Helium Ion Microscopy for Reduced Spin Orbit Torque Switching Currents.

Spin orbit torque driven switching is a favorable way to manipulate nanoscale magnetic objects for both memory and wireless communication devices. The critical current required to switch from one magnetic state to another depends on the geometry and the intrinsic properties of the materials used, which are difficult to control locally. Here, we demonstrate how focused helium ion beam irradiation can modulate the local magnetic anisotropy of a Co thin film at the microscopic scale. Real-time in situ characterization using the anomalous Hall effect showed up to an order of magnitude reduction of the magnetic anisotropy under irradiation, with multilevel switching demonstrated. The result is that spin-switching current densities, down to 800 kA cm-2, can be achieved on predetermined areas of the film, without the need for lithography. The ability to vary critical currents spatially has implications not only for storage elements but also neuromorphic and probabilistic computing.

Photon management properties of Yb-doped SnO2 nanoparticles synthesized by the sol-gel technique.

SnO2 is a transparent large band gap semiconductor, particularly interesting for optoelectronic and photovoltaic devices, mainly because its conduction can be easily tuned by doping or by modulating the amount of oxygen vacancies. Besides, rare earth doping was successfully exploited for up conversion properties. Here we report on the functionalization of SnO2 nanoparticles with optically active Yb3+ ions using the sol-gel method, which allows UV to NIR spectral (down) conversion. As starting solutions we used stable non-alkoxide metal-organic compounds, which is rather uncommon. Transmission electron microscopy analysis demonstrated the formation of small well-crystallized nanoparticles while X-ray photoelectron spectroscopy measurements have revealed that the Yb is well inserted in the host matrix and has a 3+ valence state. All nanoparticles present large absorption in the UV-visible range (250 to 550 nm) and a band gap that decreases down to 2.72 eV upon doping. The UV energy converted into NIR on the basis of efficient energy transfer from SnO2 to the Yb3+ ions ranges between 250 and 400 nm. Reference undoped SnO2 nanoparticles with a mean size of 20 nm allow converting UV light into broad visible emission centered at 650 nm. The incorporation of up to 3.5 at% of Yb3+ ions into the SnO2 host matrix results in a spectacular decrease of the nanoparticle size down to 6.6 nm. This allowed also the shift of the photoluminescence to NIR in the 970-1050 nm range. The energy level structure of Yb3+ in SnO2 was successfully determined from the deconvolution of the Yb emission. This emission is significantly enhanced by increasing the doping level. All optical measurements suggest that these nanoparticles can be efficiently used as down-shifting converters.

Tuning photovoltaic response in Bi2FeCrO6 films by ferroelectric poling.

Ferroelectric materials are interesting candidates for future photovoltaic applications due to their potential to overcome the fundamental limits of conventional single bandgap semiconductor-based solar cells. Although a more efficient charge separation and above bandgap photovoltages are advantageous in these materials, tailoring their photovoltaic response using ferroelectric functionalities remains puzzling. Here we address this issue by reporting a clear hysteretic character of the photovoltaic effect as a function of electric field and its dependence on the poling history. Furthermore, we obtain insight into light induced nonequilibrium charge carrier dynamics in Bi2FeCrO6 films involving not only charge generation, but also recombination processes. At the ferroelectric remanence, light is able to electrically depolarize the films with remanent and transient effects as evidenced by electrical and piezoresponse force microscopy (PFM) measurements. The hysteretic nature of the photovoltaic response and its nonlinear character at larger light intensities can be used to optimize the photovoltaic performance of future ferroelectric-based solar cells.

The first lead cobalt phosphite, PbCo2(HPO3)3.

Single crystals of a new lead cobalt phosphite, PbCo2(HPO3)3, have been synthesized using mild hydrothermal techniques and characterized by X-ray diffraction analysis, SQUID magnetic measurements, IR spectroscopy, UV/vis spectroscopy, thermogravimetric analysis, and scanning electron microscopy. PbCo2(HPO3)3 crystallizes in the non-centrosymmetric (NCS) R3m space group, a = 5.3145(15) Å, c = 25.494(7) Å, V = 623.6(4) Å3. The crystal structure of PbCo2(HPO3)3 is based upon 2D heteropolyhedral blocks built up from Co2O9 octahedral dimers and HPO3 pseudo-tetrahedra. Lead cations reside in the interlayer space of the structure. Here, the NCS character results reasonably from the cooperative Pb2+ lone electron pair arrangements, by analogy to the centrosymmetric compound (NH4)2Co2(HPO3)3 with similar but disordered blocks. A local twisting of specific HPO3 groups arises due to unreasonably short HH contacts between two phosphite oxoanions. In terms of the magnetic behavior, the new PbCo2(HPO3)3 phase demonstrates weak antiferromagnetic interactions inside the Co2O9 dimers between cobalt ions as expected from the phosphite µ-O bridges.

Topochemical Reduction of YMnO3 into a Composite Structure.

