One-dimensional (1D) van der Waals (vdW) materials display electronic and magnetic transport properties that make them uniquely suited as interconnect materials and for low-dimensional optoelectronic applications. However, there are only around 700 1D vdW structures in general materials databases, making database curation approaches ineffective for 1D discovery. Here, we utilize machine-learning techniques to discover 1D vdW compositions that have not yet been synthesized. Our techniques go beyond discovery efforts involving elemental substitutions and instead start with a composition space of 4741 binary and 392,342 ternary formulas. We predict up to 3000 binary and 10,000 ternary 1D compounds and further classify them by expected magnetic and electronic properties. Our model identifies MoI3, a material we experimentally confirm to exist with wire-like subcomponents and exotic magnetic properties. More broadly, we find several chalcogen-, halogen-, and pnictogen-containing compounds expected to be synthesizable using chemical vapor deposition and chemical vapor transport.

Extending knowledge of the properties of low-dimensional van der Waals materials, including their reactivity to the ambiance, is important for developing innovative electronic and optoelectronic devices. Transition metal trichalcogenides with tunable optical band gaps and anisotropic conductivity are an emerging class among low-dimensional structures with the possibility of gate tunability and photoreactivity. These properties can be combined into light-enhanced field-effect transistor gas sensors. We demonstrated prototype zirconium trisulfide (ZrS3) sensors for nitrogen dioxide, ethanol, and acetone. Photoconductivity and photogating play a critical role in photoinduced gas sensing, with the dominance of the first for blue (470 nm) and green (515 nm) and the second one prevailing for red (700 nm) irradiations. Our results suggest that surface trap states lead both to trapping and scattering of the charge carriers in the channel. The gas detection is guided by charge transfer and modulation of the carrier mobility, resulting in distinct I -V characteristics for selected irradiation conditions.

We conducted a tip-enhanced Raman scattering spectroscopy (TERS) and photoluminescence (PL) study of quasi-1D TaSe3-δ nanoribbons exfoliated onto gold substrates. At a selenium deficiency of δ ∼ 0.25 (Se/Ta = 2.75), the nanoribbons exhibit a strong, broad PL peak centered around ∼920 nm (1.35 eV), suggesting their semiconducting behavior. Such nanoribbons revealed a strong TERS response under 785 nm (1.58 eV) laser excitation, allowing for their nanoscale spectroscopic imaging. Nanoribbons with a smaller selenium deficiency (Se/Ta = 2.85, δ ∼ 0.15) did not show any PL or TERS response. The confocal Raman spectra of these samples agree with the previously-reported spectra of metallic TaSe3. The differences in the optical response of the nanoribbons examined in this study suggest that even small variations in Se content can induce changes in electronic band structure, causing samples to exhibit either metallic or semiconducting character. The temperature-dependent electrical measurements of devices fabricated with both types of materials corroborate these observations. The density-functional-theory calculations revealed that substitution of an oxygen atom in a Se vacancy can result in band gap opening and thus enable the transition from a metal to a semiconductor. However, the predicted band gap is substantially smaller than that derived from the PL data. These results indicate that the properties of van der Waals materials can vary significantly depending on stoichiometry, defect types and concentration, and possibly environmental and substrate effects. In view of this finding, local probing of nanoribbon properties with TERS becomes essential to understanding such low-dimensional systems.

We report on the temperature evolution of the polarization-dependent Raman spectrum of exfoliated MoI$_3$, a van der Waals material with a "true one-dimensional" crystal structure that can be exfoliated to individual atomic chains. The temperature evolution of several Raman features reveals anomalous behavior suggesting a phase transition of a magnetic origin. Theoretical considerations indicate that MoI$_3$ is an easy-plane antiferromagnet with alternating spins along the dimerized chains and with inter-chain helical spin ordering. The calculated frequencies of the phonons and magnons are consistent with the interpretation of the experimental Raman data. The obtained results shed light on the specifics of the phononic and magnonic states in MoI$_3$ and provide a strong motivation for future study of this unique material with potential for spintronic device applications.

We report the polarization-dependent Raman spectra of exfoliated MoI3, a van der Waals material with a “true one-dimensional” crystal structure that can be exfoliated to individual atomic chains. The temperature evolution of several Raman features reveals an anomalous behavior suggesting a phase transition of magnetic origin. Theoretical considerations indicate that MoI3 is an easy-plane antiferromagnet with alternating spins along the dimerized chains and with inter-chain helical spin ordering. The calculated frequencies of phonons and magnons are consistent with the interpretation of the experimental Raman data. The obtained results shed light on the specifics of the phononic and magnonic states in MoI3 and provide a strong motivation for further study of this unique material with potential for future spintronic applications.

