A new quasi-one-dimensional transition metal chalcogenide semiconductor (Nb$_4$Se$_{15}$I$_2$)I$_2$

TL;DR

This paper reports the synthesis, structural characterization, and electronic properties of a new quasi-one-dimensional transition metal chalcogenide semiconductor, Nb4Se15I2, expanding the family of low-dimensional materials.

Contribution

The study introduces a novel quasi-one-dimensional Nb4Se15I2 compound with detailed structural analysis and electronic characterization, including DFT calculations and resistivity measurements.

Findings

Nb4Se15I2 is a semiconductor with a ~0.6 eV direct band gap.

The material shows no structural phase transition down to 8.2 K.

Resistivity measurements indicate an activation energy of around 0.1 eV.

Abstract

The discovery of new low-dimensional transition metal chalcogenides is contributing to the already prosperous family of these materials. In this study, needle-shaped single crystals of a new quasi-one-dimensional material (Nb$_4$Se$_{15}$I$_2$)I$_2$ were grown by chemical vapor transport, and the structure was solved by single crystal X-ray diffraction (XRD). The new structure has one-dimensional (Nb$_4$Se$_{15}$I$_2$)$_n$ chains along the [101] direction, with two I$^-$ ions per formula unit directly bonded to Nb$^{5+}$. The other two I$^-$ ions are loosely coordinated and intercalate between the chains. Individual chains are chiral, and stack along the $b$ axis in opposing directions, giving space group $P2_1/c$. The phase purity and crystal structure was verified by powder XRD. Density functional theory calculations show (Nb$_4$Se$_{15}$I$_2$)I$_2$ to be a semiconductor with a direct band gap of around 0.6 eV. Resistivity measurements of bulk crystals and micro-patterned devices demonstrate that (Nb$_4$Se$_{15}$I$_2$)I$_2$ has an activation energy of around 0.1 eV, and no anomaly or transition was seen upon cooling. (Nb$_4$Se$_{15}$I$_2$)I$_2$ does not undergo structural phase transformation from room temperature down to 8.2 K, based on cryogenic temperature single crystal XRD. This compound represents a well-characterized and valence-precise member of a diverse family of anisotropic transition metal chalcogenides.