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International audience; The exotic properties of quantum spin liquids (QSLs) have continually been of interest since Anderson’s 1973 ground-breaking idea. Geometrical frustration, quantum fluctuations, and low dimensionality are the most often evoked material’s characteristics that favor the long-range fluctuating spin state without freezing into an ordered magnet or a spin glass at low temperatures. Among the few known QSL candidates, organic crystals have the advantage of having rich chemistry capable of finely tuning their microscopic parameters. Here, we demonstrate the emergence of a QSL state in [EDT-TTF-CONH2]2+[BABCO−] (EDT-BCO), where the EDT molecules with spin-1/2 on a triangular lattice form layers which are separated by a sublattice of BCO molecular rotors. By several magnetic measurements, we show that the subtle random potential of frozen BCO Brownian rotors suppresses magnetic order down to the lowest temperatures. Our study identifies the relevance of disorder in the stabilization of QSLs.

Chemical modification such as intercalation or doping of novel materials is of great importance for exploratory material science and applications in various fields of physics and chemistry. Herein, the systematic intercalation of chemically exfoliated few-layer graphene with potassium is reported while monitoring the sample resistance using microwave conductivity. It is found that the conductivity of the samples increases by about an order of magnitude upon potassium exposure. The increased number of charge carriers deduced from the electron spin resonance (ESR) intensity also reflects this increment. The doped phases exhibit two asymmetric Dysonian lines in ESR, a usual sign of the presence of mobile charge carriers. The width of the broader component increases with the doping steps; however, the narrow components seem to have a constant line width.

The performance of organic–inorganic metal halide perovskites-based (MHPs) photovoltaic devices critically depends on the design and material properties of the interface between the light-harvesting MHP layer and the electron transport layer (ETL). Therefore, the detailed insight into the transfer mechanisms of photogenerated carriers at the ETL/MHP interface is of utmost importance. Owing to its high charge mobilities and well-matched band structure with MHPs, titanium dioxide (TiO2) has emerged as the most widely used ETL material in MHPs-based photovoltaic devices. Here, we report a contactless method to directly track the photo-carriers at the ETL/MHP interface using the technique of low-temperature electron paramagnetic resonance (EPR) in combination with in situ illuminations (Photo-EPR). Specifically, we focus on a model nanohybrid material consisting of TiO2-based nanowires (TiO2NWs) dispersed in the polycrystalline methylammonium lead triiodide (MAPbI3) matrix. Our approach is based on observation of the light-induced decrease in intensity of the EPR signal of paramagnetic Ti3+ ( S = 1 / 2 ) in non-stoichiometric TiO2NWs. We associate the diminishment of the EPR signal with the photo-excited electrons that cross the ETL/MHP interface and contribute to the conversion of Ti3+ states to EPR-silent Ti2+ states. Overall, we infer that the technique of low-temperature Photo-EPR is an effective strategy to study the transfer mechanisms of photogenerated carriers at the ETL/MHP interface in MAPbI3-based photovoltaic and photoelectronic systems.

Most digital information today is encoded in the magnetization of ferromagnetic domains. The demand for ever-increasing storage space fuels continuous research for energy-efficient manipulation of magnetism at smaller and smaller length scales. Writing a bit is usually achieved by rotating the magnetization of domains of the magnetic medium, which relies on effective magnetic fields. An alternative approach is to change the magnetic state directly by acting on the interaction between magnetic moments. Correlated oxides are ideal materials for this because the effects of a small external control parameter are amplified by the electronic correlations. Here, we present a radical method for reversible, light-induced tuning of ferromagnetism at room temperature using a halide perovskite/oxide perovskite heterostructure. We demonstrate that photoinduced charge carriers from the C H 3 N H 3 P b I 3 photovoltaic perovskite efficiently dope the thin L a 0.7 S r 0.3 M n O 3 film and decrease the magnetization of the ferromagnetic state, allowing rapid rewriting of the magnetic bit. This manipulation could be accomplished at room temperature; hence this opens avenues for magnetooptical memory devices.

