Two-dimensional layered trichalcogenide materials have recently attracted the attention of the scientific community because of their robust mechanical and thermal properties and applications in opto- and nanoelectronics devices. We report the pressure dependence of out-of-plane Ag Raman modes in high quality few-layer titanium trisulfide (TiS3) nanoribbons grown using a direct solid-gas reaction method and infer their cross-plane thermal expansion coefficient. Both mechanical stability and thermal properties of the TiS3 nanoribbons are elucidated by using phonon-spectrum analyses. Raman spectroscopic studies at high pressure (up to 34 GPa) using a diamond anvil cell identify four prominent Ag Raman bands; a band at 557 cm-1 softens under compression, and others at 175, 300, and 370 cm-1 show normal hardening. Anomalies in phonon mode frequencies and excessive broadening in line width of the soft phonon about 13 GPa are attributed to the possible onset of a reversible structural transition. A complete structural phase transition at 43 GPa is inferred from the Ag soft mode frequency (557 cm-1) versus pressure extrapolation curve, consistent with recently reported theoretical predictions. Using the experimental mode Grüneisen parameters γi of Raman modes, we estimated the cross-plane thermal expansion coefficient Cv of the TiS3 nanoribbons at ambient phase to be 1.321 × 10-6 K-1. The observed results are expected to be useful in calibration and performance of next-generation nanoelectronics and optical devices under extreme stress conditions.

Phase engineering of MoS₂ transistors has recently been demonstrated and has led to record low contact resistances. The phase patterning of MoS₂ flakes with laser radiation has also been realized via spectroscopic methods, which invites the potential of controlling the metallic and semiconducting phases of MoS₂ transistors by simple light exposure. Nevertheless, the fabrication and demonstration of laser-patterned MoS₂ devices starting from the metallic polymorph have not been demonstrated yet. Here, we study the effects of laser radiation on 1T/1T′$-MoS₂ transistors with the prospect of driving an in situ phase transition to the 2H-polymorph through light exposure. We find that although the Raman peaks of 2H-MoS₂ become more prominent and the ones from the 1T/1T$′ phase fade after the laser exposure, the semiconducting properties of the laser-patterned devices are not fully restored, and the laser treatment ultimately leads to the degradation of the transport channel.

The isolation of graphene and transition metal dichalcongenides has opened a veritable world to a great number of layered materials which can be exfoliated, manipulated, and stacked or combined at will. With continued explorations expanding to include other layered materials with unique attributes, it is becoming clear that no one material will fill all the post-silicon era requirements. Here we review the properties and applications of layered, quasi-1D transition metal trichalcogenides (TMTCs) as novel materials for next generation electronics and optoelectronics. The TMTCs present a unique chain-like structure which gives the materials their quasi-1D properties such as high anisotropy ratios in conductivity and linear dichroism. The range of band gaps spanned by this class of materials (0.2 eV-2 eV) makes them suitable for a wide variety of applications including field-effect transistors, infrared, visible and ultraviolet photodetectors, and unique applications related to their anisotropic properties which opens another degree of freedom in the development of next generation electronics. In this review we survey the historical development of these remarkable materials with an emphasis on the recent activity generated by the isolation and characterization of atomically thin titanium trisulfide (TiS₃).

The high field transport characteristics of nanostructured transistors based on layered materials are not only important from a device physics perspective but also for possible applications in next generation electronics. With the growing promise of layered materials as replacements to conventional silicon technology, the high current density properties of the layered material titanium trisulfide (TiS₃) are studied here. The high breakdown current densities of up to 1.7 × 10⁶ A cm⁻² are observed in TiS₃ nanoribbon-based field-effect transistors, which are among the highest found in semiconducting nanomaterials. Investigating the mechanisms responsible for current breakdown, a thermogravimetric analysis of bulk TiS₃ is performed and the results with density functional theory and kinetic Monte Carlo calculations are compared. In conclusion, the oxidation of TiS₃ and subsequent desorption of sulfur atoms play an important role in the electrical breakdown of the material in ambient conditions. The results show that TiS₃ is an attractive material for high power applications and lend insight into the thermal and defect activated mechanisms responsible for electrical breakdown in nanostructured devices.

