Transport across model junctions built by using atomic tip or lateral techniques can generate exotic quantum signatures. However, so far, a viable industrial pathway for atom-driven electronics has been lacking. Here, we demonstrate that a commercialized device platform can help to fill this nanotechnological gap. According to conducting tip atomic force microscopy, inserting C atoms into an ultrathin MgO layer generates nanotransport paths. Across microscale magnetic tunnel junctions, resonant tunneling causes large magnetoresistance peaks that we attribute to spin accumulation onto a C nanodot that the channels transport. We ascribe the concurrent presence of a spectrally localized, nonlinear current noise and a persistent memory effect to the charging of a 'gating' C nanodot, adjacent to the 'transport' C nanodot. This nanoscale dual-dot description of quantum transport across spin states within a microscale magnetic tunnel junction should stimulate further research toward maturing spintronics into a viable quantum technological track.

An electrical current that flows across individual atoms can generate exotic quantum transport signatures in model junctions built using atomic tip or lateral techniques. So far, however, a viable industrial pathway for atom-driven devices has been lacking. Here, we demonstrate that a commercialized device platform can fill this nanotechnological gap. According to conducting tip atomic force microscopy, inserting C atoms into the MgO barrier of a magnetic tunnel junction generates nanotransport paths. Within magnetotransport experiments, this results in quantum interferences, and in Pauli spin blockade effects linked to tunneling magnetoresistance peaks that can be electrically controlled. We report an additional persistent memory effect that we attribute to the charging of a single "gating" C atom that is adjacent to a single C atom forming the microscale junction's effective nanotranport path. Local magnetometry experiments confirm the secondary role of magnetic stray fields on the C atoms. Our results show that, to exhibit atom-level properties, a device need not be nanoscaled, and position MgO tunneling spintronics as a promising platform to industrially implement quantum technologies.

Epitaxial clusters of chromium and chromium-vanadium oxides are studied by tunnel magneto-resistivity measurements, x-ray absorption spectrometry and circular magnetic circular dichroism. They turn out to carry a small magnetic moment that follows a super-paramagnetic behavior. The chromium ion contribution to this magnetization is mainly due to an original magnetic Cr2O3-like phase, whereas usual Cr2O3is known to be anti-ferromagnetic in the bulk. For mixed clusters, vanadium ions also contribute to the total magnetization and they are coupled to the chromium ion spins. By measuring the dichroic signal at different temperatures, we get insight into the possible spin configurations of vanadium and chromium ions: we propose that the magnetic dipoles observed in the clusters assembly could be related to ionic spins that couple at a very short range, as for instance in short one-dimensional spins chains.

Recent theory and experiments have showcased how to harness quantum mechanics to assemble heat/information engines with efficiencies that surpass the classical Carnot limit. So far, this has required atomic engines that are driven by cumbersome external electromagnetic sources. Here, using molecular spintronics, an implementation that is both electronic and autonomous is proposed. The spintronic quantum engine heuristically deploys several known quantum assets by having a chain of spin qubits formed by the paramagnetic Co center of phthalocyanine (Pc) molecules electronically interact with electron-spin-selecting Fe/C60 interfaces. Density functional calculations reveal that transport fluctuations across the interface can stabilize spin coherence on the Co paramagnetic centers, which host spin flip processes. Across vertical molecular nanodevices, enduring dc current generation, output power above room temperature, two quantum thermodynamical signatures of the engine's processes, and a record 89% spin polarization of current across the Fe/C60 interface are measured. It is crucially this electron spin selection that forces, through demonic feedback and control, charge current to flow against the built-in potential barrier. Further research into spintronic quantum engines, insight into the quantum information processes within spintronic technologies, and retooling the spintronic-based information technology chain, can help accelerate the transition to clean energy.

This open access book provides advanced students and researchers with the basic knowledge of X-ray light sources and X-ray spectroscopy.