Recent interest in potassium-doped p-terphenyl has been fueled by reports of superconductivity at Tc values surprisingly high for organic compounds. Despite these interesting properties, studies of the structure–function relationships within these materials have been scarce. Here, we isolate a phase-pure crystal of potassium-doped p-terphenyl: [K(222)]2[p-terphenyl3]. Emerging antiferromagnetism in the anisotropic structure is studied in depth by magnetometry and electron spin resonance. Combining these experimental results with density functional theory calculations, we describe the antiferromagnetic coupling in this system that occurs in all 3 crystallographic directions. The strongest coupling was found along the ends of the terphenyls, where the additional electron on neighboring p-terphenyls antiferromagnetically couple. This delocalized bonding interaction is reminiscent of the doubly degenerate resonance structure depiction of polyacetylene. These findings hint toward magnetic fluctuation-induced superconductivity in potassium-doped p-terphenyl, which has a close analogy with high Tc cuprate superconductors. The new approach described here is very versatile as shown by the preparation of two additional salts through systematic changing of the building blocks., C.N. thanks Sheldon and Dorothea Buckler for their generous support. Support for this research was provided by the Center for Precision Assembly of Superstratic and Superatomic Solids, an NSF MRSEC (award numbers DMR-1420634 and DMR-2011738), and the Air Force Office of Scientific Research (award number FA9550-18-1-0020). R.H.S. acknowledges support from the Columbia Nano Initiative Postdoctoral Fellowship. X.R. acknowledges support from the NSF CAREER award (NSF DMR-1751949). A.K.B. is supported by the Arnold O. Beckman Fellowship in Chemical Sciences. I.S. is supported by the National Science Foundation under award number CHE-1807654. Single-crystal X-ray diffraction was performed at the Shared Materials Characterization Laboratory at Columbia University, maintained using funding from Columbia University for which we are grateful. Work in Lausanne was supported by the Swiss National Science Foundation. Work in Spain was supported by MICIU (Spain) through Grants PGC2018-096955-B-C44 and PGC2018-093863-B-C22 and Generalitat de Catalunya (2017SGR1506 and 2017SGR1289). E.C. acknowledges support from the Spanish MINECO through the Severo Ochoa Centers of Excellence Program (SEV-2015-0496) and P.A. from the Maria de Maeztu Units of Excellence Program (MDM-2017-0767). S.C. was supported by FONDECYT (Chile) through project 11107163.

We report Electron Spin Resonance (ESR) measurements on stage-I potassium intercalated graphite (KC$_8$). Angular dependent measurements show that the spin-lattice relaxation time is longer when the magnetic field is perpendicular to the graphene layer as compared to when the magnetic field is in the plane. This anisotropy is analyzed in the framework of the Elliott-Yafet theory of spin-relaxation in metals. The analysis considers an anisotropic spin-orbit Hamiltonian and the first order perturbative treatment of Elliott is reproduced for this model Hamiltonian. The result provides an experimental input for the first-principles theories of spin-orbit interaction in layered carbon and thus to a better understanding of spin-relaxation phenomena in graphene and in other layered materials as well.

We study the vibrational, magnetic and transport properties of Few Layer Graphene (FLG) using Raman and electron spin resonance spectroscopy and microwave conductivity measurements. FLG samples were produced using wet chemical exfoliation with different post-processing, namely ultrasound treatment, shear mixing, and magnetic stirring. Raman spectroscopy shows a low intensity D mode which attests a high sample quality. The G mode is present at 1580 cm(-1) as expected for graphene. The 2D mode consists of 2 components with varying intensities among the different samples. This is assigned to the presence of single and few layer graphene in the samples. Electron Spin Resonance (ESR) spectroscopy shows a main line in all types of materials with a width of about 1 mT and a g-factor in the range of 2.005-2.010. Paramagnetic defect centers with a uniaxial g-factor anisotropy are identified, which shows that these are related to the local sp2 bonds of the material. All kinds of investigated FLGs have a temperature dependent resistance which is compatible with a small gap semiconductor. The difference in resistance is related to the different grain size of the samples. (C) 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Alkali intercalated graphite compounds represent a compelling modification of carbon with significant application potential and various fundamentally important phases. We report on the intercalation of graphite with alkali atoms (Li and K) using liquid ammonia solution as mediating agent. Alkali atoms dissolve well in liquid ammonia which simplifies and speeds up the intercalation process, and it also avoids the high temperature formation of alkali carbides. Optical microscopy, Raman, and electron spin resonance spectroscopy attest that the prepared samples are highly and homogeneously intercalated to a level approaching Stage-I intercalation compounds. The method and the synthesis route may serve as a starting point for the various forms of alkali atom intercalated carbon compounds (including carbon nanotubes and graphene), which could be exploited in energy storage and further chemical modifications.

