We present a detailed ab initio study of the electronic structure and magnetic order of an Fe monolayer on the Ir(001) surface covered by adsorbed oxygen and hydrogen. The results are compared to the clean Fe/Ir(001) system, where recent intensive studies indicated a strong tendency towards an antiferromagnetic order and complex magnetic structures. The adsorption of an oxygen overlayer significantly increases interlayer distance between the Fe layer and the Ir substrate, while the effect of hydrogen is much weaker. We show that the adsorption of oxygen (and also of hydrogen) leads to a p(2$\times $1) antiferromagnetic order of the Fe moments, which is also supported by an investigation based on a disordered local moment state. Simulated scanning tunneling images using the simple Tersoff-Hamann model hint that the proposed p(2$\times $1) antiferromagnetic order could be detected even by non-magnetic tips.
Using first-principles calculations, we systematically study the dissociation of O$_2$ molecules on different ultrathin Pb(111) films. Based on our previous work revealing the molecular adsorption precursor states for O$_2$, we further explore that why there are two nearly degenerate adsorption states on Pb(111) ultrathin films, but no precursor adsorption states exist at all on the Mg(0001) and Al(111) surfaces. And the reason is concluded to be the different surface electronic structures. For the O$_2$ dissociation, we consider both the reaction channels from gas-like and molecularly adsorbe…
Here we report the adsorption behaviour of a water soluble laser dye rhodamine onto ultrathin films prepared by LB technique without altering its photophysical behabiour.
We have grown epitaxial films a few atomic layers thick of iron oxides on ruthenium. We characterize the growth by low energy electron microscopy. Using selected area diffraction and intensity vs. voltage spectroscopy, we detect two distinct phases which are assigned to wustite and magnetite. Spin polarized low energy electron microscopy shows magnetic domain patterns in the magnetite phase at room temperature.
By means of ab initio calculations, we have investigated the effect of H adsorption in the structural, electronic and magnetic properties of ultrathin Co films on Ru(0001). Our calculations predict that H occupies hollow sites preserving the two-dimensional 3-fold symmetry. The formation of a complete H overlayer leads to a very stable surface with strong H-Co bonds. H tends to suppress surface features, in particular, the enhancement of the magnetic moments of the bare film. The H-induced effects are mostly confined to the Co atoms bonded to H, independent of the H coverage or of the thicknes…
We use Ca doping during growth of one and two monolayer thick MgO films on Ag(100) to identify the adsorption sites of individual adatoms with scanning tunneling microscopy. For this we combine atomic resolution images of the bare MgO layer with images of the adsorbates and the substitutional Ca atoms taken at larger tip-sample distance. For Ho atoms, the adsorption sites depend on MgO thickness. On the monolayer, they are distributed on the O and bridge sites according to the abundance of those sites, 1/3 and 2/3 respectively. On the MgO bilayer, Ho atoms populate almost exclusively the O sit…
We present a comprehensive study of the adsorption behavior of iron phthalocyanine on the low-index crystal faces of silver. By combining measurements of the reciprocal space by means of photoelectron momentum mapping and low energy electron diffraction, the real space adsorption geometries are reconstructed. At monolayer coverage ordered superstructures exist on all studied surfaces containing one molecule in the unit cell in case of Ag(100) and Ag(111), and two molecules per unit cell for Ag(110). The azimuthal tilt angle of the molecules against the high symmetry directions of the substrate…
Two-dimensional (2D) superconductors supply important platforms for exploring new quantum physics and high-$T_c$ superconductivity. The intrinsic superconducting properties in the 2D iron-arsenic superconductors are still unknown owing to the difficulties in the preparation of ultrathin samples. Here we report the fabrication and physical investigations of the high quality single-crystalline ultrathin films of the iron-arsenic superconductor KCa$_2$Fe$_4$As$_4$F$_2$. For the sample with the thickness of 2.6$\sim$5 nm (1$\sim$2 unit cells), a sharp superconducting transition at around 30 K (ons…
