Ferroelectricity and Crystal Phases in Mixed‐Cation Lead Iodide Perovskite Solar Cells

After the discovery of ferroelectricity in archetypal methylammonium lead iodide (MAPbI$_3$), the discussion arose, if more advanced derivatives thereof are also ferroelectric and to what extent the polar domains mitigate detrimental charge carrier recombination in perovskite solar cells. Herein, the A-site cation methylammonium is gradually substituted with formamidinium and cesium. The domain contrast measured by piezoresponse force microscopy is correlated with the distortion of the crystal structure measured by X-ray diffraction. By Rietveld analysis, a detailed structural model together with texture information is determinded, which reveals an intriguing interplay between lead iodide and the perovskite phases. Finally, the bearing of ferroelectric domains in mixed-cation perovskites on the solar cell performance is discussed

In situ neutron diffraction for analysing complex coarse-grained functional materials

Complex functional materials play a crucial role in a broad range of energy-related applications and in general for materials science. Revealing the structural mechanisms is challenging due to highly correlated coexisting phases and microstructures, especially for in situ or operando investigations. Since the grain sizes influence the properties, these microstructural features further complicate investigations at synchrotrons due to the limitations of illuminated sample volumes. In this study, it is demonstrated that such complex functional materials with highly correlated coexisting phases can be investigated under in situ conditions with neutron diffraction. For large grain sizes, these experiments are valuable methods to reveal the structural mechanisms. For an example of in situ experiments on barium titanate with an applied electric field, details of the electric-field-induced phase transformation depending on grain size and frequency are revealed. The results uncover the strain mechanisms in barium titanate and elucidate the complex interplay of stresses in relation to grain sizes as well as domain-wall densities and mobilities

Structure and relaxor ferroelectric behavior of the novel tungsten bronze type ceramic Sr5_5BiTi3_3Nb7_7O30_{30}

A novel lead-free tungsten bronze type ceramic Sr5BiTi3Nb7O30, was prepared by a conventional solid-state reaction route. The room-temperature crystal structure shows an average structure with centro-symmetric space group P4/mbm identified by synchrotron XRD. Temperature dependence of dielectric permittivity indicates that Sr5BiTi3Nb7O30 is a ferroelectric relaxor with Tm near 260 K. The ceramic displays stronger frequency dispersion and lower phase-transition temperature compared with Sr6Ti2Nb8O30. A macroscopic and phenomenological statistical model was employed to describe the temperature dependence of their dielectric responses. The calculated size of polar nanoregions (PNRs) of Sr5BiTi3Nb7O30 compared with Sr6Ti2Nb8O30 implies that the stronger diffusion phase transition for the former is related to the disorder emerged in both A and B sites. The smaller PNRs can be activated at lower temperature but have smaller electrical dipole moment. This is the origin of relaxor behavior of Sr5BiTi3Nb7O30 with lower Tm and dielectric permittivity. The PNRs is related to a local structure with a polar space group P4bm, which contributes to the dielectric frequency dispersion of relaxor behavior. This work opens up a promising feasible route to the development of relaxor ferroelectrics in tungsten bronze type oxides

Multi-analyser detector (MAD) for high-resolution and high-energy powder X-ray diffraction

For high-resolution powder diffraction in material science, high photon energies are necessary, especially for in situ and in operando experiments. For this purpose, a multi-analyser detector (MAD) was developed for the high-energy beamline P02.1 at PETRA III of the Deutsches Elektronen-Synchrotron (DESY). In order to be able to adjust the detector for the high photon energies of 60 keV, an individually adjustable analyser–crystal setup was designed. The adjustment is performed via piezo stepper motors for each of the ten channels. The detector shows a low and flat background as well as a high signal-to-noise ratio. A range of standard materials were measured for characterizing the performance. Two exemplary experiments were performed to demonstrate the potential for sophisticated structural analysis with the MAD: (i) the structure of a complex material based on strontium niobate titanate and strontium niobate zirconate was determined and (ii) an in situ stroboscopy experiment with an applied electric field on a highly absorbing piezoceramic was performed. These experiments demonstrate the capabilities of the new MAD, which advances the frontiers of the structural characterization of materials

Stress-modulated relaxor-to-ferroelectric transition in lead-free (Na1/2Bi1/2)TiO3-BaTiO3 ferroelectrics

The effect of external mechanical fields on relaxor 0.94 (Na1/2Bi1/2)TiO3−0.06 BaTiO3 was investigated by means of temperature- and stress-dependent dielectric constant measurements between 223 and 673 K. Analogous to previous investigations that showed an electric-field-induced ferroelectric long-range order in relaxor ferroelectrics, we show that compressive stress can also result in the transition to the long-range ferroelectric order, marked by the formation of an anomaly in the permittivity-temperature curves and a nonlinear, remanent change in permittivity during mechanical loading. In situ stress-dependent high-energy x-ray diffraction experiments were performed at room temperature and reveal an apparent phase transition during mechanical loading, consistent with previous macroscopic electrical measurements. The transition lines between the relaxor states and the stress-induced ferroelectric state were determined at constant temperatures with stress-dependent dielectric constant measurements, providing a stress-temperature phase diagram

Electric-field-induced strain contributions in morphotropic phase boundary composition of (Bi1/2Na1/2)TiO3-BaTiO3 during poling

The microscopic contributions to the electric-field-induced macroscopic strain in a morphotropic 0.93(Bi1/2Na1/2TiO3)-0.07(BaTiO3) with a mixed rhombohedral and tetragonal structure have been quantified using full pattern Rietveld refinement of in situ high-energy x-ray diffraction data. The analysis methodology allows a quantification of all strain mechanisms for each phase in a morphotropic composition and is applicable to use in a wide variety of piezoelectric compositions. It is shown that during the poling of this material 24%, 44%, and 32% of the total macroscopic strain is generated from lattice strain, domain switching, and phase transformation strains, respectively. The results also suggest that the tetragonal phase contributes the most to extrinsic domain switching strain, whereas the lattice strain primarily stems from the rhombohedral phase. The analysis also suggests that almost 32% of the total strain is lost or is a one-time effect due to the irreversible nature of the electric-field-induced phase transformation in the current composition. This information is relevant to on-going compositional development strategies to harness the electric-field-induced phase transformation strain of (Bi1/2Na1/2)TiO3-based lead-free piezoelectric materials for actuator applications. © 2015 AIP Publishing LLCclose0

Electric-field-induced paraelectric to ferroelectric phase transformation in prototypical polycrystalline BaTiO₃

An electric-field-induced paraelectric cubic to ferroelectric tetragonal phase transformation has been directly observed in prototypical polycrystalline BaTiO3 at temperatures above the Curie point (TC) using in situ high-energy synchrotron X-ray diffraction. The transformation persisted to a maximum temperature of 4-°C above TC. The nature of the observed field-induced transformation and the resulting development of domain texture within the induced phase were dependent on the proximity to the transition temperature, corresponding well to previous macroscopic measurements. The transition electric field increased with increasing temperature above TC, while the magnitude of the resultant tetragonal domain texture at the maximum electric field (4-kV mm-1) decreased at higher temperatures. These results provide insights into the phase transformation behavior of a prototypical ferroelectric and have important implications for the development of future large-strain phase-change actuator materials