Anomalous isoelectronic chalcogen rejection in 2D anisotropic vdW TiS_3(1-x)Se_3x trichalcogenides

Alloying in semiconductors has enabled many civilian technologies in electronics, optoelectronics, photonics, and others. While the alloying phenomenon is well established in traditional bulk semiconductors owing to a vast array of available ternary phase diagrams, alloying in 2D materials still remains at its seminal stages. This is especially true for transition metal trichalcogenides (TMTCs) such as TiS3 which has been recently predicted to be a direct gap, high carrier mobility, pseudo-1D semiconductor. In this work, we report on an unusual alloying rejection behavior in TiS3(1-x)Se3x vdW crystals. TEM, SEM, EDS, and angle-resolved Raman measurements show that only a miniscule amount (8%) of selenium can be successfully alloyed into a TiS3 host matrix despite vastly different precursor amounts as well as growth temperatures. This unusual behavior contrasts with other vdW systems such as TiS2(1-x)Se2x, MoS2(1-x)Se2x, Mo1-xWxS2, WS2(1-x)Se2x, where continuous alloying can be attained. Angle-resolved Raman and kelvin probe force microscopy measurements offer insights into how selenium alloying influences in-plane structural anisotropy as well as electron affinity values of exfoliated sheets. Our cluster expansion theory calculations show that only the alloys with a small amount of Se can be attained due to energetic instability above/below a certain selenium concentration threshold in the ternary phase diagrams. The overall findings highlight potential challenges in achieving stable Ti based TMTCs alloys.