We present a detailed study of the electrical transport properties of a recently discovered iron-based superconductor: Sm$_4$Fe$_2$As$_2$Te$_{0.72}$O$_{2.8}$F$_{1.2}$. We followed the temperature dependence of the upper critical field by resistivity measurement of single crystals in magnetic fields up to 16 T, oriented along the two main crystallographic directions. This material exhibits a zero-temperature upper critical field of 90 T and 65 T parallel and perpendicular to the Fe$_2$As$_2$ planes, respectively. An unprecedented superconducting magnetic anisotropy $\gamma_H=H_{c2}^{ab}/H_{c2}^c \sim 14$ is observed near Tc, and it decreases at lower temperatures as expected in multiband superconductors. Direct measurement of the electronic anisotropy was performed on microfabricated samples, showing a value of $\rho_c/\rho_{ab}(300K) \sim 5$ that raises up to 19 near Tc. Finally, we have studied the pressure and temperature dependence of the in-plane resistivity. The critical temperature decreases linearly upon application of hydrostatic pressure (up to 2 GPa) similarly to overdoped cuprate superconductors. The resistivity shows saturation at high temperatures, suggesting that the material approaches the Mott-Ioffe-Regel limit for metallic conduction. Indeed, we have successfully modelled the resistivity in the normal state with a parallel resistor model that is widely accepted for this state. All the measured quantities suggest strong pressure dependence of the density of states.

Albeit difficult to access experimentally, the density of states (DOS) is a key parameter in solid state systems which governs several important phenomena including transport, magnetism, thermal, and thermoelectric properties. We study DOS in an ensemble of potassium intercalated single-wall carbon nanotubes (SWCNT) and show using electron spin resonance spectroscopy that a sizeable number of electron states are present, which gives rise to a Fermi-liquid behavior in this material. A comparison between theoretical and the experimental DOS indicates that it does not display significant correlation effects, even though the pristine nanotube material shows a Luttinger-liquid behavior. We argue that the carbon nanotube ensemble essentially maps out the whole Brillouin zone of graphene thus it acts as a model system of biased graphene.

We report a study of the electrical transport properties of single crystals of $\mathrm{P}{\mathrm{r}}_{4}\mathrm{F}{\mathrm{e}}_{2}\mathrm{A}{\mathrm{s}}_{2}\mathrm{T}{\mathrm{e}}_{1\ensuremath{-}x}{\mathrm{O}}_{4}$, a recently discovered iron-based superconductor. Resistivity, Hall effect, and magnetoresistance are measured in a broad temperature range revealing the role of electrons as dominant charge carriers. The significant temperature dependence of the Hall coefficient and the violation of Kohler's law indicate multiband effects in this compound. The upper critical field and the magnetic anisotropy are investigated in fields up to 16 T, applied parallel and perpendicular to the crystallographic $c$ axis. Hydrostatic pressure up to 2 GPa linearly increases the critical temperature and the resistivity residual ratio. A simple two-band model is used to describe the transport and magnetic properties of $\mathrm{P}{\mathrm{r}}_{4}\mathrm{F}{\mathrm{e}}_{2}\mathrm{A}{\mathrm{s}}_{2}\mathrm{T}{\mathrm{e}}_{1\ensuremath{-}x}{\mathrm{O}}_{4}$. The model can successfully explain the strongly temperature-dependent negative Hall coefficient and the high magnetic anisotropy, assuming that the mobility of electrons is higher than that of holes.

