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The formation and study of a partial solid solution Az1-xFAxPbBr3, using ‘similar’ sized cations azetidinium (Az+) and formamidinium (FA+), was explored via mechanosynthesis and precipitation synthesis. The composition and lattice parameters of samples from both syntheses were analysed by 1H NMR and Rietveld refinement of the powder X-ray diffraction. A clear mismatch in the composition of the perovskite was found between the precipitated samples and the corresponding solutions. Such a mismatch was not observed for samples obtained via mechanosynthesis. The discrepancy suggests products are kinetically-controlled during precipitation, compared to thermodynamically-controlled mechanosynthesis. Furthermore, the cell volume as a function of composition in both 6H (Az-rich) and 3C (FA-rich) solid solutions suggests that FA+ is actually smaller than Az+, contradicting the literature. In the 3C (Az-poor) solid solutions, the extent of Az1-xFAxPbBr3 is unexpectedly smaller than Az1-xMAxPbBr3, again in contradiction to the expectation based on the reported cation sizes. These results indicate that other factors, as yet unidentified, must also contribute to the solid solution formation of organic-inorganic hybrid perovskites, not simply the relative sizes of the A-site cations.

Funding: School of Chemistry, University of St Andrews for funding of a studentship to GWH through the EPSRC doctoral training grant (Grant No. EP/N509759/1). This work was also facilitated by funding provided by the EPSRC (Grant No. EP/P024637/1). K.K.M. and R.S.K. acknowledge financial support from the Department of Defense, USA (DoD Grant No. FA9550-20-1-0064). The RUS component of this work was funded by EPSRC Grant No. EP/P024904/1. The recent report of an intermediate incommensurately modulated orthorhombic phase in LaTaO4 has prompted a re-examination of the phase transition sequence in LaTaO4 as a function of temperature. With falling temperature, the sequence of phases examined is (orthorhombic) Cmc21(C)↔Cmc21(IC)↔(monoclinic)P21/c, with C and IC denoting commensurate and incommensurate phases, respectively. The orthorhombic to monoclinic transition, Tm-o, is a first order reconstructive transition occurring at 440 K and TIC-C is a first-order displacive transition occurring at 500-530 K. Strain and elasticity data confirm a first-order transition between the basic and modulated Cmc21 phases, with similarities to the isostructural fluoride BaMnF4. A Raman spectroscopic study of the LaTaO4 phase transition indicates that the IC-C phase transition is driven by a soft zone-boundary phonon (unstable) of the commensurate orthorhombic (Cmc21) phase. The soft phonon is found to appear (underdamped) above 443 K and vanishes (overdamped) around 528 K. A large supercell of the monoclinic phase below Tm-o is proposed based on the Raman spectroscopic results. Publisher PDF

Repetitive elements (REs) compose ∼50% of the human genome and are normally transcriptionally silenced, although the mechanism has remained elusive. Through an RNAi screen, we identified FBXO44 as an essential repressor of REs in cancer cells. FBXO44 bound H3K9me3-modified nucleosomes at the replication fork and recruited SUV39H1, CRL4, and Mi-2/NuRD to transcriptionally silence REs post-DNA replication. FBXO44/SUV39H1 inhibition reactivated REs, leading to DNA replication stress and stimulation of MAVS/STING antiviral pathways and interferon (IFN) signaling in cancer cells to promote decreased tumorigenicity, increased immunogenicity, and enhanced immunotherapy response. FBXO44 expression inversely correlated with replication stress, antiviral pathways, IFN signaling, and cytotoxic Tcell infiltration in human cancers, while a FBXO44-immune gene signature correlated with improved immunotherapy response in cancer patients. FBXO44/SUV39H1 were dispensable in normal cells. Collectively, FBXO44/SUV39H1 are crucial repressors of RE transcription, and their inhibition selectively induces DNA replication stress and viral mimicry in cancer cells.