Gaining control over the grafting geometry is critically important for any application of surface-supported single-molecule magnets (SMMs) in data storage, spintronics, and quantum information science. Here, tetrairon(III) SMMs with a propeller-like structure are functionalized with thioacetyl-terminated alkyl chains to promote chemisorption on gold surfaces from solution and to evaluate differences in adsorption geometry and magnetic properties as a function of chain length. The prepared monolayers are investigated using X-ray absorption techniques with linearly and circularly polarized light to extract geometrical and magnetic information, respectively. All derivatives remain intact and form partially oriented monolayers on the gold surface. A ligand-field analysis of the observed X-ray natural linear dichroism shows that the threefold molecular axis is invariably biased toward the surface normal, in agreement with ab initio calculations. This preferential orientation is most pronounced in monolayers of the shortest-chain derivative, which are further studied with an ultralow temperature X-ray magnetic circular dichroism setup operating down to 350 mK. The isothermal field sweeps with the magnetic field at normal incidence show an open hysteresis loop below 1 K, while measurements at different incidence angles prove the magnetic anisotropy of the monolayers.

The metal-insulator transition and the original magnetic phase that appear in vanadium oxide nanoclusters epitaxially embedded in an MgO matrix are studied via electron transport, magneto-resistance, and X-ray circular dichroism measurements. The metal-insulator transition temperature is observed to be in the range of 1.5–27 K. We observe, from 0.3 K to at least 125 K, a superparamagnetic behavior, whereas vanadium oxide, in its bulk phase, is reported to be anti-ferromagnetic (AF) at low temperatures. This striking feature is consistent with either ferromagnetic spin pairing or spin canting in the AF spin order along the 1D vanadium ion chains of the Magnéli phase or for the VO2(A)-like phase. Finally, the observed magneto-resistive effect, which reached up to 8% at low temperatures, indicates ferromagnetic behavior for some of the nanoparticles. This enables their integration in spintronic devices that could be combined with metal-insulator switching and magneto-resistive effects.

Experiments and theory are reexamining how the laws of thermodynamics are expressed in a quantum world. Most quantum thermodynamics research is performed at sub-Kelvin temperatures to prevent thermal fluctuations from smearing the mesoscopic quantum engine's discrete energy levels that mediate the asymmetric shuffling of electrons between the electrodes. Meanwhile, several groups report that building an electron-spin based implementation by placing the discrete spin states of paramagnetic centers between ferromagnetic electrodes can not only overcome this drawback, but also induce a net electrical power output despite an apparent thermal equilibrium. We illustrate this apparent thermodynamics conundrum through measurements on several devices of large output power, which endures beyond room temperature. We've inserted the Co paramagnetic center in Co phthalocyanine molecules between electron spin-selecting Fe/C60 interfaces within vertical molecular nanojunctions. This device class behaves as a spintronically controlled switch of current flow, and of its direction. We observe dc current output over several hours, and output power as high as 450nW(24nW) at 40K(360K). This leapfrogs previous results, as well as other energy harvesting strategies involving a thermal gradient. Our data indicates that the output power is strongly altered when the partly fluctuating paramagnetic centers undergo a magnetic phase transition. This new conceptual ingredient in the spin engine can account for the device's operation beyond the boundaries of classical thermodynamics. Further clarifying the phenomenon and developing this technology could help accelerate the transition to clean energy.

Spin-resolved photoemission spectroscopy experiments are performed on perfluorinated Co-phthalocyanine (F16CoPc) deposited onto ferromagnetic Co(001) to examine how doping (here with fluorine) of an organic semiconductor influences the interfacial electronic properties and whether the formation of highly spin-polarized interface states is possible. It is found that this latter property, initially reported for the nonfluorinated Pc, is also present for the fluorinated system Co/F16CoPc. This result shows that doping an organic semiconductor, which is an important and effective method to tailor the electronic transport properties of the molecules, does not inhibit the presence of a highly polarized spinterface.

The organic spinterface describes the spin-polarized properties that develop, due to charge transfer, at the interface between a ferromagnetic metal (FM) and the molecules of an organic semiconductor. Yet, if the latter is also magnetic (e.g. molecular spin chains), the interfacial magnetic coupling can generate complexity within magnetotransport experiments. Also, assembling this interface may degrade the properties of its constituents (e.g. spin crossover or non-sublimable molecules). To circumvent these issues, one can separate the molecular and FM films using a less reactive nonmagnetic metal (NM). Spin-resolved photoemission spectroscopy measurements on the prototypical system Co(001)//Cu/Mnphthalocyanine (MnPc) reveal that the Cu/MnPc spinterface atop ferromagnetic Co is highly spin-polarized at room temperature, up to Cu spacer thicknesses of at least 10 monolayers. Ab-initio theory describes a spin polarization of the topmost Cu layer after molecular hybridization that can be accompanied by magnetic hardening effects. This spinterface's unexpected robustness paves the way for 1) integrating electronically fragile molecules within organic spinterfaces, and 2) manipulating molecular spin chains using the well-documented spin transfer torque properties of the FM/NM bilayer.