Topochemical modification methods for solids have shown great potential in generating metastable structures inaccessible through classical synthetic routes. Here, we present the enhanced topotactic reduction of the multiferroic compound YMnO3. At moderate temperature in ammonia flow, the most reduced YMnO3-δ (δ = 0.5) phase could be stabilized. XRD, PND, and HREM results show that phase separation occurs into two intimately intergrown layered sublattices with nominal compositions ∞[YMn2+O2+x](1-2x)+ and ∞[YMn2+O3-x](1-2x)- containing versatile Mn2+ coordinations. The former sublattice shows original AA stacking between Mn layers, while AB stacking in the latter results from oxygen removal from the parent YMnO3 crystal structure.

Photon management properties of rare-earth (Nd,Yb,Sm)-doped CeO2 films prepared by pulsed laser deposition.

CeO2 is a promising material for applications in optoelectronics and photovoltaics due to its large band gap and values of the refractive index and lattice parameters, which are suitable for silicon-based devices. In this study, we show that trivalent Sm, Nd and Yb ions can be successfully inserted and optically activated in CeO2 films grown at a relatively low deposition temperature (400 °C), which is compatible with inorganic photovoltaics. CeO2 thin films can therefore be efficiently functionalized with photon-management properties by doping with trivalent rare earth (RE) ions. Structural and optical analyses provide details of the electronic level structure of the films and of their energy transfer mechanisms. In particular, we give evidence of the existence of an absorption band centered at 350 nm from which energy transfer to rare earth ions occurs. The transfer mechanisms can be completely explained only by considering the spontaneous migration of Ce(3+) ions in CeO2 at a short distance from the RE(3+) ions. The strong absorption cross section of the f-d transitions in Ce(3+) ions efficiently intercepts the UV photons of the solar spectrum and therefore strongly increases the potential of these layers as downshifters and downconverters.

BaCoO2.22: the most oxygen-deficient certified cubic perovskite.

The cubic BaCoO(∼2.2) was announced in the early 50's as the final product of high temperature self-reduction within the BaCoO(3-δ) series. However, apart from this report no clear characterization has been provided to date. Here, we confirm after the preparation of single crystal and powder samples that in this compound the ratio of oxygen vacancies is close to 27% in absence of any long range ordering. It follows that BaCoO(2.22) appears as the most oxygen deficient cubic perovskite stabilized at room temperature, its tolerance factor being displaced close to 1 by the combination of large Ba(2+) and Co(2/3+) ions in the A and B sites. The tolerance factor plays a limiting role for re-oxidation and fluorination using topochemical routes, despite the high concentration of available vacancies. Single crystal XRD data and DFT structural relaxation show that the Co sites are off-centered inside pseudo-tetrahedra leading to reinforced magnetic exchanges. Robust antiferromagnetic ordering is suggested to occur above 400 K while this compound shows a semi-conducting behavior. It was also possible to prepare an even more reduced mixed metallic phase of formula BaCo(0.5)Fe(0.5)O(2.16).

pH controlled pathway and systematic hydrothermal phase diagram for elaboration of synthetic lead nickel selenites.

The PbO-NiO-SeO2 ternary system was fully studied using constant hydrothermal conditions at 473 K. It yields the establishment of the corresponding phase diagram using a systematic assignment of reaction products by both powder and single-crystal X-ray diffraction. It leads to the preparation of three novel lead nickel selenites, α-PbNi(SeO3)2 (I), ß-PbNi(SeO3)2 (II), and PbNi2(SeO2OH)2(SeO3)2 (III), and one novel lead cobalt selenite, α-PbCo(SeO3)2 (IV), which have been structurally characterized. The crystal structures of the α-forms I, IV, and III are based on a 3D complex nickel selenite frameworks, whereas the ß-PbNi(SeO3)2 modification (II) consists of nickel selenite sheets stacked in a noncentrosymmetric structure, second-harmonic generation active. The pH value of the starting solution was shown to play an essential role in the reactive processes. Magnetic measurements of I, III, and IV are discussed.

Revised Bi/M layered oxo-sulfate (M = Co, Cu): a structural and magnetic study.

The combination of oxo-bismuthite slabs with counter oxo-anions main often leads to a series of layered Sillen-related compounds. For electroneutrality, it is convenient that the structure incorporates aliovalent cations such as Bi(3+)/M(2+) ions that could be confined either in the Bi/O slabs or in the interleave. In the case of SO4(2-) oxo-anions, only two compounds have been reported for M = Co, Cu, while interesting magnetic topologies emerge in absence of any prior characterization. Our reinvestigation of these systems using crystal growth in Bi2O3 flux led to the full structural characterization of [Bi2CoO3](SO4) (I) and [Bi6.2367Cu1.6O8](SO4)3 (II), which both exhibit pleated [Bi/M/O] slabs running in doubled cells comparatively to previous reports. (I) shows an interesting weak ferromagnetism (∼0.2 µB/Co) below 17 K arising from Dzyaloshinskii-Moriya interactions in Co(2+) zigzag chains, while (II) is essentially a paramagnet despite the presence of Cu2O6 dimers. Finally in the novel [Bi6O6](CoO2)(SO4)2 (III), the Co(2+) ions are ordered with sulfate in the interleaves, leading to a noncentrosymmetric crystal structure.

