Highly Efficient Spin-to-Charge Current Conversion in Strained HgTe Surface States Protected by a HgCdTe Layer.

We report the observation of spin-to-charge current conversion in strained mercury telluride at room temperature, using spin pumping experiments. We show that a HgCdTe barrier can be used to protect the HgTe from direct contact with the ferromagnet, leading to very high conversion rates, with inverse Edelstein lengths up to 2.0±0.5 nm. The influence of the HgTe layer thickness on the conversion efficiency is found to differ strongly from what is expected in spin Hall effect systems. These measurements, associated with the temperature dependence of the resistivity, suggest that these high conversion rates are due to the spin momentum locking property of HgTe surface states.

Evidence for spin-to-charge conversion by Rashba coupling in metallic states at the Fe/Ge(111) interface.

The spin-orbit coupling relating the electron spin and momentum allows for spin generation, detection and manipulation. It thus fulfils the three basic functions of the spin field-effect transistor. However, the spin Hall effect in bulk germanium is too weak to produce spin currents, whereas large Rashba effect at Ge(111) surfaces covered with heavy metals could generate spin-polarized currents. The Rashba spin splitting can actually be as large as hundreds of meV. Here we show a giant spin-to-charge conversion in metallic states at the Fe/Ge(111) interface due to the Rashba coupling. We generate very large charge currents by direct spin pumping into the interface states from 20 K to room temperature. The presence of these metallic states at the Fe/Ge(111) interface is demonstrated by first-principles electronic structure calculations. By this, we demonstrate how to take advantage of the spin-orbit coupling for the development of the spin field-effect transistor.

Spin to Charge Conversion at Room Temperature by Spin Pumping into a New Type of Topological Insulator: α-Sn Films.

We present results on spin to charge current conversion in experiments of resonant spin pumping into the Dirac cone with helical spin polarization of the elemental topological insulator (TI) α-Sn. By angle-resolved photoelectron spectroscopy (ARPES), we first check that the Dirac cone (DC) at the α-Sn (0 0 1) surface subsists after covering Sn with Ag. Then we show that resonant spin pumping at room temperature from Fe through Ag into α-Sn layers induces a lateral charge current that can be ascribed to the inverse Edelstein effect by the DC states. Our observation of an inverse Edelstein effect length much longer than those generally found for Rashba interfaces demonstrates the potential of TIs for the conversion between spin and charge in spintronic devices. By comparing our results with data on the relaxation time of TI free surface states from time-resolved ARPES, we can anticipate the ultimate potential of the TI for spin to charge conversion and the conditions to reach it.

Spin transport in p-type germanium.

We report on the spin transport properties in p-doped germanium (Ge-p) using low temperature magnetoresistance measurements, electrical spin injection from a ferromagnetic metal and the spin pumping-inverse spin Hall effect method. Electrical spin injection is carried out using three-terminal measurements and the Hanle effect. In the 2-20 K temperature range, weak antilocalization and the Hanle effect provide the same spin lifetime in the germanium valence band (≈1 ps) in agreement with predicted values and previous optical measurements. These results, combined with dynamical spin injection by spin pumping and the inverse spin Hall effect, demonstrate successful spin accumulation in Ge. We also estimate the spin Hall angle θ(SHE) in Ge-p (6-7 x 10(-4) at room temperature, pointing out the essential role of ionized impurities in spin dependent scattering.

Enhanced Spin Pumping Efficiency in Antiferromagnetic IrMn Thin Films around the Magnetic Phase Transition.

We report the measurement of a spin pumping effect due to fluctuations of the magnetic order of IrMn thin films. A precessing NiFe ferromagnet injected spins into IrMn spin sinks, and enhanced damping was observed around the IrMn magnetic phase transition. Our data were compared to a recently developed theory and converted into interfacial spin mixing conductance enhancements. By spotting the spin pumping peak, the thickness dependence of the IrMn critical temperature could be determined and the characteristic length for the spin-spin interactions was deduced.

s-Heptazine oligomers: promising structural models for graphitic carbon nitride.

Graphitic carbon nitride (g-CN) has interesting catalytic properties but is difficult to study due to its structure and how it is produced. In this study, linear s-heptazine oligomers were synthesized to serve as well-defined molecular models for g-CN. Cyclic voltammetry, absorption and emission spectroscopies showed a clear shift of properties towards those of g-CN as the number of heptazine units increased. DFT calculations supported the characterizations, and helped refine the properties observed.

Spin-to-charge conversion using Rashba coupling at the interface between non-magnetic materials.

The Rashba effect is an interaction between the spin and the momentum of electrons induced by the spin-orbit coupling (SOC) in surface or interface states. Its potential for conversion between charge and spin currents has been theoretically predicted but never clearly demonstrated for surfaces or interfaces of metals. Here we present experiments evidencing a large spin-charge conversion by the Bi/Ag Rashba interface. We use spin pumping to inject a spin current from a NiFe layer into a Bi/Ag bilayer and we detect the resulting charge current. As the charge signal is much smaller (negligible) with only Bi (only Ag), the spin-to-charge conversion can be unambiguously ascribed to the Rashba coupling at the Bi/Ag interface. This result demonstrates that the Rashba effect at interfaces can be used for efficient charge-spin conversion in spintronics.