We report a novel synthesis route of homogeneously manganese-doped titanium dioxide nanotubes in a broad concentration range. The scroll-type trititanate (H(2)Ti(3)O(7)) nanotubes prepared by hydrothermal synthesis were used as precursors. Mn2+ ions were introduced by an ion exchange method resulting Mn(x)H(2-x)Ti(3)O(7). In a subsequent heat-treatment they were transformed into Mn(y)Ti(1-y)O(2) where y=x/(3+x). The state and the local environment of the Mn2+ ions in the precursor and final products were studied by Electron Spin Resonance (ESR) technique. It was found that the Mn2+ ions occupy two positions: the first having an almost perfect cubic symmetry while the other is in a strongly distorted octahedral site. The ratio of the two Mn2+ sites is independent of the doping level and amounts to 15:85 in Mn(x)H(2-x)Ti(3)O(7) and to 5:95 in Mn(y)Ti(1-y)O(2). SQUID magnetometry does not show long-range magnetic order in the homogeneously Mn2+-doped nanotubes., Comment: 7 pages, 6 figures

The light scattering properties of superconducting (Tc=3.8 K) heavily boron doped nanocrystalline diamond has been investigated by Raman spectroscopy using visible excitations. Fano type interference of the zone-center phonon line and the electronic continuum was identified. Lineshape analysis reveals Fano lineshapes with a significant asymmetry (q=-2). An anomalous wavelength dependence and small value of the Raman scattering amplitude is observed in agreement with previous studies.

Electron spin resonance (ESR) spectroscopy is an important tool to characterize the ground state of conduction electrons and to measure their spin-relaxation times. Observing ESR of the itinerant electrons is thus of great importance in graphene and in single-wall carbon nanotubes (SWCNTs). Often, the identification of CESR signal is based on two facts: the apparent asymmetry of the ESR signal (known as a Dysonian lineshape) and on the temperature independence of the ESR signal intensity. We argue that these are insufficient as benchmarks and instead the ESR signal intensity (when calibrated against an intensity reference) yields an accurate characterization. We detail the method to obtain the density of states from an ESR signal, which can be compared with theoretical estimates. We demonstrate the success of the method for K doped graphite powder. We give a benchmark for the observation of ESR in graphene.

Az EU alapító országaiban vállalkozói dinasztiák léteznek, illetve a kis családi vállalkozások nagy hányada is már több generációt túlélt, bőven rendelkeznek tapasztalatokkal a generációváltásban. A magyarországi vállalkozások csak most szembesülnek először ezzel a kihívással. A szerzők ezért fontosnak tartják a téma kutatását, melynek eredményei segítséget jelenthetnek a magyar vállalkozásoknak abban, hogy az első generációváltást túlélhessék, és az átadás ne váljon a vállalkozás hanyatlásának előjátékává.

We observe the electron spin resonance of conduction electrons in boron doped (6400 ppm) superconducting diamond (Tc =3.8 K). We clearly identify the benchmarks of conduction electron spin resonance (CESR): the nearly temperature independent ESR signal intensity and its magnitude which is in good agreement with that expected from the density of states through the Pauli spin-susceptibility. The temperature dependent CESR linewidth weakly increases with increasing temperature which can be understood in the framework of the Elliott-Yafet theory of spin-relaxation. An anomalous and yet unexplained relation is observed between the g-factor, CESR linewidth, and the resistivity using the empirical Elliott-Yafet relation., Comment: 10 pages, 11 figures, submitted to Phys. Rev. B

The demand for ever-increasing density of information storage and speed of manipulation boosts an intense search for new magnetic materials and novel ways of controlling the magnetic bit. Here, we report the synthesis of a ferromagnetic photovoltaic CH3NH3(Mn:Pb)I3 material in which the photo-excited electrons rapidly melt the local magnetic order through the Ruderman–Kittel–Kasuya–Yosida interactions without heating up the spin system. Our finding offers an alternative, very simple and efficient way of optical spin control, and opens an avenue for applications in low-power, light controlling magnetic devices., Functional behaviour can emerge in materials in which magnetic order is determined by the interplay of localised and itinerant magnetic interactions. Here the authors tune such magnetic order in a photovoltaic perovskite by tuning the electronic carrier concentration under visible light illumination.

A cikk a Budapesti Corvinus Egyetemen folyó vállalkozói képzés egy módszertani újítását írja le, foglalja össze. A vállalkozásindítási ötletek gyűjtésekor a tréning szakirodalomban ismert brainstorming módszerrel éltek a szerzők, a módszert azonban innovatívan alkalmazzák, a megszokott tábla, illetve flipchart technika helyett, a gyorsaságot és az áttekinthetőséget egyaránt szolgáló módon, Excel táblázatba gyűjtik az ötleteket, melyet közvetlenül kivetítővel tesznek láthatóvá a hallgatóság számára.