The adsorption of iron phthalocyanine (FePc) on the passivated H/Si(111) surface is explored from first principles. We find that the organic molecule is predominantly physisorbed with a distance to the surface of $2.6 \pm 0.1$ Angstrom, but also exhibits sizable resonance with the underlying substrate. This establishes the present system as interesting mixed covalent-van-der-Waals-bound test case, which we use to compare the impact of different approaches to van-der-Waals interactions. (Spin-polarized) scanning tunneling microscopy (SP STM) images are simulated, selectively accessing different…
Spin waves can probe the Dzyaloshinskii-Moriya interaction (DMI) which gives rise to topological spin textures, such as skyrmions. However, the DMI has not yet been reported in yttrium iron garnet (YIG) with arguably the lowest damping for spin waves. In this work, we experimentally evidence the interfacial DMI in a 7~nm-thick YIG film by measuring the nonreciprocal spin wave propagation in terms of frequency, amplitude and most importantly group velocities using all electrical spin-wave spectroscopy. The velocities of propagating spin waves show chirality among three vectors, i.e. the film no…
In this work, 6 to 12 nm iron oxide nanoparticles were synthesized and coated with poly(acrylic acid) chains of molecular weight 2100 g/mol. Based on a quantitative evaluation of the dispersions, the bare and coated particles were thoroughly characterized. The number densities of polymers adsorbed at the particle surface and of available chargeable groups were found to be 1.9 +/- 0.3 nm-2 and 26 +/- 4 nm-2, respectively. Occurring via a multi-site binding mechanism, the electrostatic coupling leads to a solid and resilient anchoring of the chains. To assess the efficacy of the particles for po…
Iron pyrite (FeS$_{2}$) is the most abundant metal sulfide on Earth. Owing to its reactivity and catalytic activity, pyrite has been studied in various research fields such as surface science, geochemistry, and prebiotic chemistry. Importantly, native iron-sulfur clusters are typically coordinated by cysteinyl ligands of iron-sulfur proteins. In the present paper, we study the adsorption of L-cysteine and its oxidized dimer, L-cystine, on the FeS$_{2}$ surface, using electronic structure calculations based density functional theory and Raman spectroscopy measurements. Our calculations suggest …
The adsorption kinetics of CO on PdAu bimetallic clusters, containing 140 $\pm$ 12 atoms and a composition varying between 0% and 55% of Pd atoms, is investigated by a pulsed molecular beam method (MBRS). The clusters are grown on a nanostructured ultrathin film of alumina on Ni3Al (111) playing the role of a template which gives a hexagonal array of bimetallic clusters having a sharp size distribution and a uniform composition. The surface concentration calculated, assuming segregation of gold to the surface, varies between 0 and 90% of Au atoms on the surface. From the adsorption-desorption …
We present a comprehensive study of the adsorption of bis(phthalocyaninato)lutetium(III) (LuPc$_2$) on highly oriented pyrolytic graphite(0001) (HOPG). The growth and self-assembly of the molecular layers as well as the electronic structure has been investigated systematically using scanning tunnelling microscopy and scanning tunnelling spectroscopy combined with density functional theory (DFT) calculations and molecular mechanics simulations. We reveal that the adsorption of LuPc$_2$ leads to the formation of a square-like close-packed structure on the almost inert surface of HOPG, which is c…
Defining the magnetic anisotropy for in-plane or out-of-plane easy axis in ferrimagnetic insulators films by controlling the strain, while maintaining high-quality surfaces, is desirable for spintronic and magnonic applications. We investigate ways to tune the anisotropy of amorphous sputtered ultrathin thulium iron garnet (TIG) films, and thus tailor their magnetic properties by the thickness (7.5 to 60 nm), substrate choice (GGG and SGGG), and crystallization process. We correlate morphological and structural properties with the magnetic anisotropy of post-growth annealed films. 30 nm thick …
We report the structural, magnetic, and interfacial spin transport properties of epitaxial terbium iron garnet (TbIG) ultrathin films deposited by magnetron sputtering. High crystallinity was achieved by growing the films on gadolinium gallium garnet (GGG) substrates either at high temperature, or at room temperature followed by thermal annealing, above 750 °C in both cases. The films display large perpendicular magnetic anisotropy (PMA) induced by compressive strain, and tunable structural and magnetic properties through growth conditions or the substrate lattice parameter choice. The ferrima…
