The first-principles and BTE investigation of phonon transport in 1T-TiSe₂

Through the first-principles density functional theory and the phonon Boltzmann transport equation, we investigated the phonon transport characteristics inside 1T-TiSe2. The calculation results of the lattice thermal conductivity (κl) show that the κl of TiSe2 is extremely low (1.28 W (m K)-1, 300 K) and decreases with the shrinkage of the sample size. Moreover, the results also prove the isotropic nature of thermal transport. By decomposing the contribution of the thermal conductivity according to the frequency, the κl of the single-layer TiSe2 is primarily attributed to the acoustic phonons and a small portion of optical phonons, with the frequency range of 0-4.5 THz. The calculation of the scattering rate further illustrates the competition of different scattering modes in this frequency range to verify the change in thermal conductivity of different sample sizes. The high scattering rate and low group velocity lead to the low thermal conductivity of the optical phonon mode in TiSe2. In addition, reducing the size of the system can significantly limit the thermal conductivity by eliminating the contribution of long mean free path phonons. When the characteristic length of the single-layer TiSe2 is about 14.92 nm, κl reduces to half. Our results also show that TiSe2 has an extremely high Grüneisen parameter (about 2.62). Further decomposition of the three-phonon scattering phase space and scattering rate demonstrates that in the range 0-4.5 THz, the absorption process is the main conversion form of phonons. We conclude that, due to the high Grüneisen parameter, the high anharmonicity in TiSe2 leads to the extremely low κl. This study provides κl related to the temperature, frequency, and MFP, and deeply discusses the phonon transport in TiSe2, which has great significance to further adjust the thermal conductivity to develop highly efficient thermoelectric materials and promote the application of devices based on TiSe2.