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Sodium intercalated manganese thiophosphate Na0.62Mn0.69PS3 powders have been synthesized by a two-step ion-exchange process. Dielectric measurements have been performed as a function of both temperature and frequency on the prepared samples in the 20–106 Hz frequency range over the 78–350 K temperature range by using the autobalancing bridge method. The temperature dependence of the dielectric constant imaginary part reveals the presence of a loss peak at the low temperatures together with a strong dispersion at the low frequencies and at the highest investigated temperatures. While the loss peak presence is characteristic for dipolar polarization processes, the strong low frequency dispersion at not very high temperatures, observed also in the dielectric constant real part, is typical for system with hopping charge carriers. A hypothesis about the nature of such carriers has been formulated on the basis of both the ion-exchange intercalation process and the comparison with the dielectric spectra previously observed for cesium intercalated manganese thiophosphate Cs0.46Mn0.77PS3 compounds. [ABSTRACT FROM AUTHOR]

Polycrystalline powders of Na2xMn1-xPS3 have been synthesized from layered MnPS3 material by successive ion-exchange intercalation of potassium and sodium ions. Their x-ray photoelectron spectroscopy (XPS) and x-ray excited Auger spectroscopy spectra have been measured at room temperature using Mg Kα (1253.6 eV) x-ray source. In particular, the Mn, P, and S 2p and Na 1s and 2p core-level regions and the Na Auger KL23L23 transition have been investigated. All the analyzed XPS core-level spectra display a single-peak structure, suggesting the absence of nonequivalent atoms of Na, Mn, P, and S. The manganese XPS spectrum shows, as observed in MnPS3 and in its cesium and potassium intercalation compounds, typical shake-up satellites, suggesting that the Mn–S bond is yet mainly ionic in nature. The comparison with the XPS spectra relative to MnPS3 and its potassium intercalation compound (K2xMn1-xPS3) does not emphasize any relevant difference in the binding energy positions of the investigated core levels, indicating that sodium ion intercalation process does not alter the electronic properties of pure host matrix. Moreover, Na 2p core levels are discrete and well localized in agreement with the hypothesis of a weak link between the guest (the Na+ ions) and the host lattice (the negatively charged Mn1-xPS3 sheets). Such a hypothesis finds confirmation by the calculation of the Na modified Auger parameter. [ABSTRACT FROM AUTHOR]

Cesium ions have been intercalated by ion exchange into layered manganese thiophosphate to produce Cs2xMn1-xPS3. Investigations have been conducted by x-ray diffraction analysis, IR absorption spectroscopy, x-ray photoemission spectroscopy (XPS), and dielectric spectroscopy. The XPS spectra, recorded at room temperature and at the Mn, P, and S 2p, Mn 3p, and Cs 3d and 4d core-level regions, indicate that no charge transfer occurs from guest species (Cs+) to pure host lattice (MnPS3). The presence of shake-up satellites at the Mn 2p and 3p core levels suggests that the cesium intercalation does not alter the nature of the Mn–S bond which is mostly ionic. Dielectric measurements, carried out between 260 and 375 K and in the 20 Hz–1 MHz frequency range, classify Cs2xMn1-xPS3 as hopping charge carrier systems. The nature of such carriers can be hypothesized on the basis of both the intercalation process by cationic substitution and the comparison with the observed dielectric response of the pure MnPS3. [ABSTRACT FROM AUTHOR]