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Halide perovskite (HaP) semiconductors are revolutionizing photovoltaic (PV) solar energy conversion by showing remarkable performance of solar cells made with HaPs, especially tetragonal methylammonium lead triiodide (MAPbI 3 ). In particular, the low voltage loss of these cells implies a remarkably low recombination rate of photogenerated carriers. It was suggested that low recombination can be due to the spatial separation of electrons and holes, a possibility if MAPbI 3 is a semiconducting ferroelectric, which, however, requires clear experimental evidence. As a first step, we show that, in operando, MAPbI 3 (unlike MAPbBr 3 ) is pyroelectric, which implies it can be ferroelectric. The next step, proving it is (not) ferroelectric, is challenging, because of the material's relatively high electrical conductance (a consequence of an optical band gap suitable for PV conversion) and low stability under high applied bias voltage. This excludes normal measurements of a ferroelectric hysteresis loop, to prove ferroelectricity's hallmark switchable polarization. By adopting an approach suitable for electrically leaky materials as MAPbI 3 , we show here ferroelectric hysteresis from well-characterized single crystals at low temperature (still within the tetragonal phase, which is stable at room temperature). By chemical etching, we also can image the structural fingerprint for ferroelectricity, polar domains, periodically stacked along the polar axis of the crystal, which, as predicted by theory, scale with the overall crystal size. We also succeeded in detecting clear second harmonic generation, direct evidence for the material's noncentrosymmetry. We note that the material's ferroelectric nature, can, but need not be important in a PV cell at room temperature., Competing Interests: The authors declare no conflict of interest.

Materials are central to our way of life and future. Energy and materials as resources are connected, and the obvious connections between them are the energy cost of materials and the materials cost of energy. For both of these, resilience of the materials is critical; thus, a major goal of future chemistry should be to find materials for energy that can last longer, that is, design principles for self-repair in these.

The riddle of anomalous polar behavior of the centrosymmetric crystal of α-glycine is resolved by the discovery of a polar, several hundred nanometer thick hydrated layer, created at the {010} faces during crystal growth. This layer was detected by two independent pyroelectric analytical methods: (i) periodic temperature change technique (Chynoweth) at ambient conditions and (ii) contactless X-ray photoelectron spectroscopy under ultrahigh vacuum. The total polarization of the surface layer is extremely large, yielding ≈1 μC·cm -2 , and is preserved in ultrahigh vacuum, but disappears upon heating to 100 °C. Molecular dynamics simulations corroborate the formation of polar hydrated layers at the sub-microsecond time scale, however with a thickness of only several nanometers, not several hundred. This inconsistency might be reconciled by invoking a three-step nonclassical crystal growth mechanism comprising (i) docking of clusters from the supersaturated solution onto the evolving crystal, (ii) surface recognition and polar induction, and (iii) annealing and dehydration, followed by site-selective recrystallization.

The validity and limitations of two quantitative approaches for estimating the height of the potential barrier at grain boundaries, Ψgb, in polycrystalline ionic conductors are examined both theoretically and experimentally. The linear diffusion model recently proposed by Kim and Lubomirsky determines Ψgb from the value of the power exponent of the current (Igb)-voltage (Ugb) relationship at the grain boundary, dln(Igb)/dln(Ugb), while the conventional approach calculates Ψgb from the ratio of the grain boundary resistivity to the grain core resistivity. The results of our theoretical analysis demonstrate that both approaches should yield consistent values for Ψgb if the ionic current through the grain boundary is limited exclusively by space charge. While the value of Ψgb obtained by the power law procedure is relatively insensitive to other causes of current obstruction, e.g. current constriction and/or local structural disorder, the resistivity ratio method, if not explicitly corrected for these additional limitations, results in a considerable overestimate of the grain boundary potential barrier. Hence, it is possible to distinguish between grain boundary resistance due to the presence of space charge and that due to additional sources by comparing the values of Ψgb determined using each of the two methods. Our theoretical analysis is confirmed experimentally with 3 mol% Gd-doped ceria with and without an additional source of current constriction across the grain boundary.