S.J.M acknowledges the EPSRC-funded CDT in Photonic Integration and Advanced Data Storage (EP/L015323/1) for his PhD studentship under which the work at the University of Glasgow was carried out. The work carried out at Queen’s University Belfast and the University of St Andrews was carried out as part of an EPSRC-funded collaboration (EP/P02453X/1 and EP/P024637/1). The improper ferroelectric CsNbW2O9 has recently been highlighted as the first material outside the manganite family to exhibit a similar meandering, six-fold domain structure to that responsible for enhanced and diminished conduction at charged domain walls in the rare earth manganites. While there is no current evidence for variation in domain wall conduction relative to bulk in CsNbW2O9, the similarities in microstructure strongly suggest that charged domain walls are present in this material. Herein, we report a comprehensive study of the domain microstructure of CsNbW2O9 using both piezoresponse force microscopy and transmission electron microscopy to reveal that there are, in fact, clear distinctions in the domain structure of the two systems. Constraints arising from the crystal structure of CsNbW2O9, namely, the connectivity of the BO6 polyhedra and atomic displacements occurring purely along the c axis, mean that domain walls preferentially run parallel to the c direction (the polar axis of the material) and thus remain uncharged. The characteristic cloverleaf domain structure reminiscent of the manganites is still present, however, the structure meanders predominantly in the ab plane and, therefore, appears differently depending on the projection direction from which it is viewed. As a result of this microstructural constraint, charged domain walls are not prevalent in this material. Publisher PDF

Funding: UK Engineering and Physical Sciences Research Council (Grant Number(s): EP/P022637/1, EP/K503162/1), Science and Technology Facilities Council (Grant Number(s): RB1820307), China Scholarship Council (CN). The layered perovskite LaTaO4 has been synthesized to be stable in both (polar) orthorhombic and (nonpolar) monoclinic polymorphs at ambient conditions. Although the structural transition between monoclinic and orthorhombic phases has been well established, there is some controversy regarding a further, unidentified transition around 500 K. Here this is identified as an incommensurate–commensurate first‐order transition between incommensurate Cmc21(α00)0s0 and commensurate Cmc21 orthorhombic phases. Transmission electron microscopy indicates partially ordered stacking of different structural units in a, identifying the local cause for the modulation, whereas variable temperature powder neutron diffraction has shown the overall macroscopic modulation vector, q ≈ (0.456, 0, 0)—roughly a 2.2 × expansion in a, corresponding to an approximate 11a commensurate superunit cell dimension. The modulation shows a continuous temperature dependence until transitioning to the basic (commensurate) cell at TIC‐C. Doping the interlayer La sites with smaller Nd cations stabilizes the incommensuration to higher temperature, suggesting the modulation is geometrically driven at the A site. Publisher PDF

Obituario.

Miospores from the clastic intervals between the Robinson Limestone and the Peghorn Limestone in the Brigantian (Mississippian) stratotype section at Janny Wood, Cumbria, are assigned to the Tripartites vetustus–Rotaspora fracta (VF) Assemblage Biozone. The species Murospora parthenopia , normally considered to be restricted to the underlying Raistrickia nigra–Triquitrites marginatus (NM) Biozone, is also recorded. Tripartites vetustus is recorded from the stratigraphically deepest sample, meaning that the base of the VF Biozone lies within the Asbian and not at the base of the Brigantian. The base of the VF Biozone cannot be proven in Janny Wood. A review of independent palaeontological controls on the age of the first appearance of T. vetustus in Britain indicates a lack of stratigraphical precision at the local level. Supplementary material: A full biostratigraphical range chart and a spreadsheet of biostratigraphical data are available at https://doi.org/10.6084/m9.figshare.c.4199306

Since the observation that the properties of ferroic domain walls (DWs) can differ significantly from the bulk materials in which they are formed, it has been realized that domain wall engineering offers exciting new opportunities for nanoelectronics and nanodevice architectures. Here, a novel improper ferroelectric, CsNbW2O9, with the hexagonal tungsten bronze structure, is reported. Powder neutron diffraction and symmetry mode analysis indicate that the improper transition (TC = 1100 K) involves unit cell tripling, reminiscent of the hexagonal rare earth manganites. However, in contrast to the manganites, the symmetry breaking in CsNbW2O9 is electronically driven (i.e., purely displacive) via the second‐order Jahn–Teller effect in contrast to the geometrically driven tilt mechanism of the manganites. Nevertheless CsNbW2O9 displays the same kinds of domain microstructure as those found in the manganites, such as the characteristic six‐domain “cloverleaf” vertices and DW sections with polar discontinuities. The discovery of a completely new material system, with domain patterns already known to generate interesting functionality in the manganites, is important for the emerging field of DW nanoelectronics.