Today's great challenges of energy and informational technologies are addressed with a singular compound, the Li and Na doped few layer graphene. All what is impossible for graphite (homogeneous and high level Na doping), and unstable for single layer graphene, works very well for this structure. The transformation of the Raman G line to a Fano lineshape and the emergence of strong, metallic-like electron spin resonance (ESR) modes, attest the high level of graphene doping in liquid ammonia for both kinds of alkali atoms. The spin-relaxation time in our materials, deduced from the ESR line-width, is 6-8 ns, which is comparable to the longest values found in spin-transport experiments on ultrahigh mobility graphene flakes. This could qualify our material as promising candidate in spintronics devices. On the other hand, the successful sodium doping, this being a highly abundant metal, could be an encouraging alternative to lithium batteries., Comment: 10 pages, 5 figures+ Supplementary Materials

Thermal conductivity (κ) plays an essential role in functional devices. It is advantageous to design materials where one can tune κ in a wide range according to its function: single-crystals and nanowires of anatase polymorph of titanium dioxide, broadly used in applications ranging from photovoltaics, reflective coatings to memristors, have been synthesized in large quantities. Here we identify a new, strong diffusion mechanism of heat by polaronic structures due to oxygen vacancies, which considerably influences both the absolute value and the temperature dependence of κ. The additional decrease of κ is achieved in anatase nanowires organized into foam, where porosity and the quasi-one-dimensional size-effect dramatically hinder the propagation of heat, resulting in an extremely low κ = 0.014 W/Km at room-temperature. Doping this anatase foam could herald promising applications, in particular in thermoelectricity. The thermal properties of a material often determine its suitability for application and use in devices. Here, the thermal conductivity of anatase TiO2 is tuned over three orders of magnitude from bulk crystals to foam samples, by controlling polaronic effects and texturing.

An efficient route to synthesize macroscopic amounts of graphene is highly desired and bulk characterization of such samples, in terms of the number of layers, is equally important. We present a Raman spectroscopy-based method to determine the typical upper limit of the number of graphene layers in chemically exfoliated graphene. We utilize a controlled vapour-phase potassium intercalation technique and identify a lightly doped stage, where the Raman modes of undoped and doped few-layer graphene flakes coexist. The spectra can be unambiguously distinguished from alkali doped graphite, and modeling with the typical upper limit of the layers yields an upper limit of flake thickness of five layers with a significant single-layer graphene content. Complementary statistical AFM measurements on individual few-layer graphene flakes find a consistent distribution of the layer numbers.

We report a detailed spectroscopic study of Ti3+ self-doped TiO2 nanowires prepared by high temperature annealing of the protonated titanate nanowires (TiONW) in hydrogen atmosphere. Hydrogenation causes a color change from white to cyan and a major increase of photocatalytic activity. Combination of synchrotron X-ray diffraction and Rutherford backscattering spectrometry revealed that the bulk of the protonated titanate and Ti3+ self-doped titania is identical. Raman spectroscopy combined with local laser heating indicated the presence of optically active states in the hydrogenated TiO2 nanowires. Using multi-frequency electron paramagnetic resonance spectroscopy (EPR), the presence of Ti3+ surface states on the cyan titania nanowires is confirmed. We argue that these surface point defects are responsible for enhanced visible light absorption and improved their photocatalytic performance. (C) 2016 Elsevier B.V. All rights reserved.

Homogeneous Mn2+ and Gd3+ intercalation of scroll-type trititanate nanotubes using a post-synthesis ion exchange method is reported. Compared to Mn2+, Gd3+ ion-exchange shows larger saturation intercalation levels. Upon co-doping, weak interactions between the dopant ions were found to modify the incorporated concentrations. Electron spin resonance (ESR) measurements, performed at several frequencies, confirmed the homogeneous distribution of Mn2+ and Gd3+. Detailed simulation of ESR spectra identified a large spread of the local structural distortions of the occupied sites as a result of a wide range of curvature radii of the titanate nanotubes. (C) 2016 Elsevier B.V. All rights reserved.