Building High-Density Polar Hybrid Perovskites via Intercalation of Cs+ and Aromatic Diamine for Passive X-ray Detection.

2D organic-inorganic hybrid perovskites (OIHPs) have shown great promise in direct X-ray detection. The development of high-performance passive X-ray detectors in 2D OIHPs calls for an increase in material density while maintaining structural polarity, which is becoming quite challenging. Here, a high-density, polar 2D alternating-cation-intercalated (ACI) perovskite, (4-AP)Cs2Pb2I8 (B, 4-AP = 4-amidinopyridinium), capable of addressing this problem is successfully constructed by introducing heavy Cs+ into the interlayer space of an aromatic Dion-Jacobson (DJ) perovskite (4-AP)PbI4 (A). Through such a DJ-to-ACI design, the newly developed 2D OIHP B not only significantly increases its density to 4.23 g cm-3 (even higher than that of 3D MAPbI3) but also crystallizes in a polar space group (Ama2), which further leads to enhanced X-ray attenuation and an obvious polar photovoltage (1.1 V) under X-ray irradiation. As a result, X-ray detectors fabricated by high-quality single crystals of B exhibit excellent and stable detection performance under self-powered mode with a high sensitivity of 107 µC Gy-1 cm-2 and a low detection limit of 289 nGy s-1. This work provides implications for the future exploration and regulation of novel ACI OIHPs for high-performance photoelectronic devices.

Polymorphic Heterogeneous Polar Structure Enabled Superior Capacitive Energy Storage in Lead-Free Relaxor Ferroelectrics at Low Electric Field.

High-performance energy storage dielectrics capable of low/moderate field operation are vital in advanced electrical and electronic systems. However, in contrast to achievements in enhancing recoverable energy density (Wrec), the active realization of superior Wrec and energy efficiency (η) with giant energy-storage coefficient (Wrec/E) in low/moderate electric field (E) regions is much more challenging for dielectric materials. Herein, lead-free relaxor ferroelectrics are reported with giant Wrec/E designed with polymorphic heterogeneous polar structure. Following the guidance of Landau phenomenological theory and rational composition construction, the conceived (Bi0.5Na0.5)TiO3-based ternary solid solution that delivers giant Wrec/E of ≈0.0168 µC cm-2, high Wrec of ≈4.71 J cm-3 and high η of ≈93% under low E of 280 kV cm-1, accompanied by great stabilities against temperature/frequency/cycling number and excellent charging-discharging properties, which is ahead of most currently reported lead-free energy storage bulk ceramics measured at same E range. Atomistic observations reveal that the correlated coexisting local rhombohedral-tetragonal polar nanoregions embedded in the cubic matrix are constructed, which enables high polarization, minimized hysteresis, and significantly delayed polarization saturation concurrently, endowing giant Wrec/E along with high Wrec and η. These findings advance the superiority and feasibility of polymorphic nanodomains in designing highly efficient capacitors for low/moderate field-region practical applications.

Observation of the Anomalous Hall Effect in a Layered Polar Semiconductor.

Progress in magnetoelectric materials is hindered by apparently contradictory requirements for time-reversal symmetry broken and polar ferroelectric electronic structure in common ferromagnets and antiferromagnets. Alternative routes can be provided by recent discoveries of a time-reversal symmetry breaking anomalous Hall effect (AHE) in noncollinear magnets and altermagnets, but hitherto reported bulk materials are not polar. Here, the authors report the observation of a spontaneous AHE in doped AgCrSe2 , a layered polar semiconductor with an antiferromagnetic coupling between Cr spins in adjacent layers. The anomalous Hall resistivity 3 µ Ω c m $\mu \Omega \, \textnormal {cm}$ is comparable to the largest observed in compensated magnetic systems to date, and is rapidly switched off when the angle of an applied magnetic field is rotated to ≈80° from the crystalline c-axis. The ionic gating experiments show that the anomalous Hall conductivity magnitude can be enhanced by modulating the p-type carrier density. They also present theoretical results that suggest the AHE is driven by Berry curvature due to noncollinear antiferromagnetic correlations among Cr spins, which are consistent with the previously suggested magnetic ordering in AgCrSe2 . The results open the possibility to study the interplay of magnetic and ferroelectric-like responses in this fascinating class of materials.

Origin and Mechanism of Piezoelectric and Photovoltaic Effects in (111) Polar Orientated NiO Films.

Based on the current piezoelectric theory, NiO with the centrosymmetric structure is not piezoelectric. However, herein, this study shows the first observation of piezoelectric generation, rectifyingand bulk photovoltaic behaviors in NiO films with [111] orientation and the change in NiO crystal structure in piezoelectric process. The piezoelectric generation, rectifying, and bulk photovoltaic performances are enhanced by increasing (111) orientation, and attenuated and eliminated by applying a persistent stress on the NiO film. The NiO [111] is polar direction, and thus a spontaneous electric field (ES ) is in the NiO film with [111] orientation. The existence of Es in (111) oriented NiO film is found to be the physical basis of the piezoelectric generators and photovoltaic and rectifying effects. Thus, NiO piezoelectric, rectifying, and bulk photovoltaic mechanism are presented at the atomic level. The mechanism may rewrite the current piezoelectric theory, and establish a unified theory of polar structure with wide implications. The polar-orientated films can be used to fabricate piezoelectric generators and other optoelectronic devices with high performances.