Polar crystals, which display pyroelectricity, have a propensity to elevate, in a heterogeneous nucleation, without epitaxy, the freezing temperature of supercooled water (SCW). Upon cooling, such crystals accumulate an electric charge at their surfaces, which creates weak electric fields,

Young's moduli of selected amino acid molecular crystals were studied both experimentally and computationally using nanoindentation and dispersion-corrected density functional theory. The Young modulus is found to be strongly facet-dependent, with some facets exhibiting exceptionally high values (as large as 44 GPa). The magnitude of Young's modulus is strongly correlated with the relative orientation between the underlying hydrogen-bonding network and the measured facet. Furthermore, we show computationally that the Young modulus can be as large as 70-90 GPa if facets perpendicular to the primary direction of the hydrogen-bonding network can be stabilized. This value is remarkably high for a molecular solid and suggests the design of hydrogen-bond networks as a route for rational design of ultra-stiff molecular solids., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The conclusions reached by a diverse group of scientists who attended an intense 2-day workshop on hybrid organic-inorganic perovskites are presented, including their thoughts on the most burning fundamental and practical questions regarding this unique class of materials, and their suggestions on various approaches to resolve these issues., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We demonstrate the applicability of the linear diffusion model recently proposed for the current-voltage, Igb-Ugb, characteristics of blocking grain boundaries in solid electrolytes to various oxygen-ion and proton conductors: the model precisely reproduces the Igb-Ugb characteristics of La-, Sm-, Gd-, and Y-doped ceria as well as Y-doped barium zirconate to provide accurate explanations to the "power law" behavior of the Igb-Ugb relationship, i.e. Igb ∝ Ugb(n), experimentally observed. The model also predicts that the grain-boundary potential, Ψgb, in doped ceria weakly depends on temperature, if the trapped charge remains constant, and that the value of Ψgb can be determined from the value of the power n. Furthermore, the model provides a plausible explanation for the increase in the Ψgb with temperature observed for the proton conductor in which the concentration of the charge carrier decreases with temperature. Hence, it is evident that the linear diffusion model is robust and applicable to grain boundaries in a large variety of practically important solid electrolytes.

A new model based on a linear diffusion equation is proposed to explain the current-voltage characteristics of blocking grain boundaries in Y-doped CeO2 in particular. One can also expect that the model can be applicable to the ionic conductors with blocking grain boundaries, in general. The model considers an infinitely long chain of identical grains separated by grain boundaries, which are treated as regions in which depletion layers of mobile ions are formed due to trapping of immobile charges that do not depend on the applied voltage as well as temperature. The model assumes that (1) the grain boundaries do not represent physical blocking layers, which implies that if there is a second phase at the grain boundaries, then it is too thin to impede ion diffusion and (2) the ions follow Boltzmann distribution throughout the materials. Despite its simplicity, the model successfully reproduces the "power law": current proportional to voltage power n and illustrated with the experimental example of Y-doped ceria. The model also correctly predicts that the product nT, where T is the temperature in K, is constant and is proportional to the grain boundary potential as long as the charge at the grain boundaries remains trapped. The latter allows its direct determination from the current-voltage characteristics and promises considerable simplification in the analysis of the electrical characteristics of the grain boundaries with respect to the models currently in use.

Gd-doped CeO(2) exhibits an anomalously large electrostriction effect generating stress that can reach 500 MPa. In situ XANES measurements indicate that the stress develops in response to the rearrangement of cerium-oxygen vacancy pairs. This mechanism is fundamentally different from that of materials currently in use and suggests that Gd-doped ceria is a representative of a new family of high-performance electromechanical materials., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Dr Williams (AIP Adv., 2012, 2, 010701) suggested that cleaning Teflon by high pressure oxygen plasma may have affected our result that Cu(2+) and Pd(2+) ions can be absorbed but not chemically reduced by a Teflon surface rubbed by PMMA (Phys. Chem. Chem. Phys., 2012, 14, 5551). In response, we show that this treatment does not affect the adsorption of Cu(2+) and Pd(2+). We reaffirm our statement that Cu(2+) and Pd(2+) ions can be adsorbed by a Teflon surface only after rubbing with the organic polymers, not before rubbing.

The characterization of pyroelectric materials is a necessary stage in the design of a large variety of pyroelectric-based devices ranging from intrusion alarms to IR cameras. The sample configurations and measurement techniques currently in use vary widely and require careful attention in order to avoid artifacts. In this review, we provide a practical guide to the measurement of the pyroelectric coefficient, paying particular attention to the new instrumental possibilities (fast sinusoidally modulated light sources, low impedance broad band current meters, and fast averaging oscilloscopes) that have become available during the last decade. Techniques applicable to bulk specimens, substrate-supported films, and self-supported films are described in detail. The most commonly used procedures are classified according to the type of thermal excitation: continuous ramping, heat pulse, and continuous oscillation. In the appendices, we describe the practical realization of these measurement schemes and provide mathematical descriptions for the extraction of the pyroelectric coefficient from the measured data.