We thank the Science and Technology Facilities Council (STFC) for the provision of neutron diffraction facilities at ISIS (HRPD experiment RB1710021, doi: 10.5286/ISIS.E.RB1710021) and the School of Chemistry, University of St Andrews for funding of a studentship to JAM through the EPSRC doctoral training grant (EP/K503162/1). The ambient temperature structures (orthorhombic, space group, Cmc21) of the polar hexagonal tungsten bronzes RbNbW2O9 and KNbW2O9 have been determined by high-resolution powder neutron diffraction. Displacement of the A-site cation in the polar c-axis, with concomitant octahedral tilting, occurs to optimise the A-cation bonding environment reducing the coordination from 18 to 16. This effect is more evident in KNbW2O9 due to decreased A-cation size. The octahedral tilting in both compositions results in a doubling of the c-axis that has not previously been reported, highlighting the importance of neutron diffraction as a complementary technique for structural determination of such systems. Publisher PDF

We thank the Chinese Scholarship Council for Ph.D. Studentship support (to JT). Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under grant no. 2.5020.11. D.B. is an FNRS Research Director. We report the synthesis and properties of a new organic–inorganic hybrid lead perovskite (OIHP), azetidinium lead bromide (AzPbBr3), possessing the 6H perovskite structure (space group P63/mmc with a = 8.745 Å and c = 21.329 Å). This compound has a band gap of 2.81 eV and remains stable for >6 months in the ambient environment. DFT simulations are in fairly good agreement with experiments and indicate that AzPbBr3 is a direct band gap semiconductor. A partial solid solution with the cubic (3C) perovskite methylammonium lead bromide (Az1–xMAxPbBr3) is possible. In Az-rich 6H compositions the lattice volume and band gap are invariant with x (≤0.3), whereas in the MA-rich 3C phase (0.8 ≤ x ≤ 1.0) the lattice parameters and band gap increase with increasing Az content. Although the relatively large band gap of AzPbBr3 makes it unsuitable for photovoltaic applications, the results indicate Az+ is a suitable alternative organic A cation for band gap tuning of OHIPs. Postprint

The ambient-temperature structures (orthorhombic, space group Cmc2

This work at St Andrews was supported by EPSRC grant EP/P024637/1. EKHS thanks EPSRC for support. Crackling noise of ferroelectric lead zirconate titanate samples during ferroelectric switching is demonstrated to be compatible with avalanche statistics. The peaks of the slew rate (time derivative of current dI/dt squared), defined as "jerks," were statistically analyzed and shown to obey power laws. The critical exponent obtained is 1.64 ± 0.15, in agreement with predictions from avalanche theory. The exponent is independent of temperature within experimental error margins. Postprint

The authors would like to thank to the following funding organisations: the Royal Society for providing a research fellowship (F.D.M.), EPSRC for providing the PhD student grant (A.R.) and Roberto Rocca Education Program for providing an additional fellowship grant (A.R.). The electrical properties of a family of tetragonal tungsten bronze (TTB) materials, Ba6Sc1-xInxNb9O30 (x = 0.25, 0.5, 0.75), which display relaxor properties were characterised using high-temperature impedance spectroscopy and low-temperature dielectric spectroscopy. All powders were synthesized at 1250°C (24hours) + 1350°C (6.5hours), while the pellets were further sintered at 1350°C (12hours). At high temperature, the electrical conductivity in all samples is dominated by a single response, attributed to the bulk response, while the subtle asymmetry of the imaginary impedance peak suggests a minor contribution of the grain boundary response. In general, the Sc-In solid solutions samples exhibit similar electrical behaviour to the Sc compound, x = 1 reported previously (Ceram. Int. 2016, 42, 11810–11821). At low temperature all compounds exhibit frequency dependent relaxor behaviour. With increasing the content of In, the dielectric peaks are more asymmetric and the curves flatten more at temperatures above the transition temperature. The dipole freezing temperature, TVF, determined by Vogel-Fulcher (VF) analysis does not simply increases linearly as a function of M3+ (Sc3+,In3+) cation size, the extrapolation of VF-like curves results in considerably different values when compared to those found previously, since the acquired dielectric data are very sensitive to preparative conditions. Postprint

