Mixology of MA1-x EA x PbI3 Hybrid Perovskites: Phase Transitions, Cation Dynamics, and Photoluminescence.

Mixing molecular cations in hybrid lead halide perovskites is a highly effective approach to enhance the stability and performance of optoelectronic devices based on these compounds. In this work, we prepare and study novel mixed 3D methylammonium (MA)-ethylammonium (EA) MA1-x EA x PbI3 (x < 0.4) hybrid perovskites. We use a suite of different techniques to determine the structural phase diagram, cation dynamics, and photoluminescence properties of these compounds. Upon introduction of EA, we observe a gradual lowering of the phase-transition temperatures, indicating stabilization of the cubic phase. For mixing levels higher than 30%, we obtain a complete suppression of the low-temperature phase transition and formation of a new tetragonal phase with a different symmetry. We use broad-band dielectric spectroscopy to study the dielectric response of the mixed compounds in an extensive frequency range, which allows us to distinguish and characterize three distinct dipolar relaxation processes related to the molecular cation dynamics. We observe that mixing increases the rotation barrier of the MA cations and tunes the dielectric permittivity values. For the highest mixing levels, we observe the signatures of the dipolar glass phase formation. Our findings are supported by density functional theory calculations. Our photoluminescence measurements reveal a small change of the band gap upon mixing, indicating the suitability of these compounds for optoelectronic applications.

0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 Phosphate Composites: Dielectric and Ferroelectric Properties.

Composite materials with 83 wt.% of the 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 distributed in phosphate-bonded ceramics were prepared at three different pressures. A phosphate matrix comprises a mixture of an aluminum phosphate binder and melted periclase, MgO. All samples demonstrate a homogeneous distribution of the ferroelectric perovskite phase and are thermally stable up to 900 K. At higher temperatures, the pyrochlore cubic phase forms. It has been found that the density of the composites non-monotonously depends on the pressure. The dielectric permittivity and losses substantially increase with the density of the samples. The fabricated composites demonstrate diffused ferroelectric-paraelectric transition and prominent piezoelectric properties.

Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites.

Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA1-xDMAxPbBr3 hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr3, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles.

Phase Transitions in the Metastable Perovskite Multiferroics BiCrO3 and BiCr0.9Sc0.1O3: A Comparative Study.

The temperature behavior of the crystal structure as well as dielectric and magnetic properties of the perovskite bismuth chromate ceramics with the 10 mol % Cr3+-to-Sc3+ substitution were studied and compared with those of the unmodified compound. Using a high-pressure synthesis, BiCrO3 and BiCr0.9Sc0.1O3 were obtained as metastable perovskite phases which are monoclinic C2/c with the √6ap × âˆš2ap × âˆš6ap superstructure (where ap is the primitive perovskite unit-cell parameter) under ambient conditions. At room temperature, the unit cell volume of BiCr0.9Sc0.1O3 is ∼1.3% larger than that of BiCrO3. Both perovskites undergo a reversible structural transition into a nonpolar GdFeO3-type phase (orthorhombic Pnma, √2ap × 2ap × âˆš2ap) in the temperature ranges of 410-420 K (BiCrO3) and 470-520 K (BiCr0.9Sc0.1O3) with a relative jump of the primitive perovskite unit cell volume of about -1.6 and -2.0%, respectively. Temperature dependences of the complex dielectric permittivity demonstrate anomalies in the phase transition ranges. The Pnma-to-C2/c crossover in BiCrO3 is accompanied by a decrease in the direct current (dc) conductivity, while in BiCr0.9Sc0.1O3 the conductivity increases. The onset of an antiferromagnetic order in BiCr0.9Sc0.1O3 is observed at the Néel temperature (TN) of about 85 K as compared with TN = 110 K in BiCrO3. In contrast to BiCrO3, which exhibits a spin reorientation at Tsr ∼ 72 K, no such a transition occurs in BiCr0.9Sc0.1O3.

Dielectric Spectroscopy of Water Dynamics in Functionalized UiO-66 Metal-Organic Frameworks.

We present a dielectric spectroscopy study of dipolar dynamics in the hydrated UiO-66(Zr) type metal-organic frameworks (MOFs) functionalized with -NH2 and -F groups. Experiments are performed in a broad temperature and frequency ranges allowing us to probe several dipolar relaxations. For both samples at temperature below 220 K, we observe confined supercooled water dynamics, which can be described by the Arrhenius law. At slightly higher temperature, a second less pronounced dipolar relaxation is identified, and its origin is discussed. At even higher temperature, the dielectric permittivity exhibits anomalous increase with increasing temperature due to the proton conductivity. Upon further heating, the permittivity shows a sudden decrease indicating a reversible removal of water molecules. Measurements of the dehydrated samples reveal absence of all three dipolar processes.