Observation of Hidden Polar Phases and Flux Closure Domain Topology in Bi2WO6 Thin Films.

Topological textures of ferroelectric polarizations have promise as alternative devices for future information technology. A polarization rotation inevitably deviates from the stable orientation in axial ferroelectrics, but local energy losses compromise the global symmetry, resulting in a distorted shape of the topological vortex or inhibiting the vortex. Easy planar isotropy helps to promote rotating structures and, accordingly, to facilitate access to nontrivial textures. Here, we investigate the domain structure of an epitaxial thin film of bismuth tungsten oxide (Bi2WO6) grown on a (001) SrTiO3 substrate. By using angle-resolved piezoresponse force microscopy and scanning transmission electron microscopy, we find the existence of a hidden phase with ⟨100⟩-oriented ferroelectric polarizations in the middle of the four variant ⟨110⟩-oriented polarization domains, which assists in the formation of flux closure domains. The results suggest that this material is one step closer to becoming an isotropic two-dimensional polar material.

Polar Nitride Perovskite LaWN3-δ with Orthorhombic Structure.

Nitride perovskite LaWN3 has been predicted to be a promising ferroelectric material with unique properties for diverse applications. However, due to the challenging sample preparation at ambient pressure, the crystal structure of this nitride remains unsolved, which results in many ambiguities in its properties. Here, the authors report a comprehensive study of LaWN3 based on high-quality samples synthesized by a high-pressure method, leading to a definitive resolution of its crystal structure involving nitrogen deficiency. Combined with theoretical calculations, these results show that LaWN3 adopts an orthorhombic Pna21 structure with a polar symmetry, possessing a unique atomic polarization along the c-axis. The associated atomic polar distortions in LaWN3 are driven by covalent hybridization of W: 5d and N: 2p orbitals, opening a direct bandgap that explains its semiconducting behaviors. The structural stability and electronic properties of this nitride are also revealed to be closely associated with its nitrogen deficiency. The success in unraveling the structural and electronic ambiguities of LaWN3 would provide important insights into the structures and properties of the family of nitride perovskites.

Spontaneous helielectric nematic liquid crystals: Electric analog to helimagnets.

Recently, a type of ferroelectric nematic fluid has been discovered in liquid crystals in which the molecular polar nature at molecule level is amplified to macroscopic scales through a ferroelectric packing of rod-shaped molecules. Here, we report on the experimental proof of a polar chiral liquid matter state, dubbed helielectric nematic, stabilized by the local polar ordering coupled to the chiral helicity. This helielectric structure carries the polar vector rotating helically, analogous to the magnetic counterpart of helimagnet. The helielectric state can be retained down to room temperature and demonstrates gigantic dielectric and nonlinear optical responses. This matter state opens a new chapter for developing the diverse polar liquid crystal devices.

Effect of TC(002) on the Output Current of a ZnO Thin-Film Nanogenerator and a New Piezoelectricity Mechanism at the Atomic Level.

Understanding the piezoelectricity mechanism is crucial for developing new materials for better performance. Here, we developed a nanogenerator based on the ZnO thin films having various TC(002) values. The output current well correlated to the magnitude of (002) texture coefficient (TC(002)). Additionally, the TC(002)-dependent photovoltaic and rectification properties are observed. When the film is subjected to persistent compression, the photovoltaic, rectification, and piezoelectric properties fade away. Based on our observation that the ZnO polar structure always shows a spontaneous electron field (SEF), we thus propose a new piezoelectricity mechanism. The [001]-orientated ZnO thin film with the SEF is equivalent to a capacitor, the compression functions as a discharging process, and the removal of the external stress serves as a charging process. The physical mechanism provides an insight into various energy conversion processes that will inspire advanced designs of high-performance nanogenerators, solar cells, and other optoelectronic devices.

[(CH3 )3 NH]3 Bi2 I9 : A Polar Lead-Free Hybrid Perovskite-Like Material as a Potential Semiconducting Absorber.

Perovskite hybrids of lead organometal halides, most notably CH3 NH3 PbI3 , have shown extremely promising applications in the field of optoelectronics, because of their remarkable semiconducting and light-absorbing properties. However, two key issues-the toxicity of lead and the poor ambient instabilities-have restrained their further commercialization. Herein, we have designed a new stable polar lead-free hybrid material by utilizing the strategy of cation substitution, [(CH3 )3 N]3 Bi2 I9 (1), which adopts the 0D inorganic perovskite-like architecture by face-sharing BiI6 octahedra. It is interesting that 1 displays excellent absorbing properties with a narrow optical band gap of ≈2.0 eV, and positive temperature-dependent conductivity confirms its semiconducting behaviors. In addition, 1 has good phase stability against decomposition under ambient conditions, much superior to that of CH3 NH3 PbI3 . This work suggests the potential of 1 as a lead-free semiconducting absorber with high phase stability for photoelectric applications.