The temperature dependence (15±293 K) of the six Raman-active mode frequencies and linewitdhs in gallium sul®de has been measured in the frequency range from 15 to 380 cm 21. We observed softening and broadening of the optical phonon lines with increasing temperature. Comparison between the experimental data and theories of the shift and broadening of the interlayer and intralayer phonon lines during the heating of the crystal showed that the experimental dependencies can be explained by the contributions from thermal expansion and lattice anharmonicity. The pure-temperature contribution (phonon± phonon coupling) is due to three-and four-phonon processes. q

TlInS 2 single crystals are studied through the conductivity and Hall effect measurements in the temperature regions of 100-400 and 170-400 K, respectively. An anomalous behavior of Hall voltage, which changes sign below 315 K, is interpreted through the existence of deep donor impurity levels that behave as acceptor levels when are empty. The hole and electron mobility are limited by the hole-and electron-phonon short range interactions scattering above and below 315 K, respectively. An energy level of 35 meV and a set of donor energy levels located at 360, 280, 220 and 170/152 meV are determined from the temperature dependencies of the carrier concentration and conductivity. A hole, electron, hole-electron pair effective masses of 0.24 m o , 0.14 m o and 0.09 m o and hole-and electron-phonon coupling constants of 0.50 and 0.64, respectively, are obtained from the Hall effect measurements. The theoretical fit of the Hall coefficient reveals a hole to electron mobility ratio of 0.8.

Low temperature photoluminescence of GaS single crystals shows three broad emission bands below 2.4 eV. Temperature and excitation light intensity dependencies of these bands reveal that all of them originate from close donor-acceptor pair recombination processes. Temperature dependence of the peak energies of two of these bands in the visible range follow, as expected, the band gap energy shift of GaS. However, the temperature dependence of the peak energy of the third band in the near infrared shows complex behavior by blueshifting at low temperatures followed by a redshift at intermediate temperatures and a second blueshift close to room temperature, which could only be explained via a configuration coordinate model. A simple model calculation indicates that the recombination centers are most likely located at the nearest neighbor lattice or interstitial sites.

The polarization properties of bands in Raman scattering and IR reflection spectra are studied experimentally in TlGaS2, TlGaSe2, and TlInS2 layer single crystals and in solid solutions based on them. Additionally the angular dependence of IR‐active modes on the angle between the phonon wave vector and the direction of the optical axis c of single crystals is investigated. It is shown that the observed phonon spectra can be interpreted on the basis of a primitive cell which contains two tetragonal‐symmetry layers bonded to each other by an inversion operation. Bands corresponding to cells with a mixed composition are observed in the Raman spectra of the solid solutions.

Photoluminescence (PL) spectra of TlInS2 layered single crystals were investigated in the 500-860 nm wavelength region and in the 11.5-100 K temperature range. We observed two PL bands centred at 515 nm (2.41 eV, A band) and 816 nm (1.52 eV, B band) at T = 11.5 K and an excitation intensity of 7.24 W cm−2. A detailed study of the A band was carried out as a function of temperature and excitation laser intensity. A red shift of the A band position was observed for both increasing temperature and decreasing excitation laser intensity in the range from 0.12 to 7.24 W cm −2. Analysis of the data indicates that the A band is due to radiative transitions from the moderately deep donor level located at 0.25 eV below the bottom of the conduction band to the shallow acceptor level located at 0.02 eV above the top of the valence band. An energy-level diagram for radiative donor-acceptor pair transitions in TlInS2 layered single crystals is proposed.