S.R.P. and J.W.G.B. acknowledge the EPSRC (grant EP/N01717X/1) and Leverhulme Trust (grant RPG-2012-576) for financial support and the STFC for the provision of beam time at ISIS. F.D.M. acknowledges the EPSRC for financial support (grant EP/P024637/1). M.S.S. acknowledges the Royal Society for a University Research Fellowship (grant UF160265). The phonon-glass electron crystal concept is one of the key guiding principles for the development of efficient thermoelectric materials. Here, we confirm that SrTiO 3 becomes a phonon-glass for large numbers of A-site vacancies in the Sr 1-x La 0.67x → 0.33x TiO 3 series and show that its electron crystal properties are stymied by the presence of a core-shell grain structure. Thermal conductivity, heat capacity, and neutron powder diffraction, complemented by representational analysis and phonon calculations, were used to investigate the thermal transport. This reveals that the heat carrying modes are dominated by Sr motions and that these become more localized upon the introduction of the A-site vacancies, consistent with the observed phonon-glass state. Impedance spectroscopy and direct current electrical measurements were used to probe the electrical properties of insulating and conducting samples. This reveals the coring of grains due to oxidation on cooling from sintering temperatures. The resultant insulating shell limits the thermoelectric power factor to S 2 /ρ = 0.45 mW m -1 K -2 and the figure-of merit to ZT = 0.15 at 900 K for Sr 0.20 La 0.53 → 0.27 Ti 0.95 Nb 0.05 O 3?δ . The thermal properties of these materials are, therefore, controlled by an intrinsic feature of the microstructure (i.e., the A-site vacancies), whereas the electrical properties are grain boundary limited, which in principle can be controlled independently to raise S 2 /ρ and ZT. Postprint

The authors would like to thank to the following funding organisations: the Royal Society for providing a research fellowship (F.D.M.), EPSRC for providing the PhD student grant (A.R.) and Roberto Rocca Education Program for providing an additional fellowship (A.R.). This work reports on the microstructural and high-temperature impedance spectroscopy study of a family of dielectric ceramics Ba6MNb9O30 (M=Ga, Sc, In) of tetragonal tungsten bronze (TTB) structure with relaxor properties. For Ba6GaNb9O30 and Ba6InNb9O30 pellets, the SEM images have revealed good, dense internal microstructures, with well-bonded grains and only discrete porosity; in contrast Ba6ScNb9O30 pellets had a poorer microstructure, with many small and poorly-bonded grains gathered in agglomerates, resulting in significant continuous porosity and poorly defined grain boundary regions. The electroactive regions were characterised by the bulk and grain boundaries capacitances and resistances, while their contribution to the electrical conduction process was estimated by determining activation energies from the temperature (Arrhenius) dependence of both electric conductivities and time constants. For Ga and In analogues the electronic conductivity are dominated by the bulk response, while for Sc analogue, the poorly defined grain boundaries give a bulk-like response, mixing with the main bulk contribution. Postprint

JG would like to thank the EPSRC for provision of a studentship via the doctoral training grant (EP/K503162/1). The research data (and/or materials) supporting this publication can be accessed at [http://dx.doi.org/10.17630/a7a9bc13-b5cb-485d-914a-923832f25190] Combined temperature-dependent structural and electrical characterization of a series of “empty” ferroelectric tetragonal tungsten bronzes (TTBs) of composition Ba4(La1- xNdx)0.67□1.33Nb10O30 are reported. The La-material exhibits a temperature dependent crossover from relaxor-ferroelectric to polar (but non-ferroelectric) to linear dielectric behavior. The loss of ferroelectric switching in the polar, non-ferroelectric phase is accompanied by disorder associated with structural relaxation due the significant vacancy concentration at the A1-perovskite-like site. In this disordered regime, large polarization can be re-established with application of sufficient electric field, however relaxation back into the disordered phase occurs on removal of the field as indicated by the loss of remenant polarization. The field against which “backswitching” (depolarization) occurs increases with temperature indicating increasing stability of the disordered regime. The disordered phase can be de-stabilized by substituting Nd for La at the A1-site and which reintroduces “normal” ferroelectric behavior. Postprint