high magnetic anisotropy materials in single-phase HEA thin films. Thin films of FeCoNiMnCu sputtered on thermally oxidized Si/SiO2 substrates at room temperature are magnetically soft, with a coercivity on the order of 10 Oe. After post-deposition rapid thermal annealing (RTA), the films exhibit a single face-centered-cubic phase, with an almost 40-fold increase in coercivity. Inclusion of 50 at.% Pt in the film leads to ordering of a single L10 high entropy intermetallic phase after RTA, along with high magnetic anisotropy and 3 orders of magnitude coercivity increase. These results demonstrate a promising HEA approach to achieve high magnetic anisotropy materials using RTA.

Isotopic effects on in-plane hyperbolic phonon polaritons in MoO3.

Hyperbolic phonon polaritons (HPhPs), hybrids of light and lattice vibrations in polar dielectric crystals, empower nanophotonic applications by enabling the confinement and manipulation of light at the nanoscale. Molybdenum trioxide (α-MoO3) is a naturally hyperbolic material, meaning that its dielectric function deterministically controls the directional propagation of in-plane HPhPs within its reststrahlen bands. Strategies such as substrate engineering, nano- and heterostructuring, and isotopic enrichment are being developed to alter the intrinsic die ectric functions of natural hyperbolic materials and to control the confinement and propagation of HPhPs. Since isotopic disorder can limit phonon-based processes such as HPhPs, here we synthesize isotopically enriched 92MoO3 (92Mo: 99.93 %) and 100MoO3 (100Mo: 99.01 %) crystals to tune the properties and dispersion of HPhPs with respect to natural α-MoO3, which is composed of seven stable Mo isotopes. Real-space, near-field maps measured with the photothermal induced resonance (PTIR) technique enable comparisons of inplane HPhPs in α-MoO3 and isotopically enriched analogues within a reststrahlen band (≈820 cm-1 to ≈ 972 cm-1). Results show that isotopic enrichment (e.g., 92MoO3 and 100MoO3) alters the dielectric function, shifting the HPhP dispersion (HPhP angular wavenumber × thickness vs IR frequency) by ≈-7% and ≈ +9 %, respectively, and changes the HPhP group velocities by ≈ ±12 %, while the lifetimes (≈ 3 ps) in 92MoO3 were found to be slightly improved (≈ 20 %). The latter improvement is attributed to a decrease in isotopic disorder. Altogether, isotopic enrichment was found to offer fine control over the properties that determine the anisotropic in-plane propagation of HPhPs in α-MoO3, which is essential to its implementation in nanophotonic applications.

Electrolyte stability determines scaling limits for solid-state 3D Li ion batteries.

Rechargeable, all-solid-state Li ion batteries (LIBs) with high specific capacity and small footprint are highly desirable to power an emerging class of miniature, autonomous microsystems that operate without a hardwire for power or communications. A variety of three-dimensional (3D) LIB architectures that maximize areal energy density has been proposed to address this need. The success of all of these designs depends on an ultrathin, conformal electrolyte layer to electrically isolate the anode and cathode while allowing Li ions to pass through. However, we find that a substantial reduction in the electrolyte thickness, into the nanometer regime, can lead to rapid self-discharge of the battery even when the electrolyte layer is conformal and pinhole free. We demonstrate this by fabricating individual, solid-state nanowire core-multishell LIBs (NWLIBs) and cycling these inside a transmission electron microscope. For nanobatteries with the thinnest electrolyte, ≈110 nm, we observe rapid self-discharge, along with void formation at the electrode/electrolyte interface, indicating electrical and chemical breakdown. With electrolyte thickness increased to 180 nm, the self-discharge rate is reduced substantially, and the NWLIBs maintain a potential above 2 V for over 2 h. Analysis of the nanobatteries' electrical characteristics reveals space-charge limited electronic conduction, which effectively shorts the anode and cathode electrodes directly through the electrolyte. Our study illustrates that, at these nanoscale dimensions, the increased electric field can lead to large electronic current in the electrolyte, effectively shorting the battery. The scaling of this phenomenon provides useful guidelines for the future design of 3D LIBs.

Emergent ferromagnetism with superconductivity in Fe(Te,Se) van der Waals Josephson junctions.

Ferromagnetism and superconductivity are two key ingredients for topological superconductors, which can serve as building blocks of fault-tolerant quantum computers. Adversely, ferromagnetism and superconductivity are typically also two hostile orderings competing to align spins in different configurations, and thus making the material design and experimental implementation extremely challenging. A single material platform with concurrent ferromagnetism and superconductivity is actively pursued. In this paper, we fabricate van der Waals Josephson junctions made with iron-based superconductor Fe(Te,Se), and report the global device-level transport signatures of interfacial ferromagnetism emerging with superconducting states for the first time. Magnetic hysteresis in the junction resistance is observed only below the superconducting critical temperature, suggesting an inherent correlation between ferromagnetic and superconducting order parameters. The 0-π phase mixing in the Fraunhofer patterns pinpoints the ferromagnetism on the junction interface. More importantly, a stochastic field-free superconducting diode effect was observed in Josephson junction devices, with a significant diode efficiency up to 10%, which unambiguously confirms the spontaneous time-reversal symmetry breaking. Our work demonstrates a new way to search for topological superconductivity in iron-based superconductors for future high Tc fault-tolerant qubit implementations from a device perspective.

Rydberg Excitons and Trions in Monolayer MoTe2.

