Estudo das propriedades vibracionais das perovskitas híbridas de azida

Abstract

Recently, perovskite-type organic-inorganic hybrid compounds have attracted considerable interest due to their structural versatility, which allows for the manifestation of various interesting physical properties for application in devices. These materials exhibit a wide range of functionalities, including photovoltaic, ferroelectric, and multiferroic properties. In this thesis, we used the slow evaporation method to obtain three perovskite-type hybrid compounds, [(CH3)3N][Mn(N3)3] (TrMAMnN3), [(CH3)2NH][Mn(N3)3] (DMAMnN3), [(CH3)2NH]2[CoNa(N3)6], whose structural, thermal, and vibrational properties were investigated as a function of temperature. In the case of the compound [(CH3)3NH][Mn(N3)3], we analyzed in detail the wavenumber and full-width half-height (FWHM) of lattice modes and internal modes of the NC3 skeleton, N3– and CH3 molecular groups. In general, the modes exhibited unusual behavior during phase transitions, including discontinuity in phonon wavenumber, bandwidth, and unconventional changes due to temperature variation. Furthermore, we used differential scanning calorimetry (DSC) to confirm a subtle monoclinic-to-monoclinic phase transition (P21/c →C2/c) around 330 K; and the phase transition to trigonal structure (R m) above 359 K, whose associated entropy variation becomes |ΔS| ~ 22.3 J·kg⁻¹ K⁻¹ and exhibits a barocaloric coefficient (BC) |δTt/δP| ~ 3.17 K kbar⁻¹. For DMAMnN₃, a first-order structural transition from the orthorhombic phase (Cmca) to the monoclinic phase (P2₁) was identified, with an entropy variation of ~37.2 J·kg⁻¹·K⁻¹ and a barocaloric coefficient of ~2.94 K·kbar⁻¹, in agreement with the Clausius-Clapeyron method. Room-temperature Fourier transform infrared (FTIR) reflectivity spectra identified polar phonons and their damping coefficients. Minimal contributions from the DMA+ mode were observed in the intrinsic dielectric constant (~4.3). An anomaly was observed at ~85 K, indicating a transition from the paramagnetic to the antiferromagnetic state (PM-AFM). Finally, we present a new compound obtained through the slow evaporation synthesis [(CH3)2NH]2[CoNa(N3)6], where single-crystal XRD measurements resolved the material's structure, showing that up to 100 K the structure does not exhibit a structural phase transition. A room-temperature Raman spectrum was also obtained, and mode assignment was performed.