Effects of Synthesis and Processing on Optoelectronic Properties of Titanium Carbonitride MXene

MXenes, a relatively new class of two-dimensional (2D) transition-metal carbides, carbonitrides, and nitrides, exhibit unique properties such as high electronic conductivity, a wide range of optical characteristics, hydrophilicity, and mechanical stability. Because of the high electronic conductivity, MXenes have shown promise in many applications, such as energy storage, electromagnetic interference shielding, antennas, and transparent coatings. 2D titanium carbide (Ti₃C₂T_x, where T_x represents surface terminations), the first discovered and most studied MXene, has the highest electronic conductivity exceeding 10 000 S cm^–1. There have been several efforts to alter the conductivity of MXenes, such as manipulation of the transition-metal layer and control of surface terminations. However, the impact of the C and N site composition on electronic transport has not been explored. In this study, the effects of synthesis methods on optoelectronic properties of 2D titanium carbonitride, Ti₃CNT_x, were systematically investigated. We show that Ti₃CNT_x, which hosts a mix of carbon and nitrogen atoms in the X layer, has lower electronic conductivity and a blue shift of the main absorption feature within the UV–visible spectrum, compared to Ti₃C₂T_x. Moreover, intercalants such as water and tetraalkylammonium hydroxides decrease the electronic conductivity of MXene due to increased interflake resistance, leading to an increase in resistivity with decreasing temperature as observed in ensemble transport measurements. When the intercalants are removed, Ti₃CNT_x exhibits its intrinsic metallic behavior in good agreement with Hall measurements and transport properties measured on single-flake field-effect transistor devices. Finally, the dependence of conductivity of Ti₃CNT_x on the presence of intercalants opens wide opportunities for creating MXene-based materials with tunable electronic properties.