CuInP2S6 Room Temperature Layered Ferroelectric.

We explore ferroelectric properties of cleaved 2-D flakes of copper indium thiophosphate, CuInP2S6 (CITP), and probe size effects along with limits of ferroelectric phase stability, by ambient and ultra high vacuum scanning probe microscopy. CITP belongs to the only material family known to display ferroelectric polarization in a van der Waals, layered crystal at room temperature and above. Our measurements directly reveal stable, ferroelectric polarization as evidenced by domain structures, switchable polarization, and hysteresis loops. We found that at room temperature the domain structure of flakes thicker than 100 nm is similar to the cleaved bulk surfaces, whereas below 50 nm polarization disappears. We ascribe this behavior to a well-known instability of polarization due to depolarization field. Furthermore, polarization switching at high bias is also associated with ionic mobility, as evidenced both by macroscopic measurements and by formation of surface damage under the tip at a bias of 4 V-likely due to copper reduction. Mobile Cu ions may therefore also contribute to internal screening mechanisms. The existence of stable polarization in a van-der-Waals crystal naturally points toward new strategies for ultimate scaling of polar materials, quasi-2D, and single-layer materials with advanced and nonlinear dielectric properties that are presently not found in any members of the growing "graphene family".

Epoxy resin/carbon black composites below the percolation threshold.

A set of epoxy resin composites filled with 0.25-2.0 wt.% of commercially available ENSACO carbon black (CB) of high and low surface area (CBH and CBL respectively) has been produced. The results of broadband dielectric spectroscopy of manufactured CB/epoxy below the percolation threshold in broad temperature (200 K to 450 K) and frequency (20 Hz to 1 MHz) ranges are reported. The dielectric properties of composites below the percolation threshold are mostly determined by alpha relaxation in pure polymer matrix. The glass transition temperature for CB/epoxy decreases in comparison with neat epoxy resin due to the extra free volume at the polymer-filler interface. At room temperature, the dielectric permittivity is higher for epoxy loaded with CBH additives. In contrast, at high temperature, the electrical conductivity was found to be higher for composites with CBL embedded. The established influence of the CB surface area on the broadband dielectric characteristics can be exploited for the production of effective low-cost antistatic paints and coatings working at different temperatures.

Magnetic excitation and readout of methyl group tunnel coherence.

Methyl groups are ubiquitous in synthetic materials and biomolecules. At sufficiently low temperature, they behave as quantum rotors and populate only the rotational ground state. In a symmetric potential, the three localized substates are degenerate and become mixed by the tunnel overlap to delocalized states separated by the tunnel splitting ν t . Although ν t can be inferred by several techniques, coherent superposition of the tunnel-split states and direct measurement of ν t have proven elusive. Here, we show that a nearby electron spin provides a handle on the tunnel transition, allowing for its excitation and readout. Unlike existing dynamical nuclear polarization techniques, our experiment transfers polarization from the electron spin to methyl proton spins with an efficiency that is independent of the magnetic field and does not rely on an unusually large tunnel splitting. Our results also demonstrate control of quantum states despite the lack of an associated transition dipole moment.

Correction to: Vilnius Declaration on chronic respiratory diseases: multisectoral care pathways embedding guided self-management, mHealth and air pollution in chronic respiratory diseases.

An amendment to this paper has been published and can be accessed via the original article.

Isostructural phase transition, quasielastic neutron scattering and magnetic resonance studies of a bistable dielectric ion-pair crystal [(CH3)2NH2]2KCr(CN)6.

We have synthesised and characterised a novel organic-inorganic hybrid crystal, [(CH3)2NH2]2KCr(CN)6. The thermal DSC, TMA, DTG and DTA analyses indicate two solid-to-solid structural phase transitions (PTs). According to the X-ray diffraction experiments, the first PT at 220 K is isostructural, since it does not involve a change of the space group. This transition occurs between the states, where the (CH3)2NH2+ cations are orientationally disordered and ordered (frozen). The other reversible PT at 481 K leads to a melt-like phase similar to the one observed in plastic crystals or polar liquids. Dielectric spectroscopy has been used to characterise the switching properties of the dipole moments in the vicinity of the PTs. Continuous-wave electron paramagnetic resonance spectroscopy was employed to investigate the effect of ordering on the local environment of the Cr3+ ions. We have also applied the quasielastic neutron scattering (QENS) technique as well as 1H NMR spectroscopy to measure the dynamics of the (CH3)2NH2+ cations residing in the inorganic framework.

Vilnius Declaration on chronic respiratory diseases: multisectoral care pathways embedding guided self-management, mHealth and air pollution in chronic respiratory diseases.

BACKGROUND: Over 1 billion people suffer from chronic respiratory diseases such as asthma, COPD, rhinitis and rhinosinusitis. They cause an enormous burden and are considered as major non-communicable diseases. Many patients are still uncontrolled and the cost of inaction is unacceptable. A meeting was held in Vilnius, Lithuania (March 23, 2018) under the patronage of the Ministry of Health and several scientific societies to propose multisectoral care pathways embedding guided self-management, mHealth and air pollution in selected chronic respiratory diseases (rhinitis, chronic rhinosinusitis, asthma and COPD). The meeting resulted in the Vilnius Declaration that was developed by the participants of the EU Summit on chronic respiratory diseases under the leadership of Euforea. CONCLUSION: The Vilnius Declaration represents an important step for the fight against air pollution in chronic respiratory diseases globally and has a clear strategic relevance with regard to the EU Health Strategy as it will bring added value to the existing public health knowledge.