Magnetic properties and chiral states of a trimetallic uranium complex.

The magnetic properties of the triangular molecular nanomagnet [UO2L]3 (L = 2-(4-tolyl)-1,3-bis(quinolyl)malondiiminate) have been investigated through electron paramagnetic resonance spectroscopy, high-field magnetization and susceptibility measurements. The experimental findings are well reproduced by a microscopic model including exchange interactions and local crystal fields. These results show that [UO2L]3 is characterized by a non-magnetic ground doublet corresponding to two oppositely twisted chiral arrangements of the uranium moments. The non-axial character of single-ion crystal fields leads to quantum tunneling of the noncollinear magnetization in the presence of a magnetic field applied perpendicularly to the triangle plane.

Biomimetic assembly and activation of [FeFe]-hydrogenases.

Hydrogenases are the most active molecular catalysts for hydrogen production and uptake, and could therefore facilitate the development of new types of fuel cell. In [FeFe]-hydrogenases, catalysis takes place at a unique di-iron centre (the [2Fe] subsite), which contains a bridging dithiolate ligand, three CO ligands and two CN(-) ligands. Through a complex multienzymatic biosynthetic process, this [2Fe] subsite is first assembled on a maturation enzyme, HydF, and then delivered to the apo-hydrogenase for activation. Synthetic chemistry has been used to prepare remarkably similar mimics of that subsite, but it has failed to reproduce the natural enzymatic activities thus far. Here we show that three synthetic mimics (containing different bridging dithiolate ligands) can be loaded onto bacterial Thermotoga maritima HydF and then transferred to apo-HydA1, one of the hydrogenases of Chlamydomonas reinhardtii algae. Full activation of HydA1 was achieved only when using the HydF hybrid protein containing the mimic with an azadithiolate bridge, confirming the presence of this ligand in the active site of native [FeFe]-hydrogenases. This is an example of controlled metalloenzyme activation using the combination of a specific protein scaffold and active-site synthetic analogues. This simple methodology provides both new mechanistic and structural insight into hydrogenase maturation and a unique tool for producing recombinant wild-type and variant [FeFe]-hydrogenases, with no requirement for the complete maturation machinery.

Crossover from spin accumulation into interface states to spin injection in the germanium conduction band.

Electrical spin injection into semiconductors paves the way for exploring new phenomena in the area of spin physics and new generations of spintronic devices. However the exact role of interface states in the spin injection mechanism from a magnetic tunnel junction into a semiconductor is still under debate. In this Letter, we demonstrate a clear transition from spin accumulation into interface states to spin injection in the conduction band of n-Ge. We observe spin signal amplification at low temperature due to spin accumulation into interface states followed by a clear transition towards spin injection in the conduction band from 200 K up to room temperature. In this regime, the spin signal is reduced to a value compatible with the spin diffusion model. More interestingly, the observation in this regime of inverse spin Hall effect in germanium generated by spin pumping and the modulation of the spin signal by a gate voltage clearly demonstrate spin accumulation in the germanium conduction band.

Decoherence window and electron-nuclear cross relaxation in the molecular magnet V15.

Rabi oscillations in the V(15) single molecule magnet embedded in the surfactant (CH(3))(2)[CH(3)(CH(2))(16)CH(2)](2)N(+) have been studied at different microwave powers. An intense damping peak is observed when the Rabi frequency Ω(R) falls in the vicinity of the Larmor frequency of protons ω(N). The experiments are interpreted by a model showing that the damping (or Rabi) time τ(R) is directly associated with decoherence caused by electron-nuclear cross relaxation in the rotating reference frame. This decoherence induces energy dissipation in the range ω(N) - σ(e) < Ω(R) < ω(N), where σ(e) is the mean superhyperfine field induced by protons at V(15). Weaker decoherence without dissipation takes place outside this window. Specific estimations suggest that this rapid cross relaxation in a resonant microwave field, observed for the first time in V(15), should also take place, e.g., in Fe(8) and Mn(12).

Spin-orbit qubits of rare-earth-metal ions in axially symmetric crystal fields.

Contrary to the well-known spin qubits, rare-earth-metal qubits are characterized by a strong influence of crystal field due to large spin-orbit coupling. At low temperature and in the presence of resonance microwaves, it is the magnetic moment of the crystal-field ground state which nutates (for several micros) and the Rabi frequency Omega(R) is anisotropic. Here, we present a study of the variations of Omega(R)(H(0)) with the magnitude and direction of the static magnetic field H(0) for the odd 167Er isotope in a single crystal CaWO(4):Er(3+). The hyperfine interactions split the Omega(R)(H(0)) curve into eight different curves which are fitted numerically and described analytically. These "spin-orbit qubits" should allow detailed studies of decoherence mechanisms which become relevant at high temperature and open new ways for qubit addressing using properly oriented magnetic fields.

Site-specific insertion of nitroxide-spin labels into DNA probes by click chemistry for structural analyses by ELDOR spectroscopy.