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(H2B(pz)2)2(NH2-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.

Molecular complexes based on Prussian Blue analogues have recently attracted considerable interest for their unique bistable properties combined to ultimately reduced dimensions. Here, we investigate the first dinuclear FeCo complex exhibiting both thermal and photomagnetic bistability in the solid state. Through an experimental and theoretical approach combining local techniques-X-ray absorption spectroscopy (XAS), X-ray magnetic circular dichroism (XMCD), and ligand field multiplet calculations-we were able to evidence the changes occurring at the atomic scale in the electronic and magnetic properties. The spectroscopic studies were able to fully support at the atomic level the following conclusions: (i) the 300 K phase and the light-induced excited state at 4 K are both built from FeLSIII-CoHSII paramagnetic pairs with no apparent reorganization of the local structure, (ii) the 100 K phase is composed of FeLSII-CoLSIII diamagnetic pairs, and (iii) the light-induced excited state is fully relaxed at an average temperature of ≈50 K. In the paramagnetic phase at 2 K, XAS and XMCD reveal that both Fe and Co ions exhibit a rather large orbital magnetic moment (0.65 μB and 0.46 μB, respectively, under an external magnetic induction of 6.5 T), but it was not possible to detect a magnetic interaction between spin centers above 2 K.

A new ultralow-temperature setup dedicated to soft X-ray absorption spectroscopy and X-ray magnetic circular dichroism (XMCD) experiments is described. Two experiments, performed on the DEIMOS beamline (SOLEIL synchrotron), demonstrate the outstanding performance of this new platform in terms of the lowest achievable temperature under X-ray irradiation ( T = 220 mK), the precision in controlling the temperature during measurements as well as the speed of the cooling-down and warming-up procedures. Moreover, owing to the new design of the setup, the eddy-current power is strongly reduced, allowing fast scanning of the magnetic field in XMCD experiments; these performances lead to a powerful device for X-ray spectroscopies on synchrotron-radiation beamlines facilities.

We apply X-ray magnetic circular dichroism to study the internal magnetic structure of two very promising star shaped macrocyclic complexes with a CuII3TbIII core. These complexes are rare examples prepared with a macrocyclic ligand that show indications of SMM (Single Molecule Magnet) behavior, and they differ only in ring size: one has a propylene linked macrocycle, [CuII3TbIII(LPr)(NO3)2(MeOH)(H2O)2](NO3)·3H2O (nickname: Cu3Tb(LPr)), and the other has the butylene linked analogue, [CuII3TbIII(LBu)(NO3)2(MeOH)(H2O)](NO3)·3H2O (nickname: Cu3Tb(LBu)). We analyze the orbital and spin contributions to the Cu and Tb ions quantitatively by applying the spin and orbital sum rules concerning the L2 (M4)/L3 (M5) edges. In combination with appropriate ligand field simulations, we demonstrate that the Tb(iii) ions contribute with high orbital magnetic moments to the magnetic anisotropy, whereas the ligand field determines the easy axis of magnetization. Furthermore, we confirm that the Cu(ii) ions in both molecules are in a divalent valence state, the magnetic moments of the three Cu ions appear to be canted due to 3d-3d intramolecular magnetic interactions. For Cu3Tb(LPr), the corresponding element specific magnetization loops reflect that the Cu(ii) contribution to the overall magnetic picture becomes more important as the temperature is lowered. This implies a low value for the 3d-4f coupling.

Spin‐polarized charge transfer at the interface between a ferromagnetic (FM) metal and a molecule can lead to ferromagnetic coupling and to a high spin polarization at room temperature. The magnetic properties of these interfaces can not only alter those of the ferromagnet but can also stabilize molecular spin chains with interesting opportunities toward quantum computing. With the aim to enhance an organic spintronic device's functionality, external control over this spin polarization may thus be achieved by altering the ferromagnet/molecule interface's magnetic properties. To do so, the magnetoelectric properties of an underlying ferroelectric/ferromagnetic interface are utilized. Switching the ferroelectric polarization state of a PbZr 0.2 Ti 0.8 O 3 (PZT) bottom layer within a PZT/Co/FePc‐based (Pc ‐ phthalocyanine) device alters the X‐ray magnetic circular dichroism of the Fe site within the phthalocyanine molecular top layer. Thus, how to electrically alter the magnetic properties of an interface with high spin polarization at room temperature is demonstrated. This expands electrical control over spin‐polarized FM/molecule interfaces, which is first demonstrated using ferroelectric molecules, to all molecular classes.

