TiSe2

TiSe2 has received much attention among the transition metals chalcogenides because of its thrilling physical properties concerning atypical resistivity behavior, emerging of charge density wave (CDW) state, induced superconductivity etc. Here, we report discovery of new feature of TiSe2, namely, observation of resistive switching in voltage biased point contacts (PCs) based on TiSe2 and its derivatives doped by S and Cu (TiSeS, CuxTiSe2). The switching is taking place between a low resistive mainly metallic-type state and a high resistive semiconducting-type state by applying bias voltage (usually below 0.5V), while reverse switching takes place by applying voltage of opposite polarity (usually below 0.5V). The difference in resistance between these two states can reach up to two orders of magnitude at the room temperature. The origin of the effect can be attributed to the variation of stoichiometry in PC core due to drift/displacement of Se/Ti vacancies under high electric field. Additionally, we demonstrated, that heating takes place in PC core, which can facilitate the electric field induced effect. At the same time, we did not found any evidence for CDW spectral features in our PC spectra for TiSe2. The observed resistive switching allows to propose TiSe2 and their derivatives as the promising materials, e.g., for non-volatile resistive random access memory (ReRAM) engineering.

Published in: "arXiv Material Science".

TiSe2 is a known Topological semimetal (TSM) having both the semi-metallic and topological characters simultaneously and the Charge density wave (CDW) at below 200K. In the current short article, we study the impact of Pd addition on the CDW character of TiSe2 and the possible induction of superconductivity at low temperatures. Bulk samples of TiSe2 and Pd0.1TiSe2 are synthesized by solid-state reaction route, which is further characterized by powder X-ray diffraction (PXRD) and field emission scanning electron microscopy (FESEM), respectively, for their structural and micro-structural details. The vibrational modes of both samples are being analyzed by Raman spectroscopy, showing the occurrence of both A1g and Eg modes. CDW of pure TiSe2 seen at around 200K in electrical transport measurements, in terms of sharp semi-metallic to metallic transition peak with hysteresis in cooling/warming cycles is not seen in Pd0.1TiSe2, and rather a near metallic transport is seen down to 2K. Although superconductivity is not seen down to 2K, the CDW transition is seemingly completely suppressed in Pd0.1TiSe2. Pd addition in TiSe2 suppresses CDW drastically. Trials are underway to induce superconductivity in Pd-added TiSe2. Density functional theory (DFT) calculations show primary evidence of suppression of CDW by adding Pd in TiSe2 due to an increase in the density of states.

Published in: "arXiv Material Science".

Femtosecond core-level transient absorption spectroscopy is utilized to investigate photoinduced dynamics of the charge density wave in 1T-TiSe2 at the Ti M2,3 edge (30-50 eV). Photoexcited carriers and phonons are found to primarily induce spectral red-shifts of core-level excitations, and a carrier relaxation time and phonon heating time of approximately 360 fs and 1.0 ps are extracted, respectively. Pronounced oscillations in delay-dependent absorption spectra are assigned to coherent excitations of the optical $A_{1g}$ phonon (6.0 THz) and the $A_{1g}^*$ charge density wave amplitude mode (3.3 THz). By comparing the measured spectra with time-dependent density functional theory simulations, we determine the directions of the momentary atomic displacements of both coherent modes and estimate their amplitudes. This work presents a first look on charge density wave excitations with table-top core-level transient absorption spectroscopy, enabling simultaneous access to electronic and lattice excitation and relaxation.

Published in: "arXiv Material Science".

The doping of correlated materials with various atomic and molecular species is a staple in the tuning and understanding of their electronic ground states and in the engineering of exotic quantum phenomena. In particular, the recent discovery of near-to-room temperature superconductivity in hydrides under pressure has highlighted the potential of hydrogen as a dopant and to tune the electronic and the phononic spectra of a material. Here, we demonstrate the non-volatile control of the electronic ground state of octahedral titanium diselenide (1T-TiSe$_2$) by means of electric field-driven hydrogen intercalation via the ionic liquid gating method. We show that in H$_x$TiSe$_2$ charge-density waves and superconductivity coexist through most of the phase diagram, with nearly doping-independent transition temperatures. The superconducting phase of H$_x$TiSe$_2$ is gapless-like and possibly multi-band in nature, setting it apart from what observed in TiSe$_2$ via electrostatic gating and copper- or lithium- intercalation. The uniqueness of hydrogen doping is supported by ab initio calculations showing that its impact is not limited to a rigid electron doping of pristine TiSe$_2$, but it can attain a full reconstruction of the band structure. These findings open a new route towards high-temperature superconductivity in hydrogen-rich layered compounds at ambient pressure.

Published in: "arXiv Material Science".

Charge density wave (CDW) materials can undergo an ultrafast phase transition after an ultrashort laser pulse excitation, and the suggested underlying mechanisms have always been associated with two main features: excitonic interaction-induced CDW charge order and electron-phonon coupling-induced periodic lattice distortion (PLD). Here, beyond these two mechanisms, we reveal that photoexcitation induced CDW phase transition in the prototypic CDW example 1T-TiSe2 is similar to a puppet on a string: six Ti-Se bonds connected to each distorted Ti atom acting as six strings controlling the PLD and in turn the CDW orders. The photoexcitation induced modulation on charge population of the Ti-Se bonds generates a laser-fluence-dependent interatomic-repulsive force along each Ti-Se bond. The nonequal length of these six Ti-Se bonds gives rise to a net force exerted on the central distorted Ti atom to push it toward the suppressing of the PLD and thus the CDW orders. We further illustrate that the dynamics of each distorted Ti atom behaves as though it attached to a spring in a simple harmonic motion with a fluence-dependent oscillation frequency, uniting two previously reported scaling laws for phase transition time. These findings significantly advance the understanding of CDW instability and provide new insights into how photoexcitation induced modulation on charge population may lead to phase transitions by directly connecting interatomic forces with reaction pathways.

Published in: "arXiv Material Science".

Besides magnetic and charge order, regular arrangements of orbital occupation constitute a fundamental order parameter of condensed matter physics. Even though orbital order is difficult to identify directly in experiments, its presence was firmly established in a number of strongly correlated, three-dimensional Mott insulators. Here, reporting resonant X-ray scattering experiments on the layered Van der Waals compound $1T$-TiSe$_2$, we establish the emergence of orbital order in a weakly correlated, quasi-two-dimensional material. Our experimental scattering results are consistent with first-principles calculations that bring to the fore a generic mechanism of close interplay between charge redistribution, lattice displacements, and orbital order. It demonstrates the essential role that orbital degrees of freedom play in TiSe$_2$, and their importance throughout the family of correlated Van der Waals materials.

Published in: "arXiv Material Science".