A new approach is described for the insertion of nitroxide spin-labels at specific positions within DNA oligomers. The latter bioconjugaison strategy is based on a click chemistry 1,3-dipolar cycloaddition between a spin-labeling reagent, namely the 4-azido-TEMPO, and alkyne modified uridine-containing oligonucleotides. This highly efficient labeling method was applied for site-specific incorporation of two TEMPO units within a set of double-stranded DNA constructs. Then the determination of the inter-nitroxide distances was achieved by using a four-pulses DEER technique that successfully validates the new site-directed spin labeling strategy.

Quantum oscillations in a molecular magnet.

The term 'molecular magnet' generally refers to a molecular entity containing several magnetic ions whose coupled spins generate a collective spin, S (ref. 1). Such complex multi-spin systems provide attractive targets for the study of quantum effects at the mesoscopic scale. In these molecules, the large energy barriers between collective spin states can be crossed by thermal activation or quantum tunnelling, depending on the temperature or an applied magnetic field. There is the hope that these mesoscopic spin states can be harnessed for the realization of quantum bits--'qubits', the basic building blocks of a quantum computer--based on molecular magnets. But strong decoherence must be overcome if the envisaged applications are to become practical. Here we report the observation and analysis of Rabi oscillations (quantum oscillations resulting from the coherent absorption and emission of photons driven by an electromagnetic wave) of a molecular magnet in a hybrid system, in which discrete and well-separated magnetic clusters are embedded in a self-organized non-magnetic environment. Each cluster contains 15 antiferromagnetically coupled S = 1/2 spins, leading to an S = 1/2 collective ground state. When this system is placed into a resonant cavity, the microwave field induces oscillatory transitions between the ground and excited collective spin states, indicative of long-lived quantum coherence. The present observation of quantum oscillations suggests that low-dimension self-organized qubit networks having coherence times of the order of 100 micros (at liquid helium temperatures) are a realistic prospect.

Ferromagnetic spins interaction in poly(m-p-aniline).

Alternating poly(m-p-aniline) can be oxidized to radical cations with spins S = 1/2. For high spin density, ferromagnetic spin interaction is observed, and some of the generated radical cations are found to be in a ground triplet state.

Single-crystal (57)Fe Q-band ENDOR study of the 4 iron-4 sulfur cluster in its reduced [4Fe-4S](1+) state.

(57)Fe Q-band ENDOR has been used to study the [4Fe-4S](1+) state created by gamma irradiation of single crystals of the synthetic model compound [N(C(2)H(5))(4)](2)[Fe(4)S(4)(SCH(2)C(6)H(5))(4)] enriched in (57)Fe. This compound is an excellent biomimetic model of the active sites of many 4 iron-4 sulfur proteins, enabling detailed and systematic studies of its oxidized [4Fe-4S](3+) and reduced [4Fe-4S](1+) paramagnetic states. Taking advantage of the fact that Q-band ENDOR, in contrast with X-Band ENDOR, allows for a very good separation of the (57)Fe transitions from those of the protons, the complete hyperfine tensors of the four iron atoms for the [4Fe-4S](1+) species has been measured with precision. For each iron atom, the electron orbital and electron spin isotropic contributions have been determined separately. Moreover, it is remarkable that two (57)Fe hyperfine tensors attributed to the ferrous pair of iron atoms are very different. In effect, one tensor presents a much larger anisotropic part and a much smaller isotropic part than those of the other. This difference has been interpreted in terms of a differential electron orbital hyperfine interaction among the two ferrous ions.

Formation of a tyrosyl radical intermediate in Proteus mirabilis catalase by directed mutagenesis and consequences for nucleotide reactivity.

Proteus mirabilis catalase (PMC) belongs to the family of NADPH binding catalases. The function of NADPH in these enzymes is still a matter of debate. This study presents the effects of two independent phenylalanine mutations (F194 and F215), located between NADPH and heme in the PMC structure. The phenylalanines were replaced with tyrosines which we predicted could carry radicals in a NADPH-heme electron transfer. The X-ray crystal structures of the two mutants indicated that neither the binding site of NADPH nor the immediate environment of the residues was affected by the mutations. Measurements using H2O2 as a substrate confirmed that the variants were as active as the native enzyme. With equivalent amounts of peroxoacetic acid, wild-type PMC, F215Y PMC, and beef liver catalase (BLC) formed a stable compound I, while the F194Y PMC variant produced a compound I which was rapidly transformed into compound II and a tyrosyl radical. EPR studies showed that this radical, generated by the oxidation of Y194, was not related to the previously observed radical in BLC, located on Y369. In the presence of excess NADPH, compound I was reduced to a resting enzyme (k(obs) = 1.7 min(-1)) in a two-electron process. This was independent of the enzyme's origin and did not require any thus far identified tyrosyl radicals. Conversely, the presence of a tyrosyl radical in F194Y PMC greatly enhanced the oxidation of reduced beta-nicotinamide mononucleotide under a steady-state H2O2 flow with observable compound II. This process could involve a one-electron reduction of compound I via Y194.