Inelastic electron tunneling spectroscopy (IETS) within the junction of a scanning tunneling microscope (STM) uses current-driven spin-flip excitations for an all-electrical characterization of the spin state of a single object. Usually decoupling layers between the single object, atom or molecule, and the supporting surface are needed to observe these excitations. Here we study the surface magnetism of a sandwich nickelocene molecule (Nc) adsorbed directly on Cu(100) by means of X-ray magnetic circular dichroism (XMCD) and density functional theory (DFT) calculations and show with IETS that it exhibits an exceptionally efficient spin-flip excitation. The molecule preserves its magnetic moment and magnetic anisotropy not only on Cu(100), but also in different metallic environments including the tip apex. By taking advantage of this robusteness, we are able to functionalize the microscope tip with a Nc, which can be employed as a portable source of inelastic excitations as exemplified by a double spin-flip excitation process.

We use x-ray magnetic circular dichroism to evidence the effect of correlations on the local impurity magnetic moment in an archetypal Kondo system, namely, a dilute Cu: Fe alloy. Applying the sum rules on the Fe L-2,L-3 absorption edges, the evolution of the spin and orbital moments across the Kondo temperature are determined separately. The spin moment presents a crossover from a nearly temperature-independent regime belowtheKondo temperature to a paramagnetic like regime above. Conversely, the weak orbital moment shows a temperature-independent behavior in the whole temperature range, suggesting different Kondo screening temperature scales for the spin and orbital moments.

Materials science and device studies have, when implemented jointly as “operando” studies, better revealed the causal link between the properties of the device's materials and its operation, with applications ranging from gas sensing to information and energy technologies. Here, as a further step that maximizes this causal link, the paper focuses on the electronic properties of those atoms that drive a device's operation by using it to read out the materials property. It is demonstrated how this method can reveal insight into the operation of a macroscale, industrial‐grade microelectronic device on the atomic level. A magnetic tunnel junction's (MTJ's) current, which involves charge transport across different atomic species and interfaces, is measured while these atoms absorb soft X‐rays with synchrotron‐grade brilliance. X‐ray absorption is found to affect magnetotransport when the photon energy and linear polarization are tuned to excite FeO bonds parallel to the MTJ's interfaces. This explicit link between the device's spintronic performance and these FeO bonds, although predicted, challenges conventional wisdom on their detrimental spintronic impact. The technique opens interdisciplinary possibilities to directly probe the role of different atomic species on device operation, and shall considerably simplify the materials science iterations within device research.

We report on the realization of functional infrared light concentrators based on a thick layer of air-polymer metamaterial with controlled pore size gradients. The design features an optimum gradient index profile leading to light focusing in the Fresnel zone of the structures for two selected operating wavelength domains near 5.6 and 10.4 μm. The metamaterial which consists in a thick polymer containing air holes with diameters ranging from λ/20 to λ/8 is made using a 3D lithography technique based on the two-photon polymerization of a homemade photopolymer. Infrared imaging of the structures reveals a tight focusing for both structures with a maximum local intensity increase by a factor of 2.5 for a concentrator volume of 1.5 λ3, slightly limited by the residual absorption of the selected polymer. Such porous and flat metamaterial structures offer interesting perspectives to increase infrared detector performance at the pixel level for imaging or sensing applications.

Subsequent to the similar [MnIII6CrIII]3+ single-molecule magnets (SMM), the recently studied [FeIII6CrIII]3+ structural type adsorbed thin films prepared on Si and gold-coated glass substrates have been experimentally studied by means of spin-polarized electron spectroscopy (SPES) and X-ray magnetic circular dichroism (XMCD) at the Fe L3,2 edge using circularly-polarized synchrotron radiation. The results are cross-compared to the corresponding data obtained from the recently published measurements with Mn-based SMM [1], also in terms of the local spin and orbital magnetic moments obtained. Furthermore, [FeIII6CrIII]3+ single crystals have been experimentally studied by means of magnetometry and X-ray diffraction.