We report on the chemical vapor deposition (CVD) growth of quasi-one-dimensional zirconium tritelluride (ZrTe3) at temperatures below 600 degrees C and process times under an hour, which results in a material on a SiO2/Si wafer substrate that offers electrical conductivity comparable to the bulk. This study combines tailored CVD processing using a tube-in-a-tube technique with characterization by optical microscopy, Raman spectroscopy, and scanning electron microscopy. Transmission electron microscopy validates the composition and offers atomic contrast. Electrical transport measurements employ an yttrium-gold stack to achieve good adhesion and low contact resistance. A positive temperature coefficient is observed, as expected for a metallic material. The obtained results are important for the proposed applications of quasi-one-dimensional van der Waals materials in the next-generation electronic devices.

Low turn-on (knee) voltage (∼0.3 V) Schottky-diode behavior of a four-layer (4L) MoS2/GaN junction is achieved by optimizing the in situ interface preparation of the GaN substrate prior to MoS2 overlayer growth in a vacuum system using metallic molybdenum and hydrogen sulfide gas as precursors. The process leads to a clean nitrogen-terminated GaN surface that bonds well to the MoS2 film revealing a 2 × 2 reconstruction at the interface observed in low-energy electron diffraction (LEED). Atomic force microscopy and X-ray photoelectron spectroscopy provide clear images of the GaN terraces through the MoS2 overlayer confirming close adhesion and absence of oxygen and other contaminants. Density functional theory calculations predict the formation of the 2 × 2 superstructure at a clean interface. Transport measurements show diode behavior at an on/off ratio of ∼105 for ±1 V with a forward direction for the positive voltage applied to the MoS2 layer. Combining transport and photoelectron spectroscopy measurements with theory, we deduce a Fermi-level position in the MoS2 gap consistent with interface charge transfer from MoS2 to the substrate. The high performance of the MoS2/Gan diode highlights the technological potential of devices based on GaN/MoS2 interfaces.

Homogenous single-layer MoS2 films coated with sub-single layer amounts of gold are found to isolate the reaction of methanol with carbon monoxide, the fundamental step toward higher alcohols, from an array of possible surface reactions. Active surfaces were prepared from homogenous single-layer MoS2 films coated with sub-single layer amounts of gold. These gold atoms formed clusters on the MoS2 surface. A gas mixture of carbon monoxide (CO) and methanol (CH3OH) was partially converted to acetaldehyde (CH3CHO) under mild process conditions (308 kPa and 393 K). This carbonylation of methanol to a C2 species is a critical step toward the formation of higher alcohols. Density functional theory modeling of critical steps of the catalytic process identify a viable reaction pathway. Imaging and spectroscopic methods revealed that the single layer of MoS2 facilitated formation of nanoscale gold islands, which appear to sinter through Ostwald ripening. The formation of acetaldehyde by the catalytic carbonylation of methanol over supported gold clusters is an important step toward realizing controlled production of useful molecules from low carbon-count precursors.

We report on nanosecond-long, gate-dependent valley lifetimes of free charge carriers in monolayer WSe2, unambiguously identified by the combination of time-resolved Kerr rotation and electrical transport measurements. While the valley polarization increases when tuning the Fermi level into the conduction or valence band, there is a strong decrease of the respective valley lifetime consistent with both electron-phonon and spin-orbit scattering. The longest lifetimes are seen for spin-polarized bound excitons in the band gap region. We explain our findings via two distinct, Fermi-level-dependent scattering channels of optically excited, valley-polarized bright trions either via dark or bound states. By electrostatic gating we demonstrate that the transition-metal dichalcogenide WSe2 can be tuned to be either an ideal host for long-lived localized spin states or allow for nanosecond valley lifetimes of free charge carriers (>10 ns).

An in-depth analysis of valley physics in 2D materials like transition metal dichalcogenides requires the measurement of many material properties as a function of Fermi level position within the electronic band structure. This is normally done by changing the charge carrier density of the 2D material via the gate electric field effect. Here, we show that a comparison of gate-dependent measurements, which were acquired under different measurement conditions can encounter significant problems due to the temporal evolution of the charging of trap states inside the dielectric layer or at its interfaces. The impact of, e.g., the gate sweep direction and the sweep rate on the overall gate dependence gets especially prominent in optical measurements due to photo-excitation of donor and acceptor states. Under such conditions the same nominal gate-voltage may lead to different gate-induced charge carrier densities and, hence, Fermi level positions. We demonstrate that a current flow from or even through the dielectric layer via leakage currents can significantly diminish the gate tunability in optical measurements of 2D materials.