Slow spin dynamics between ferromagnetic chains in a pure-inorganic framework.

The crystal structure of the new phase BaCo(II)2(As(III)3O6)2·2(H2O) is built from the stacking of infinite [BaCo2(As3O6)2·H2O] sheets containing ∞[Co(II)O4](6-) chains interconnected by perpendicular ∞[As(III)O2](-) chains. It shows a metamagnetic transition below ∼9 K at a critical field of ∼0.11 T, leading to a moment value of 70% of the expected saturation, related to the spin flip between individual robust canted ferromagnetic chains. We propose a field-dependent scenario with magnetic moments lying in the Co(II)O6 octahedral basal planes, fully compatible with our experimental results. Magnetic measurements under ac-field show slow spin dynamics with an intrinsic single-chain magnet (SCM)-like component slightly modified in the field-aligned regime. The characteristic relaxation time and energy barrier are about τo = 5.1 × 10(-10) s and Δτ = 35.3 K at H(dc) = 0, respectively, which falls close to values found for other (but organometallic) SCM Co(II) chains. This magnetic behavior is unique in the field of pure-inorganic compounds.

Effect of the nanometric scale thickness on the magnetization steps in Ca3Co2O6 thin films.

We report on the effect of the film thickness on the magnetic properties of Ca3Co2O6films with an emphasis on the magnetization steps usually observed in the M-H curves below 10 K. Films with thicknesses between 35 and 200 nm all present two magnetic transitions at about T(C1) = 22 K and T(C2) = 10 K, corresponding to a 3D long range ferrimagnetic order and the transition to the formation of a frozen spin state, respectively. The magnetization curves at 10 K exhibit the expected stepped variation. However, by decreasing the thickness below a critical value of about 60 nm, no magnetization plateau is observed when the M-H curve is recorded at 2 K. Moreover, an additional transition in the susceptibility curve is observed at 45 K. These changes can be attributed to the reduced coherence length of the propagation vector along and perpendicular to the chains, and are supported by the magnetization relaxation measurements which indicate a reduction of the relaxation time. These results are helpful for understanding the origin of the magnetization steps in the one-dimensional Ca3Co2O6 cobaltite and confront the theoretical models aimed at explaining the magnetic properties in this system.

Evidence of superparamagnetic co clusters in pulsed laser deposition-grown Zn0.9Co0.1O thin films using atom probe tomography.

Nanosized Co clusters (of about 3 nm size) were unambiguously identified in Co-doped ZnO thin films by atom probe tomography. These clusters are directly correlated to the superparamagnetic relaxation observed by ZFC/FC magnetization measurements. These analyses provide strong evidence that the room-temperature ferromagnetism observed in the magnetization curves cannot be attributed to the observed Co clusters. Because there is no experimental evidence of the presence of other secondary phases, our results reinforce the assumption of a defect-induced ferromagnetism in Co-doped ZnO diluted magnetic semiconductors.

Correlation of structural properties with energy transfer of Eu-doped ZnO thin films prepared by sol-gel process and magnetron reactive sputtering.

We investigated the structural and optical properties of Eu-doped ZnO thin films made by sol-gel technique and magnetron reactive sputtering on Si (100) substrate. The films elaborated by sol-gel process are polycrystalline while the films made by sputtering show a strongly textured growth along the c-axis. X-ray diffraction patterns and transmission electron microscopy analysis show that all samples are free of spurious phases. The presence of Eu(2+) and Eu(3+) into the ZnO matrix has been confirmed by x-ray photoemission spectroscopy. This means that a small fraction of Europium substitutes Zn(2+) as Eu(2+) into the ZnO matrix; the rest of Eu being in the trivalent state. This is probably due to the formation of Eu(2)O(3) oxide at the surface of ZnO particles. This is at the origin of the strong photoluminescence band observed at 2 eV, which is characteristic of the (5)D(0)-->(7)F(2) Eu(3+) transition. In addition the photoluminescence excitonic spectra showed efficient energy transfer from the ZnO matrix to the Eu(3+) ion, which is qualitatively similar for both films although the sputtered films have a better structural quality compared to the sol-gel process grown films.

Formation of ferrimagnetic films with functionalized magnetite nanoparticles using the Langmuir-Blodgett technique.

The formation of ferrimagnetic films of 39 nm magnetite nanoparticles functionalized by stilbene derivatives has been studied using the Langmuir-Blodgett technique. The stilbene moieties are grafted to the particles either via a phosphonate or a carboxylate group; in both cases the nanoparticles display similar isotherms although the microscopic initial and final states of the films are different. Two different mechanisms of film formation are proposed, based on the inorganic-organic bond stability.