It has recently been reported that Teflon and polyethylene (PE) if rubbed by polymethylmethacrylate (PMMA) or Nylon as well as non-rubbed PMMA and Nylon induce "redox" reactions, including those of the reduction of Pd(+2) and Cu(+2) ions. On this basis, it was deduced that these dielectric materials may hold ≅10(13)-10(14) of "hidden" electrons cm(-2), a value at least three orders of magnitude higher than the charge that a dielectric surface can accumulate without being discharged in air. The "hidden" electrons were termed "cryptoelectrons". In variance to these reports, we offer here an alternative interpretation. Our model is supported by X-ray photoelectron spectroscopy, contact angle and vibrating electrode (modified Kelvin probe) measurements performed on representative examples. Rubbing of the polymers was found to transfer polymer fragments between the rubbed surfaces altering their physical properties. The transferred polymer fragments promote adsorption of Cu(2+) and Pd(2+) ions. It was found that Teflon and PE rubbed with PMMA and Nylon, and non-rubbed PMMA and non-rubbed Nylon do not induce "redox" reactions of Cu(2+) and Pd(2+) ions but adsorb these ions on their surfaces. Furthermore, the earlier reported reduction of Pd(2+) to Pd(0) by electrons, as detected by catalytic activity of Pd(0) in a Cu-plating bath, can be alternatively explained by reduction of adsorbed Pd(2+) by the reducing agents of the bath itself. Based on these findings, we support the hypothesis that charging of dielectric polymers is due to ions or free radicals rather than electrons and there is no evidence to invoke a hypothesis of "cryptoelectrons"., (This journal is © the Owner Societies 2012)

Quasi-amorphous thin films of BaTiO3, SrTiO3, and BaZrO3 are the only known examples of inorganic, non-crystalline, polar materials. The conditions under which they are formed and the origin of their polarity set these materials apart from other classes of inorganic materials. The most important feature of the quasi-amorphous phase is that the polarity is the result of the orientational ordering of local bonding units but without any detectable spatial periodicity. This mechanism is reminiscent of that observed in ferroelectric polymers and permits compounds that do not have polar crystalline polymorphs, such as SrTiO3 and BaZrO3, to form polar non-crystalline solids. In the present report, we provide an overview of the essential features of these materials including preparation, structure, and chemical composition. The report also reviews our current level of understanding and offers some guidelines for further development and application of non-crystalline inorganic polar materials.

Although ice melts and water freezes under equilibrium conditions at 0 degrees C, water can be supercooled under homogeneous conditions in a clean environment down to -40 degrees C without freezing. The influence of the electric field on the freezing temperature of supercooled water (electrofreezing) is of topical importance in the living and inanimate worlds. We report that positively charged surfaces of pyroelectric LiTaO3 crystals and SrTiO3 thin films promote ice nucleation, whereas the same surfaces when negatively charged reduce the freezing temperature. Accordingly, droplets of water cooled down on a negatively charged LiTaO3 surface and remaining liquid at -11 degrees C freeze immediately when this surface is heated to -8 degrees C, as a result of the replacement of the negative surface charge by a positive one. Furthermore, powder x-ray diffraction studies demonstrated that the freezing on the positively charged surface starts at the solid/water interface, whereas on a negatively charged surface, ice nucleation starts at the air/water interface.

Although neither SrTiO3 nor BaZrO3 has any polar crystalline polymorphs, they may form noncrystalline pyro- and piezoelectric phases [Adv. Mater. 19, 1515 (2007)10.1002/adma.200602149]. These phases and the similar phase of BaTiO3 have been called quasiamorphous. In this Letter, the structure of the quasiamorphous phase of SrTiO3 is examined by the x-ray absorption fine structure technique and found to be built of a random network of polar octahedral TiO6 local bonding units. While in crystalline SrTiO3 all TiO6 octahedra are apex sharing only, in its amorphous and quasiamorphous phases, some octahedra share edges. The polarity of the quasiamorphous phase is due to the partial alignment of the TiO6 octahedra. Such a mechanism is completely different from that of inorganic polar crystals. This mechanism should be possible in a large variety of other compounds that contain similar local bonding units.

Two mechanisms by which an inorganic thin film may reversibly adapt to externally imposed strain have been considered: (1) the chemical strain effect and (2) self-organization of polycrystalline macro-domains. The chemical strain effect is due to the transformation of the elastic energy of an externally applied stress into chemical energy of interacting point defects. This effect may be observed in solids with a large concentration of interacting point defects if the interaction is accompanied by a large change in specific volume. Self-organization of polycrystalline macro-domains may take place when single-domain ferroelastic grains minimize intergrain strain via approximate mutual alignment of their crystallographic axes. Each such macro-domain region has a preferred size and direction of alignment. In the presence of externally applied stress, these regions may reorganize, thereby partially converting the elastic energy of the external stress into the elastic energy of intergrain stress. Although very different in nature, both mechanisms result in reversible strain-relaxation. The conditions under which each of these effects may be present are understood well enough to provide clear guidance for preparation of materials and for their incorporation into practical devices.