One of the main tasks in the investigation of 2-dimensional transition metal dichalcogenides is the determination of valley lifetimes. In this work, we combine time-resolved Kerr rotation with electrical transport measurements to explore the gate-dependent valley lifetimes of free conduction band electrons of monolayer WSe2. When tuning the Fermi energy into the conduction band we observe a strong decrease of the respective valley lifetimes which is consistent with both spin-orbit and electron-phonon scattering. We explain the formation of a valley polarization by the scattering of optically excited valley polarized bright trions into dark states by intervalley scattering. Furthermore, we show that the conventional time-resolved Kerr rotation measurement scheme has to be modified to account for photo-induced gate screening effects. Disregarding this adaptation can lead to erroneous conclusions drawn from gate-dependent optical measurements and can completely mask the true gatedependent valley dynamics.

Micron-scale single-crystal nanowires of metallic TaSe3, a material that forms -Ta-Se-3-Ta-Se-3- stacks separated from one another by a tubular van der Waals (vdW) gap, have been synthesized using chemical vapor deposition (CVD) on a SiO2/Si substrate, in a process compatible with semiconductor industry requirements. Their electrical resistivity was found unaffected by downscaling from the bulk to as little as 7 nm in nanowire width and height, in striking contrast to the resistivity of copper for the same dimensions. While the bulk resistivity of TaSe3 is substantially higher than that of bulk copper, at the nanometer scale the TaSe3 wires become competitive to similar-sized copper ones. Moreover, we find that the vdW TaSe3 nanowires sustain current densities in excess of 10(8) A/cm(2) and feature an electromigration energy barrier twice that of copper. The results highlight the promise of quasi-one-dimensional transition metal trichalcogenides for electronic interconnect applications and the potential of van der Waals materials for downscaled electronics.

Atomically thin 2D materials such as transition metal dichalcogenides (TMDs) provide a wide range of basic building blocks with unique properties, making them ideal for heterogeneous integration with a mature chip platform for advances in optical communication technology. The control and understanding of the precise value of the optical index of these materials, however, is challenging, as the standard metrology techniques such as the millimeter-large ellipsometry is often not usable due the small lateral 2D material flake dimension. Here, we demonstrate an approach of passive tunable coupling by integrating few layers of MoTe2 onto a microring resonator connected to a waveguide bus. We find the TMD-to-ring circumference coverage length ratio required to precisely place the ring into a critical coupling condition to be about 10% as determined from the variation of spectral resonance visibility and loss as a function of TMD coverage. Using this TMD-ring heterostructure, we further demonstrate a semiempirical method to determine the index of a 2D material (n(MoTe2) of 4.36 + 0.011i) near telecommunication-relevant wavelength. The placement, control, and optical property understanding of 2D materials with integrated photonics pave the way for further studies of active 2D material-based optoelectronics and circuits.

We demonstrate that a fused silica substrate can be rendered active for acetaldehyde (CH 3 CHO) synthesis from a gas mixture of carbon monoxide (CO) and methanol (CH 3 OH) under mild process conditions (308 kPa and 393 K) by deposition first of a homogenous single-layer MoS 2 film and subsequently of a sub-mnonolayer (1 Angstrom) loading of gold. In operando monitoring of the catalyst performance in a flow reactor reveals uncompromised activity even after 2 hours on stream. The carbonylation of methanol to a C 2 species represents a crucial step toward the formation of higher alcohols from syngas derived from methane or biomass. Characterization of the film by imaging and spectroscopy reveals that the single-layer MoS 2 film disperses the gold loading into nanoscale islands; density functional theory (DFT) calculations identify low-coordinated edge sites on these islands as active centers for the carbon-carbon coupling at barriers significantly below 1 eV.

Layered two-dimensional (2D) materials provide a wide range of unique properties as compared to their bulk counterpart, making them ideal for heterogeneous integration for on-chip interconnects. Hence, a detailed understanding of the loss and index change on Si integrated platform is a prerequisite for advances in opto-electronic devices impacting optical communication technology, signal processing, and possibly photonic-based computing. Here, we present an experimental guide to characterize transition metal dichalcogenides (TMDs), once monolithically integrated into the Silicon photonic platform at 1.55 um wavelength. We describe the passive tunable coupling effect of the resonator in terms of loss induced as a function of 2D material layer coverage length and thickness. Further, we demonstrate a TMD-ring based hybrid platform as a refractive index sensor where resonance shift has been mapped out as a function of flakes thickness which correlates well with our simulated data. These experimental findings on passive TMD-Si hybrid platform open up a new dimension by controlling the effective change in loss and index, which may lead to the potential application of 2D material based active on chip photonics.

We demonstrate the facile deposition of catalytically active stable Au nanoparticles on single-layer MoS2, on an inert oxide substrate (SiO2). Unlike a gold surface, adsorption of CO on these gold particles proceeds even at room temperature. Subsequent exposure to oxygen leads to CO2 formation and desorption along a reaction pathway described, in detail, by density functional theory. The barrier to CO oxidation, along this pathway, is less than 300 meV, corroborating the facile nature of the CO oxidation reactions in this system. X-ray photoelectron spectroscopy directly reveals that the carbon monoxide, adsorbed on Au nanoparticles on single-layer MoS2, can be repeatedly titrated off the substrate by exposure to oxygen. Comparison of computational results assuming a defect-laden and pristine MoS2 substrate suggest that the pristine single-layer material may be superior in supporting this reaction.