Monolayer transition metal dichalcogenide (TMDC) semiconductors exhibit strong excitonic optical resonances, which serve as a microscopic, noninvasive probe into their fundamental properties. Like the hydrogen atom, such excitons can exhibit an entire Rydberg series of resonances. Excitons have been extensively studied in most TMDCs (MoS2, MoSe2, WS2, and WSe2), but detailed exploration of excitonic phenomena has been lacking in the important TMDC material molybdenum ditelluride (MoTe2). Here, we report an experimental investigation of excitonic luminescence properties of monolayer MoTe2 to understand the excitonic Rydberg series, up to 3s. We report a significant modification of emission energies with temperature (4 to 300 K), thereby quantifying the exciton-phonon coupling. Furthermore, we observe a strongly gate-tunable exciton-trion interplay for all the Rydberg states governed mainly by free-carrier screening, Pauli blocking, and band gap renormalization in agreement with the results of first-principles GW plus Bethe-Salpeter equation approach calculations. Our results help bring monolayer MoTe2 closer to its potential applications in near-infrared optoelectronics and photonic devices.

Correlation between the performance and microstructure of Ti/Al/Ti/Au Ohmic contacts to p-type silicon nanowires.

Understanding the electrical and microstructural aspects of contact formation at nanoscale is essential for the realization of low-resistance metallization suitable for the next generation of nanowire based devices. In this study, we present detailed electrical and microstructural characteristics of Ti/Al/Ti/Au metal contacts to p-type Si nanowires (SiNWs) annealed at various temperatures. Focused ion beam cross-sectioning techniques and scanning transmission electron microscopy (STEM) were used to determine the microstructure of the source/drain metal contacts of working SiNW field-effect transistors (FETs) annealed for 30 s in the 450-850 °C temperature range in inert atmosphere. Formation of titanium silicides is observed at the metal/semiconductor interface after the 750 °C anneal. Extensive Si out-diffusion from the nanowire after the 750 °C anneal led to Kirkendall void formation. Annealing at 850 °C led to almost complete out-diffusion of Si from the nanowire core. Devices with 550 °C annealed contacts had linear electrical characteristics; whereas the devices annealed at 750 °C had the best characteristics in terms of linearity, symmetric behavior, and yield. Devices annealed at 850 °C had poor yield, which can be directly attributed to the microstructure of the contact region observed in STEM.

Thermomagnetic properties of Bi2Te3 single crystal in the temperature range from 55 K to 380 K.

Magneto-thermoelectric transport provides an understanding of coupled electron-hole-phonon current in topological materials and has applications in energy conversion and cooling. In this work, we study the Nernst coefficient, the magneto-Seebeck coefficient, and the magnetoresistance of single-crystalline Bi2Te3 under external magnetic field in the range of -3 T to 3 T and in the temperature range of 55 K to 380 K. Moreau's relation is employed to justify both the overall trend of the Nernst coefficient and the temperature at which the Nernst coefficient changes sign. We observe a non-linear relationship between the Nernst coefficient and the applied magnetic field in the temperature range of 55 K to 255 K. An increase in both the Nernst coefficient and the magneto-Seebeck coefficient is observed as the temperature is reduced which can be attributed to the increased mobility of the carriers at lower temperatures. First-principles density functional theory calculations were carried out to physically model the experimental data including electronic and transport properties. Simulation findings agreed with the experiments and provide a theoretical insight to justify the measurements.

Substrate-mediated hyperbolic phonon polaritons in MoO3.

Hyperbolic phonon polaritons (HPhPs) are hybrid excitations of light and coherent lattice vibrations that exist in strongly optically anisotropic media, including two-dimensional materials (e.g., MoO3). These polaritons propagate through the material's volume with long lifetimes, enabling novel mid-infrared nanophotonic applications by compressing light to sub-diffractional dimensions. Here, the dispersion relations and HPhP lifetimes (up to ≈12 ps) in single-crystalline α-MoO3 are determined by Fourier analysis of real-space, nanoscale-resolution polariton images obtained with the photothermal induced resonance (PTIR) technique. Measurements of MoO3 crystals deposited on periodic gratings show longer HPhPs propagation lengths and lifetimes (≈2×), and lower optical compressions, in suspended regions compared with regions in direct contact with the substrate. Additionally, PTIR data reveal MoO3 subsurface defects, which have a negligible effect on HPhP propagation, as well as polymeric contaminants localized under parts of the MoO3 crystals, which are derived from sample preparation. This work highlights the ability to engineer substrate-defined nanophotonic structures from layered anisotropic materials.

Localized Excitons in NbSe2-MoSe2 Heterostructures.

Neutral and charged excitons (trions) in atomically thin materials offer important capabilities for photonics, from ultrafast photodetectors to highly efficient light-emitting diodes and lasers. Recent studies of van der Waals (vdW) heterostructures comprised of dissimilar monolayer materials have uncovered a wealth of optical phenomena that are predominantly governed by interlayer interactions. Here, we examine the optical properties in NbSe2-MoSe2 vdW heterostructures, which provide an important model system to study metal-semiconductor interfaces, a common element in optoelectronics. Through low-temperature photoluminescence (PL) microscopy, we discover a sharp emission feature, L1, that is localized at the NbSe2-capped regions of MoSe2. L1 is observed at energies below the commonly studied MoSe2 excitons and trions and exhibits temperature- and power-dependent PL consistent with exciton localization in a confining potential. This PL feature is robust, observed in a variety of samples fabricated with different stacking geometries and cleaning procedures. Using first-principles calculations, we reveal that the confinement potential required for exciton localization naturally arises from the in-plane band bending due to the changes in the electron affinity between pristine MoSe2 and NbSe2-MoSe2 heterostructure. We discuss the implications of our studies for atomically thin optoelectronics devices with atomically sharp interfaces and tunable electronic structures.