Spin-crossover metal complexes are highly promising magnetic molecular switches for prospective molecule-based devices. The spin-crossover molecular photoswitches developed so far operate either at very low temperatures or in the liquid phase, which hinders practical applications. Herein, we present a molecular spin-crossover iron(II) complex that can be switched between paramagnetic high-spin and diamagnetic low-spin states with light at room temperature in the solid state. The reversible photoswitching is induced by alternating irradiation with ultraviolet and visible light and proceeds at the molecular level.
properties of SCO compounds is fundamental, to understand how they behave under electronic stimuli, especially when prepared as thin films. [8,9] Indeed, these molecules can be switched between two electronic states-termed high-spin (HS) and low-spin (LS)-with different magnetic, optical, and structural properties by the action of external stimuli (pressure, temperature, light-irradiation) [10][11][12][13][14] making them promising systems for new functional materials. [7] This is particularly important since the use of electrical stimuli to control (read/write) the spinstate of the system would provide a great advantage toward technological applications, compared to other conventional addressing methods such as light irradiation, and changes in temperature or pressure, that are less easily implemented. In this paper, we show that it is possible to design large area switchable molecular tunnel junctions, in which the switchable tunneling barrier is made of a thin film of a SCO compound. Those thin films, made by evaporation on TS Au (template-stripped gold), were thoroughly characterized using highly-sensitive and specific surface tools. Electrical switching has been studied as a function of temperature in a tunnel junction configuration, and the experimental results have been rationalized thanks to a theoretical model based on energy levels and electronic densities obtained at density functional theory (DFT) level. The good correlation we establish between experimental measurements and modeling proves the feasibility to design, manipulate, and read such ultrathin film devices, an important prerequisite for the development of future active multistable devices. The most critical issues toward the development of large-area spin-crossover based molecular junctions are i) to obtain high quality SCO thin films over large areas and ii) to have a measurement methodology that allows to measure their properties in an efficient and reliable manner. Moreover, to facilitate further developments and applications of those systems, it is highly desirable to have a transition temperature (and thus, possibly, a switching temperature) close to room temperature. For those reasons, we have chosen the [Fe(HB(trz) 3 ) 2 ] SCO complex, hereafter called 1 (HB(trz) 3 = tris(1H-1,2,4-triazol-1-yl)borohydride), [15][16][17][18] for which it was shown recently that it can be deposited as continuous thin films on surfaces by thermal evaporation. [19,20] Some recent efforts have focused on vertical large area SCO junctions with film thicknesses in the 10-200 nm range Thin films of a molecular spin crossover (SCO) Iron(II) complex featuring a high transition temperature are grown by sublimation in high vacuum on TS Au and investigated by X-ray and UV photoelectron spectroscopies. Temperaturedependent studies demonstrate that the thermally induced spin crossover behavior is preserved in thin films. A large-area ultrathin switchable spin crossover molecular vertical tunnel junction with top electrodes of the liquid eutectic of gallium and indium...
TiO2 is commonly used as the active switching layer in resistive random access memory. The electrical characteristics of these devices are directly related to the fundamental conditions inside the TiO2 layer and at the interfaces between it and the surrounding electrodes. However, it is complex to disentangle the effects of film “bulk” properties and interface phenomena. The present work uses hard X‐ray photoemission spectroscopy (HAXPES) at different excitation energies to distinguish between these regimes. Changes are found to affect the entire thin film, but the most dramatic effects are confined to an interface. These changes are connected to oxygen ions moving and redistributing within the film. Based on the HAXPES results, post‐deposition annealing of the TiO2 thin film was investigated as an optimisation pathway in order to reach an ideal compromise between device resistivity and lifetime. The structural and chemical changes upon annealing are investigated using X‐ray absorption spectroscopy and are further supported by a range of bulk and surface sensitive characterisation methods. In summary, it is shown that the management of oxygen content and interface quality is intrinsically important to device behavior and that careful annealing procedures are a powerful device optimisation technique.
