Phase Transition and Point Defects in the Ferroelectric Molecular Perovskite (MDABCO)(NH4)I3.

We measured the anelastic, dielectric and structural properties of the metal-free molecular perovskite (ABX3) (MDABCO)(NH4)I3, which has already been demonstrated to become ferroelectric below TC= 448 K. Both the dielectric permittivity measured in air on discs pressed from powder and the complex Young's modulus measured on resonating bars in a vacuum show that the material starts to deteriorate with a loss of mass just above TC, introducing defects and markedly lowering TC. The elastic modulus softens by 50% when heating through the initial TC, contrary to usual ferroelectrics, which are stiffer in the paraelectric phase. This is indicative of improper ferroelectricity, in which the primary order parameter of the transition is not the electric polarization, but the orientational order of the MDABCO molecules. The degraded material presents thermally activated relaxation peaks in the elastic energy loss, whose intensities increase together with the decrease in TC. The peaks are much broader than pure Debye due to the general loss of crystallinity. This is also apparent from X-ray diffraction, but their relaxation times have parameters typical of point defects. It is argued that the major defects should be of the Schottky type, mainly due to the loss of (MDABCO)2+ and I-, leaving charge neutrality, and possibly (NH4)+ vacancies. The focus is on an anelastic relaxation process peaked around 200 K at ∼1 kHz, whose relaxation time follows the Arrhenius law with τ0 ∼ 10-13 s and E≃0.4 eV. This peak is attributed to I vacancies (VX) hopping around MDABCO vacancies (VA), and its intensity presents a peculiar dependence on the temperature and content of defects. The phenomenology is thoroughly discussed in terms of lattice disorder introduced by defects and partition of VX among sites that are far from and close to the cation vacancies. A method is proposed for calculating the relative concentrations of VX, that are untrapped, paired with VA or forming VX-VA-VX complexes.

Structural Transitions and Stability of FAPbI3 and MAPbI3: The Role of Interstitial Water.

We studied the influence of water on the structural stability and transformations of MAPI and FAPI by anelastic and dielectric spectroscopies under various temperature and H2O partial pressure protocols. Before discussing the new results in terms of interstitial water in MAPI and FAPI, the literature is briefly reviewed, in search of other studies and evidences on interstitial water in hybrid halide perovskites. In hydrated MAPI, the elastic anomaly between the cubic α and tetragonal ß phases may be depressed by more than 50%, demonstrating that there are H2O molecules dispersed in the perovskite lattice in interstitial form, that hinder the long range tilting of the PbI6 octahedra. Instead, in FAPI, interstitial water accelerates in both senses the reconstructive transformations between 3D α and 1D δ phases, which is useful during the crystallization of the α phase. On the other hand, the interstitial H2O molecules increase the effective size of the MA and FA cations to which are bonded, shifting the thermodynamic equilibrium from the compact perovskite structure to the open δ and hydrated phases of loosely bonded chains of PbI6 octahedra. For this reason, when fabricating devices based on hybrid metal-organic halide perovskites, it is important to reduce the content of interstitial water as much as possible before encapsulation.

Stability of Cubic FAPbI3 from X-ray Diffraction, Anelastic, and Dielectric Measurements.

Among the hybrid metal-organic perovskites for photovoltaic applications, FAPbI3 (FAPI) has the best performance regarding efficiency and the worst regarding stability, even though the reports on its stability are highly contradictory. In particular, since at room temperature the cubic α phase, black and with high photovoltaic efficiency, is metastable against the yellow hexagonal δ phase, it is believed that α-FAPI spontaneously transforms into δ-FAPI within a relatively short time. We performed X-ray diffraction and thermogravimetric measurements on loose powder of FAPI, and present the first complete dielectric and anelastic spectra of compacted FAPI samples under various conditions. We found that α-FAPI is perfectly stable for at least 100 days, the duration of the experiments, unless extrinsic factors induce its degradation. In our tests, degradation was detected after exposure to humidity, strongly accelerated by grain boundaries and the presence of δ phase, but it was not noticeable on the loose powder kept in air under normal laboratory illumination. These findings have strong implications on the strategies for improving the stability of FAPI without diminishing its photovoltaic efficiency through modifications of its composition.

Damage from Coexistence of Ferroelectric and Antiferroelectric Domains and Clustering of O Vacancies in PZT: An Elastic and Raman Study.