Precision and chip contamination-free placement of two-dimensional (2D) materials is expected to accelerate both the study of fundamental properties and novel device functionality. Current transfer methods of 2D materials onto an arbitrary substrate deploy wet chemistry and viscoelastic stamping. However, these methods produce a) significant cross contamination of the substrate due to the lack of spatial selectivity b) may not be compatible with chemically sensitive device structures, and c) are challenged with respect to spatial alignment. Here, we demonstrate a novel method of transferring 2D materials resembling the functionality known from printing; utilizing a combination of a sharp micro-stamper and viscoelastic polymer, we show precise placement of individual 2D materials resulting in vanishing cross contamination to the substrate. Our 2D printer-method results show an aerial cross contamination improvement of two to three orders of magnitude relative to state-of-the-art dry and direct transfer methods. Moreover, we find that the 2D material quality is preserved in this transfer method. Testing this 2D material printer on taped-out integrated Silicon photonic chips, we find that the micro-stamper stamping transfer does not physically harm the underneath Silicon nanophotonic structures such as waveguides or micro-ring resonators receiving the 2D material. Such accurate and substrate-benign transfer method for 2D materials could be industrialized for rapid device prototyping due to its high time-reduction, accuracy, and contamination-free process.

Wafer-scale MoS2 growth at arbitrary integer layer number is demonstrated by a technique based on the decomposition of carbon disulfide on a hot molybdenum filament, which yields volatile MoS x precursors that precipitate onto a heated wafer substrate. Colorimetric control of the growth process allows precise targeting of any integer layer number. The method is inherently free of particulate contamination, uses inexpensive reactants without the pyrophoricity common to metal-organic precursors, and does not rely on particular gas-flow profiles. Raman mapping and photoluminescence mapping, as well as imaging by electron microscopy, confirm the layer homogeneity and crystalline quality of the resultant material. Electrical characterization revealed microampere output current, outstanding device-to-device consistency, and exceptionally low noise level unparalleled even by the exfoliated material, while other transport properties are obscured by high-resistance contacts typical to MoS2 devices.

Schottky-like barriers are an important limitation of the performance of single-layer transition metal dichalcogenide (TMD) transistors; because of the small number of charge carriers in a 2D semiconductor, the screening of metal contacts is inefficient leading to large depletion zones and enhanced reduction of performance compared to conventional bulk Schottky Barriers. Here we demonstrate that lithographic pre-patterning of a growth substrate prior to chemical vapor deposition of a TMD film can shape the TMD material into nanoscale hybrid 2D/3D structures whose bulk-like (3D) portion can be used for metal contacts and efficient charge injection into the single-layer (2D) areas which serve as transistor channels with excellent mobilities and on-off ratios. We observe mobilities of nearly 100 cm(2) V-1 s(-1) with an on/off ratio > 105 for bottom-gated devices (through 300 nm of oxide) at realistic operation temperatures near 100 degrees C using comparatively long channels (> 5 microns) and absent other contact optimization. Our process involves lithographic patterning of a hafnium (IV) dioxide film onto the SiO2/Si substrate prior to TMD growth. Bulk-like 3D WSe2 is observed to grow at the location of the hafnia, while 2D single-layer material is grown in regions of bare SiO2. Systematic evaluation of transport data allows us to extract Schottky barrier heights and other fundamental properties of our hybrid devices.

Spin-orbit coupling (SOC) in graphene can be greatly enhanced by proximity coupling it to transition metal dichalcogenides (TMDs) such as WSe2. We find that the strength of the acquired SOC in graphene depends on the stacking order of the heterostructures when using hexagonal boron nitride ( h-BN) as the capping layer, i.e., SiO2/graphene/WSe2/ h-BN exhibiting stronger SOC than SiO2/WSe2/graphene/ h-BN. We utilize photoluminescence (PL) as an indicator to characterize the interaction between graphene and monolayer WSe2 grown by chemical vapor deposition. We observe much stronger PL quenching in the SiO2/graphene/WSe2/ h-BN stack than in the SiO2/WSe2/graphene/ h-BN stack and, correspondingly, a much larger weak antilocalization (WAL) effect or stronger induced SOC in the former than in the latter. We attribute these two effects to the interlayer distance between graphene and WSe2, which depends on whether graphene is in immediate contact with h-BN. Our observations and hypothesis are further supported by first-principles calculations, which reveal a clear difference in the interlayer distance between graphene and WSe2 in these two stacks.