Phase Transition across Anisotropic NbS3 and Direct Gap Semiconductor TiS3 at Nominal Titanium Alloying Limit.

Abstract

Alloying selected layered transitional metal trichalcogenides (TMTCs) with unique chain-like structures offers the opportunities for structural, optical, and electrical engineering thus expands the regime of this class of pseudo-one-dimensional materials. Here, the novel phase transition in anisotropic Nb(1- x ) Tix S3 alloys is demonstrated for the first time. Results show that Nb(1- x ) Tix S3 can be fully alloyed across the entire composition range from triclinic-phase NbS3 to monoclinic-phase TiS3 . Surprisingly, incorporation of a small concentration of Ti (x ≈ 0.05-0.18) into NbS3 host matrix is sufficient to induce triclinic to monoclinic transition. Theoretical studies suggest that Ti atoms effectively introduce hole doping, thus rapidly decreases the total energy of monoclinic phase and induces the phase transition. When alloyed, crystalline and optical anisotropy are largely preserved as evidenced by high resolution transmission electron microscopy and angle-resolved Raman spectroscopy. Further Raman measurements identify Raman modes to determine crystalline anisotropy direction and offer insights into the degree of anisotropy. Overall results introduce Nb(1- x ) Tix S3 as a new and easy phase change material and mark the first phase engineering in anisotropic van der Waals (vdW) trichalcogenide systems for their potential applications in two-dimensional superconductivity, electronics, photonics, and information technologies.