It is often suggested that oxygen vacancies (V O ) are involved in fatigue and pinning of domain walls in ferroelectric (FE) materials, but generally without definite evidence or models. Here the progress of damage induced by the coexistence of FE and antiferroelectric (AFE) domains in the absence of electric cycling is probed by monitoring the Young's modulus, which may undergo more than fourfold softenings without significant changes in the Raman spectra, but may end with the disaggregation of PZT with ∼5% Ti. At these compositions, the FE and AFE phases coexist at room temperature, as also observed with micro-Raman, and hence the observations are interpreted in terms of the aggregation of V O at the interfaces between FE and AFE domains, which are sources of internal electric and stress fields. The V O would coalesce into planar defects whose extension grows with time but can be dissolved by annealing above 600 K, which indeed restores the original stiffness. The observed giant softening is interpreted by assimilating the planar aggregations of V O to flat inclusions with much reduced elastic moduli, due to the missing Zr/Ti-O bonds. A relationship between the coalescence of a fixed concentration of V O into planar defects and softening is then obtained from the existing literature on the effective elastic moduli of materials with inclusions of various shapes.

Competition between Polar and Antiferrodistortive Modes and Correlated Dynamics of the Methylammonium Molecules in MAPbI3 from Anelastic and Dielectric Measurements.

The mechanisms behind the exceptional photovoltaic properties of the metallorganic perovskites are still debated and include a ferroelectric (FE) state from the ordering of the electric dipoles of the organic molecules. We present the first anelastic (complex Young's modulus) and new dielectric measurements on CH3NH3PbI3, which provide new insight into the reorientation dynamics of the organic molecules and the reason why they do not form a FE state. The permittivity is fitted within the tetragonal phase with an expression that includes the coupling between FE and octahedral tilt modes, indicating that the coupling is competitive and prevents FE ordering. The onset of the orthorhombic phase is accompanied by sharp stiffening, analogous to the drop of permittivity, due to the hindered molecular dynamics. On further cooling, an intense anelastic relaxation process without a dielectric counterpart suggests the reorientation of clusters of molecules with strong antiferroelectric correlations.

Combined use of Mössbauer spectroscopy, XPS, HRTEM, dielectric and anelastic spectroscopy for estimating incipient phase separation in lead titanate-based multiferroics.

The formation of separate phases in crystalline materials is promoted by doping with elements with different valences and ionic radii. Control of the formation of separate phases in multiferroics is extremely important for their magnetic, ferroelectric and elastic properties, which are relevant for multifunctional applications. The ordering of dopants and incipient phase separation were studied in lead titanate-based multiferroics with the formula (Pb0.88Nd0.08)(Ti0.98-xFexMn0.02)O3 (x = 0.00, 0.03, 0.04, 0.05) by means of a combination of Mössbauer spectroscopy, XPS, HRTEM, dielectric and anelastic spectroscopy. We found that Fe ions are substituted as Fe3+ at Ti sites and preferentially exhibit pentahedral coordination, whereas Ti ions have coexisting valences of Ti4+/Ti3+. Fe3+ ions are preferentially ordered in clusters, and there exists a transition temperature TC1, below which phase separation occurs between a tetragonal phase T1 free of magnetic clusters and a cubic phase, and a lower transition temperature TC2, below which the cubic phase rich in magnetic clusters is transformed into a tetragonal phase T2. The phase separation persists at the nanoscale level down to room temperature and is visible in HRTEM images as a mixing of nanodomains with different tetragonality ratios. This phase separation was observed over the whole studied concentration range of xFe values. It occurs progressively with the value of xFe, and the transition temperature TC2 decreases with the concentration from about 620 K (xFe = 0.03) to about 600 K (xFe = 0.05), while TC1 remains nearly constant.

Elastic Properties and Enhanced Piezoelectric Response at Morphotropic Phase Boundaries.

The search for improved piezoelectric materials is based on the morphotropic phase boundaries (MPB) between ferroelectric phases with different crystal symmetry and available directions for the spontaneous polarization. Such regions of the composition x - T phase diagrams provide the conditions for minimal anisotropy with respect to the direction of the polarization, so that the polarization can easily rotate maintaining a substantial magnitude, while the near verticality of the TMPB(x) boundary extends the temperature range of the resulting enhanced piezoelectricity. Another consequence of the quasi-isotropy of the free energy is a reduction of the domain walls energies, with consequent formation of domain structures down to nanoscale. Disentangling the extrinsic and intrinsic contributions to the piezoelectricity in such conditions requires a high level of sophistication from the techniques and analyses for studying the structural, ferroelectric and dielectric properties. The elastic characterization is extremely useful in clarifying the phenomenology and mechanisms related to ferroelectric MPBs. The relationship between dielectric, elastic and piezoelectric responses is introduced in terms of relaxation of defects with electric dipole and elastic quadrupole, and extended to the response near phase transitions in the framework of the Landau theory. An account is provided of the anelastic experiments, from torsional pendulum to Brillouin scattering, that provided new important information on ferroelectric MPBs, including PZT, PMN-PT, NBT-BT, BCTZ, and KNN-based systems.