We report the study of anatase TiO(001)-oriented thin films grown by pulsed laser deposition on LaAlO(001). A combination of in situ and ex situ methods has been used to address both the origin of the Ti-localized states and their relationship with the structural and electronic properties on the surface and the subsurface. Localized in-gap states are analyzed using resonant X-ray photoelectron spectroscopy and are related to the Ti electronic configuration, homogeneously distributed over the entire film thickness. We find that an increase in the oxygen pressure corresponds to an increase in Ti only in a well-defined range of deposition pressure; outside this range, Ti and the strength of the in-gap states are reduced.
We report on epitaxial growth of Bi2Se3 topological insulator thin films by Pulsed Laser Deposition (PLD). X-ray diffraction investigation confirms that Bi2Se3 with a single (001)-orientation can be obtained on several substrates in a narrow (i.e., 20 °C) range of deposition temperatures and at high deposition pressure (i.e., 0.1 mbar). However, only films grown on (001)-Al2O3 substrates show an almost-unique in-plane orientation. In-situ spin-resolved angular resolved photoemission spectroscopy experiments, performed at the NFFA-APE facility of IOM-CNR and Elettra (Trieste), show a single Dirac cone with the Dirac point at E B ∼ 0.38 eV located in the center of the Brillouin zone and the spin polarization of the topological surface states. These results demonstrate that the topological surface state can be obtained in PLD-grown Bi2Se3 thin films
In the rapidly growing field of spintronics, simultaneous control of electronic and magnetic properties is essential, and the perspective of building novel phases is directly linked to the control of tuning parameters, for example, thickness and doping. Looking at the relevant effects in interface-driven spintronics, the reduced symmetry at a surface and interface corresponds to a severe modification of the overlap of electron orbitals, that is, to a change of electron hybridization. Here we report a chemically and magnetically sensitive depth-dependent analysis of two paradigmatic systems, namely La1−xSrxMnO3 and (Ga,Mn)As. Supported by cluster calculations, we find a crossover between surface and bulk in the electron hybridization/correlation and we identify a spectroscopic fingerprint of bulk metallic character and ferromagnetism versus depth. The critical thickness and the gradient of hybridization are measured, setting an intrinsic limit of 3 and 10 unit cells from the surface, respectively, for (Ga,Mn)As and La1−xSrxMnO3, for fully restoring bulk properties.
One promising route toward encoding information is to utilize the two stable electronic states of a spin crossover molecule. Although this property is clearly manifested in transport across single molecule junctions, evidence linking charge transport across a solid-state device to the molecular film's spin state has thus far remained indirect. To establish this link, we deploy materials-centric and device-centric operando experiments involving X-ray absorption spectroscopy. We find a correlation between the temperature dependencies of the junction resistance and the Fe spin state within the device's [Fe(HB(pz))(NH-phen)] molecular film. We also factually observe that the Fe molecular site mediates charge transport. Our dual operando studies reveal that transport involves a subset of molecules within an electronically heterogeneous spin crossover film. Our work confers an insight that substantially improves the state-of-the-art regarding spin crossover-based devices, thanks to a methodology that can benefit device studies of other next-generation molecular compounds.
Controlling magnetism by using electric fields is a goal of research towards novel spintronic devices and future nano-electronics. For this reason, multiferroic heterostructures attract much interest. Here we provide experimental evidence, and supporting DFT analysis, of a transition in La0.65Sr0.35MnO3 (LSMO) thin film to a stable ferromagnetic phase, that is induced by the structural and strain 2 properties of the ferroelectric BaTiO3 (BTO) substrate, which can be modified by applying external electric fields. X-ray Magnetic Circular Dichroism (XMCD) measurements on Mn L edges with a synchrotron radiation show, in fact two magnetic transitions as a function of temperature that correspond to structural changes of the BTO substrate. We also show that ferromagnetism, absent in the pristine condition at room temperature, can be established by electrically switching the BTO ferroelectric domains in the out-of-plane direction. The present results confirm that electrically induced strain can be exploited to control magnetism in multiferroic oxide heterostructures.
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