Superconductors containing magnetic impurities exhibit intriguing phenomena derived from the competition between Cooper pairing and Kondo screening. At the heart of this competition are the Yu-Shiba-Rusinov (Shiba) states which arise from the pair breaking effects a magnetic impurity has on a superconducting host. Hybrid superconductor-molecular junctions offer unique access to these states but the added complexity in fabricating such devices has kept their exploration to a minimum. Here, we report on the successful integration of a model spin 1/2 impurity, in the form of a neutral and stable all organic radical molecule, in proximity-induced superconducting break junctions. Our measurements reveal excitations which are characteristic of a spin-induced Shiba state due to the radical's unpaired spin strongly coupled to a superconductor. By virtue of a variable molecule-electrode coupling, we access both the singlet and doublet ground states of the hybrid system which give rise to the doublet and singlet Shiba excited states, respectively. Our results show that Shiba states are a robust feature of the interaction between a paramagnetic impurity and a proximity-induced superconductor where the excited state is mediated by correlated electron-hole (Andreev) pairs instead of Cooper pairs.

The fabrication of van der Waals heterostructures, artificial materials assembled by individual stacking of 2D layers, is among the most promising directions in 2D materials research. Until now, the most widespread approach to stack 2D layers relies on deterministic placement methods, which are cumbersome and tend to suffer from poor control over the lattice orientations and the presence of unwanted interlayer adsorbates. Here, we present a different approach to fabricate ultrathin heterostructures by exfoliation of bulk franckeite which is a naturally occurring and air stable van der Waals heterostructure (composed of alternating SnS 2-like and PbS-like layers stacked on top of each other). Presenting both an attractive narrow bandgap (<0.7 eV) and p-type doping, we find that the material can be exfoliated both mechanically and chemically down to few-layer thicknesses. We present extensive theoretical and experimental characterizations of the material's electronic properties and crystal structure, and explore applications for near-infrared photodetectors.

Carbon nanotubes (CNTs) are a promising material for high-performance electronics beyond silicon. But unlike silicon, the nature of the transport band gap in CNTs is not fully understood. The transport gap in CNTs is predicted to be strongly driven by electron-electron (e-e) interactions and correlations, even at room temperature. Here, we use dielectric liquids to screen e-e interactions in individual suspended ultra-clean CNTs. Using multiple techniques, the transport gap is measured as dielectric screening is increased. Changing the dielectric environment from air to isopropanol, we observe a 25% reduction in the transport gap of semiconducting CNTs, and a 32% reduction in the band gap of narrow-gap CNTs. Additional measurements are reported in dielectric oils. Our results elucidate the nature of the transport gap in CNTs, and show that dielectric environment offers a mechanism for significant control over the transport band gap.

Two-dimensional (2D) semiconducting materials are particularly appealing for many applications. Although theory predicts a large number of 2D materials, experimentally only a few of these materials have been identified and characterized comprehensively in the ultrathin limit. Lead iodide, which belongs to the transition metal halides family and has a direct bandgap in the visible spectrum, has been known for a long time and has been well characterized in its bulk form. Nevertheless, studies of this material in the nanometer thickness regime are rather scarce. In this article we demonstrate an easy way to synthesize ultrathin, highly crystalline flakes of PbI₂ by precipitation from a solution in water. We thoroughly characterize the produced thin flakes with different techniques ranging from optical and Raman spectroscopy to temperature-dependent photoluminescence and electron microscopy. We compare the results to ab initio calculations of the band structure of the material. Finally, we fabricate photodetectors based on PbI₂ and study their optoelectronic properties.