Reorientational dynamics of organic cations in perovskite-like coordination polymers.

Here we report the dynamics of organic cations as guest molecules in a perovskite host-framework. The molecular motion of CH3NH3+ (MAFe), (CH3)2NH2+ (DMAFe) and (CH3)3NH+ (TrMAFe) in the cage formed by KFe(CN)63- units was studied using a combination of experimental methods: (i) thermal analysis, (ii) dielectric and electric studies, (iii) optical observations, (iv) EPR and 1H NMR spectroscopy and (v) quasielastic neutron scattering (QENS). In the case of MAFe and TrMAFe, the thermal analysis reveals one solid-to-solid phase transition (PT) and two PTs for the DMAFe crystal. A markedly temperature-dependent dielectric constant indicates the tunable and switchable properties of the complexes. Also, their semiconducting properties are confirmed by a dc conductivity measurement. The broadband dielectric relaxation is analyzed for the TrMAFe sample in the frequency range of 100 Hz-1 GHz. QENS shows that we deal rather with the localized motion of the cation than a diffusive one. Three models, which concern the simultaneous rotation of the CH3 and/or NH3 group, π-flips and free rotations of the organic cation, are used to fit the elastic incoherent structure factor. The 1H NMR spin-lattice relaxation time for all compounds under study, as well as the second moments, has been measured in a wide temperature range. In all studied samples, the temperature dependence of the second moment of the proton NMR line indicated the gradual evolution of the molecular movements from the rigid state up to a highly disordered one.

Full-wave finite space model of open-ended coaxial line for dielectric spectroscopy of liquids.

The physical equipment was built according to the mathematical model and tested. The performance of equipment is demonstrated measuring two known liquids, methanol and isopropanol, up to 40 GHz. The accuracy and sensitivity, and the versatility and ease of manufacturing of the measurement cell are discussed.

Size effects in a relaxor: further insights into PMN.

Dielectric measurements of PbMg1/3Nb2/3O3 (PMN) powder and dense ceramics with grain sizes between 15 nm and two microns were carried out in a broad frequency range (20 Hz-1 GHz). Clear grain size dependence of relaxor behavior was evidenced. A progressive transformation from Vogel-Fulcher behavior towards the Arrhenius process in the PMN with reduction of grain size in both ceramics and powder was observed. In the case of ceramics we were able to extract deeper information from the distributions of relaxation times and an analysis using the Vogel-Fulcher law, revealing two main contributions: a fast part of distribution of relaxation times with a maximum close to 10(-11) s, which is almost grain-size independent and has a non-polar origin; whereas, a process with long relaxation times (in the time range of 10(-8) to 10(-5) s) is associated with the dynamics of the polar nanoregions and is strongly suppressed with reduction of grain size. The results of dielectric investigations are confirmed by Nuclear Magnetic Resonance experiments.

The perfect soft mode: giant phonon instability in a ferroelectric.

Previous studies of unstable ('soft') optical modes in ferroelectrics have reported minimum frequencies of 1 cm(-1) (30 GHz) for underdamped phonons. In this work we fabricate a cylindrical coaxial specimen and rectangular plate waveguide specimens of tris-sarcosine calcium chloride (TSCC) and follow its soft mode several orders of magnitude lower to 1 GHz. Below 30 GHz the relaxation time is probably characteristic of domain wall motion; the new theory of Pakhomov et al (2013 Ferroelectrics at press) predicts 0.5 THz far from TC and a (T - T(C))/T(C) dependence, in agreement with our experimental values. This discovery has implications for GHz electronics such as phased array radar or other voltage-tunable low-loss components. The mean-field frequency description of the soft mode response f(T) is supported via precision calorimetry on TSCC with and without Br-doping. The ferroelectric-antiferroelectric phase transition, previously suggested from high-pressure data, is confirmed at 45 K at 1 atm.

Terahertz emission from tubular pB(Zr,Ti)O3 nanostructures.

We report intense terahertz emission from lead zirconate titanate (PZT) tubular nanostructures, which have a wall thickness around 40 nm and protrude on n-type Si substrates. Such emission is totally absent in flat PZT films or bulk; hence the effect is attributed to the nanoscale geometry of the tubes. The terahertz radiation is emitted within 0.2 ps, and the spectrum exhibits a broad peak from 2 to 8 THz. This is a gap in the frequency spectrum of conventional semiconductor terahertz devices, such as ZnTe, and an order of magnitude higher frequency peak than that in the well-studied p-InAs, due to the abnormally large carrier concentration gradient in the nanostructured PZT. The inferred mechanism is optical rectification within a surface accumulation layer, rather than the Dember effect. The terahertz emission is optically pumped, but since the tubes exhibit ferroelectric switching, electrically driven emission may also be possible. EPR reveals 02 molecules adsorbed onto the nanotubes, which may play some role in the emission.