Broad-band measurements of dielectric permittivity in coaxial line using partially filled circular waveguide.

The full-wave analysis was applied for a coaxial line (i.e., transmission line) that has a "short-circuited" discontinuity. The discontinuity has a radius less than or equal to the inner radius of the coaxial line. The "sample region" can be considered as a partially filled circular waveguide. Such a structure is very practical and is of particular interest for the dielectric spectroscopy applications. It takes into account the inhomogeneous field distribution, which is the limiting factor for the determination of high dielectric permittivity values at microwave frequencies. The direct problem was solved by using the mode-matching technique, and the relationship between the complex reflection coefficient and the dielectric permittivity of the cylindrical sample was obtained. By solving the inverse problem, it is possible to obtain the complex dielectric permittivity from the experimental values of the scattering matrix. The results were verified by the finite element modeling of the system and applied for particular materials. The correspondence between these approaches is excellent. This method is very suitable for the determination of permittivity, which exceeds several thousands (it is applicable for any type of material). It extends the frequency range where the permittivity can be determined reliably. There is no necessity to prepare samples with different geometries (i.e., surface area and thickness).

Temperature-Induced Structural Transformations in Undoped and Eu3+-Doped Ruddlesden-Popper Phases Sr2SnO4 and Sr3Sn2O7: Relation to the Impedance and Luminescence Behaviors.

We report that luminescence of Eu3+ ion incorporated into Ruddlesden-Popper phases allows monitoring phase transition in powders (instead of single crystals), in a time-efficient manner (compared to neutron diffraction), and importantly, with greater sensitivity than previous methods. Crystal structure and dielectric response of undoped and 0.5%Eu3+-doped Sr3Sn2O7 ceramics were studied as a function of temperature over the temperature range of 300-800 K. The luminescence studies of 0.5%Eu3+-doped Sr2SnO4 and Sr3Sn2O7 samples were performed in the temperature range of 80-500 K. These results were compared with the respective dependences for the undoped compounds. The structural transformations in 0.5%Eu3+-doped Sr3Sn2O7 were found at 390 and 740 K. The former is associated with the isostructural atomic rearrangement that resulted in a negative thermal expansion along two of three orthorhombic crystallographic axes, while the latter corresponds to the structural transition from the orthorhombic Amam phase to the tetragonal I4/mmm one. A similar temperature behavior with the structural transformations in the same temperature ranges was observed in undoped Sr3Sn2O7, although the values of lattice parameters of the Eu3+-doped and undoped compounds were found to be slightly different indicating an incorporation of europium in the crystal lattice. A dielectric anomaly associated with a structural phase transition was observed in Sr3Sn2O7 at 390 K. Optical measurements performed over a wide temperature range demonstrated a clear correlation between structural transformations in Eu3+-doped Sr2SnO4 and Sr3Sn2O7 and the temperature anomalies of their luminescence spectra, suggesting the efficacy of this method for the determination of subtle phase transformations.

Coexistence of ferroelectric and relaxor states in Ba2PrxNd1-xFeNb4O15.

We have investigated the dielectric response of Ba(2)Pr(x)Nd(1-x)FeNb(4)O(15) ceramics (x = 0, 0.2, 0.5, 0.6, 0.8, 1) in the frequency range from 20 Hz to 1 GHz. The obtained results confirmed the continuous transformation from the ferroelectric behavior of Ba2NdFeNb4O15 to the pure relaxor response of Ba(2)PrFeNb(4)O(15) with increasing x. For intermediate x values, coexisting ferroelectric transition and relaxor dielectric signatures were observed, corresponding to two different phenomena in the framework of these materials. Increasing the amount of Pr decreases the ferroelectric phase transition temperatures in these ceramics; a large cooling¿heating hysteresis exceeding 50K was also observed.

Dielectric investigations and theoretical calculations of size effect in lead titanate nanocrystals.

The dielectric properties of nanograin ferroelectric lead titanate crystals are presented. The PbTiO3 samples were prepared by pressing nanopowders into plates and were studied experimentally by dielectric permittivity measurements in a wide frequency and temperature range. The TC dependence obtained showed a critical change of behavior with increasing mean nanoparticle size in the 9-nm region. The theoretical calculations based on Monte Carlo simulation were performed to describe the behavior of this material. It was shown that the distribution of nanoparticle sizes in the sample taken into account with the Monte Carlo method describes the dielectric properties of PbTiO3 nanocrystals quite well.