Recent experiments showed that thinning gallium, iron selenide and 2H tantalum disulfide to single/several monoatomic layer(s) enhances their superconducting critical temperatures. Here, we characterize these superconductors by extracting the absolute values of the London penetration depth, the superconducting energy gap, and the relative jump in specific heat at the transition temperature from their self-field critical currents. Our central finding is that the enhancement in transition temperature for these materials arises from the opening of an additional superconducting gap, while retaining a largely unchanged 'bulk' superconducting gap. Literature data reveals that ultrathin niobium films similarly develop a second superconducting gap. Based on the available data, it seems that, for type-II superconductors, a new superconducting band appears when the film thickness becomes smaller than the out-of-plane coherence length. The same mechanism may also be the cause of enhanced interface superconductivity.

Wereport on observations of thickness dependent Josephson coupling and multiple Andreev reflections (MAR) in vertically stacked molybdenum disulfide (MoS₂)-molybdenum rhenium (MoRe) Josephson junctions. MoRe, a chemically inert superconductor, allows for oxide free fabrication of high transparency vertical MoS₂ devices. Single and bilayer MoS₂ junctions display relatively large critical currents (up to 2.5 μA) and the appearance of sub-gap structure given by MAR. In three and four layer thick devices we observe orders of magnitude lower critical currents (sub-nA) and reduced quasiparticle gaps due to proximitized MoS₂ layers in contact with MoRe.Weanticipate that this device architecture could be easily extended to other 2D materials.

We report on the large-scale synthesis of highly oriented ultrathin MoO₃ layers using a simple and low-cost atmospheric pressure, van der Waals epitaxy growth on muscovite mica substrates. By this method, we are able to synthesize high quality centimeter-scale MoO₃ crystals with thicknesses ranging from 1.4 nm (two layers) up to a few nanometers. The crystals can be easily transferred to an arbitrary substrate (such as SiO₂) by a deterministic transfer method and be extensively characterized to demonstrate the high quality of the resulting crystal. We also study the electronic band structure of the material by density functional calculations. Interestingly, the calculations demonstrate that bulk MoO₃ has a rather weak electronic interlayer interaction, and thus, it presents a monolayer-like band structure. Finally, we demonstrate the potential of this synthesis method for optoelectronic applications by fabricating large-area field-effect devices (10 μm × 110 μm in lateral dimensions) and find responsivities of 30 mA W^-1 for a laser power density of 13 mW cm^-2 in the UV region of the spectrum and also as an electron acceptor in a MoS₂-based field-effect transistor.

Thin layers of black phosphorus present an ideal combination of a 2Dmaterial with a tunable direct bandgap and high carrier mobility. However the material suffers from degradation in ambient conditions due to an oxidation reaction which involves water, oxygen and light. Wehave measured the spatial profile of the conductivity on flakes of black phosphorus as a function of time using scanning microwave impedance microscopy. Amicrowave excitation (3 GHz) allows to image a conducting sample even when covered with a dielectric layer. Weobserve that on bare black phosphorus, the conductivity changes drastically over the whole surface within a day. Wedemonstrate that the degradation process is slowed down considerably by covering the material with a 10 nmlayer of hafnium oxide. It is stable for more than a week, opening up a route towards stable black phosphorus devices in which the high dielectric constant of hafnium oxide can be exploited. Covering black phosphorus with a 15 nmboron nitride flake changes the degradation process qualitatively, it is dominated by the edges of the flake indicating a diffusive process and happens on the scale of days.

The ability to exfoliate layered materials down to the single layer limit has presented the opportunity to understand how a gradual reduction in dimensionality affects the properties of bulk materials. Here we use this top-down approach to address the problem of superconductivity in the two-dimensional limit. The transport properties of electronic devices based on 2H tantalum disulfide flakes of different thicknesses are presented. We observe that superconductivity persists down to the thinnest layer investigated (3.5 nm), and interestingly, we find a pronounced enhancement in the critical temperature from 0.5 to 2.2 K as the layers are thinned down. In addition, we propose a tight-binding model, which allows us to attribute this phenomenon to an enhancement of the effective electron-phonon coupling constant. This work provides evidence that reducing the dimensionality can strengthen superconductivity as opposed to the weakening effect that has been reported in other 2D materials so far.