The field emission (FE) properties of TiS3 nanosheets and nanoribbons, synthesized by direct sulfuration of bulk titanium, are investigated. The nanosheets show an enhanced FE behavior with a low turn-on field of ∼0.3 V/μm, required for drawing an emission current density of ∼10 μA/cm2. Interestingly, the TiS3 nanosheet emitter delivered a large emission current density of ∼0.9 mA/cm2 at a relatively low applied electric field of ∼0.4 V/μm. We have estimated the values of the field enhancement factor (β), which are found to be ∼5 × 104 for the TiS3 nanosheet emitter and ∼4 × 103 for the nanoribbon emitter. We attribute the superior FE performance to the presence of atomically sharp edges and the reduced thickness of TiS3, as reflected in the high value of β. In fact, the nanosheet sample presents a higher density of ultrathin layers (∼12 nm-thick), and thus, they have a larger edge to volume ratio than the nanoribbon samples (which are ∼19 nm-thick). The superior FE behavior of TiS3 nanosheets over nanoribbons makes them a propitious field emitter and can be utilized for various FE-based applications, demanding large emission currents and lower operational voltages. Moreover, the FE current stability recorded on these samples confirms their promising performance. Thus, the present investigation brings out a great promise of TiS3 nanosheets and nanoribbons as field emitters for vacuum nanoelectronics devices.

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.

We have studied electrical transport as a function of carrier density, temperature and bias in multi-terminal devices consisting of hexagonal boron nitride (h-BN) encapsulated titanium trisulfide (TiS₃) sheets. Through the encapsulation with h-BN, we observe metallic behavior and high electron mobilities. Below ∼60 K an increase in the resistance, and non-linear transport with plateau-like features in the differential resistance are present, in line with the expected charge density wave (CDW) formation. Importantly, the critical temperature and the threshold field of the CDW phase can be controlled through the back-gate.

TiS₃ nanosheets have proven to be promising candidates for ultrathin optoelectronic devices due to their direct narrow band-gap and the strong light-matter interaction. In addition, the marked in-plane anisotropy of TiS₃ is appealing for the fabrication of polarization sensitive optoelectronic devices. Herein, we study the optical contrast of TiS₃ nanosheets of variable thickness on SiO₂/Si substrates, from which we obtain the complex refractive index in the visible spectrum. We find that TiS₃ exhibits very large birefringence, larger than that of well-known strong birefringent materials like TiO₂ or calcite, and linear dichroism. These findings are in qualitative agreement with ab initio calculations that suggest an excitonic origin for the birefringence and linear dichroism of the material.

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.

In the framework of the European Cooperation in Science and Technology (COST) Action MP1103 Nanostructured Materials for Solid-State Hydrogen Storage were synthesized, characterized and modeled. This Action dealt with the state of the art of energy storage and set up a competitive and coordinated network capable to define new and unexplored ways for Solid State Hydrogen Storage by innovative and interdisciplinary research within the European Research Area. An important number of new compounds have been synthesized: metal hydrides, complex hydrides, metal halide ammines and amidoboranes. Tuning the structure from bulk to thin film, nanoparticles and nanoconfined composites improved the hydrogen sorption properties and opened the perspective to new technological applications. Direct imaging of the hydrogenation reactions and in situ measurements under operando conditions have been carried out in these studies. Computational screening methods allowed the prediction of suitable compounds for hydrogen storage and the modeling of the hydrogen sorption reactions on mono-, bi-, and three-dimensional systems. This manuscript presents a review of the main achievements of this Action.