Density-functional-theory calculations for the adsorption of molecular nitrogen on ruthenium surface are reported. It is found that nitrogen molecule is adsorbed while standing perpendicular to the triangular surface of ruthenium. The doping by K atoms favours the adsorption of molecular nitrogen. The calculation of the adsorption energy has also been performed on iron and osmium clusters which shows that ruthenium adsorbs better than iron or osmium. It is found that potential for atomic nitrogen is deeper and more stable than that of molecular nitrogen and hence atomic nitrogen is important f…
We report on the structure, magnetization, magnetic anisotropy, and domain morphology of ultrathin yttrium iron garnet (YIG)/Pt films with thickness ranging from 3 to 90 nm. We find that the saturation magnetization is close to the bulk value in the thickest films and decreases towards low thickness with a strong reduction below 10 nm. We characterize the magnetic anisotropy by measuring the transverse spin Hall magnetoresistance as a function of applied field. Our results reveal strong easy plane anisotropy fields of the order of 50-100 mT, which add to the demagnetizing field, as well as wea…
Recently, there have been intense efforts in searching for new topological insulator (TI) materials. Based on first-principles calculations, we find that all the ultrathin Bi (111) films are characterized by a nontrivial Z2 number independent of the film thickness, without the odd-even oscillation of topological triviality as commonly perceived. The stable nontrivial Z2 topology is retained by the concurrent band gap inversions at multiple time-reversal-invariant k-points and associated with the intermediate inter-bilayer coupling of the multi-bilayer Bi film. Our calculations further indicate…
Certain two-dimensional (2D) materials exhibit intriguing properties such as valley polarization, ferroelectricity, superconductivity and charge-density waves. Many of these materials can be manually assembled into atomic-scale multilayer devices under ambient conditions, owing to their exceptional chemical stability. Efforts have been made to add a magnetic degree of freedom to these 2D materials via defects, but only local magnetism has been achieved. Only with the recent discoveries of 2D materials supporting intrinsic ferromagnetism have stacked spintronic devices become realistic. Assembl…
The adsorption of methanol (CH3OH) at the Fe3O4(001)-c(2x2) surface was studied using X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and temperature-programmed desorption (TPD). CH3OH adsorbs exclusively at surface defects sites at room temperature to form hydroxyl groups and methoxy (CH3O) species. Active sites are identified as step edges, iron adatoms, antiphase domain boundaries in the c(2x2) reconstruction, and above Fe atoms incorporated in the subsurface. In TPD, recombinative desorption is observed around 300 K, and a disproportionation reaction to form me…
Ultrathin bismuth-yttrium iron garnet films with tunable magnetic anisotropy
ETH Zurich（苏黎世联邦理工学院）；Université Grenoble Alpes, CNRS, Institut Néel（格勒诺布尔阿尔卑斯大学，法国国家科学研究中心，内耳研究所）；Kyoto University（京都大学）；University of Konstanz（康斯坦茨大学）；Instituto de Nanociencia y Materiales de Aragón, CSIC（阿拉贡纳米科学与材料研究所，西班牙国家研究委员会）；Universidad de Zaragoza（萨拉戈萨大学）
Using ab-initio density functional theory we study the role of interstitial hydrogen on the energetics of the phase transformation of iron from bcc to hcp along Bain's pathway. The impurity creates an internal stress field that can be released through a tetragonal distortion of the lattice, promoting the bcc (ferromagnetic) $\rightarrow$ fcc (frustrated antiferromagnetic) $\rightarrow$ hcp (ferromagnetic) transition. The transformation between crystal systems is accompanied by a drastic magnetic reorganization and sudden variations of the unit cell volume, that can be one of the reasons for em…
Defect engineering of ultrathin gallium nitride via electric fields for advanced electronic, magnetic, and gas sensing applications
Nanyang Technological University（南洋理工大学）；Infineon Technologies Asia Pacific Pte. Ltd.（英飞凌亚太私人有限公司）；China-Singapore International Joint Research Institute（中新国际联合研究院）
Graphene - transition metal phthalocyanine (G-MPc) hybrid systems constitute promising platforms for densely-packed single-molecule magnets (SMMs). Here, we selected iron(II) phthalocyanine (FePc) and investigated its interaction with pristine and defective graphene layers employing density functional theory. Our calculations indicate that thorough proper dehydrogenation of the benzol rings in the FePc molecule its adsorption to graphene is thermodynamically favorable. In general, the presence of anchoring sites on the graphene layer, i.e. point defects, additionally facilitates the adsorption…
We demonstrate an instrument for time-resolved magnetic imaging that is highly sensitive to the in-plane magnetization state and dynamics of thin-film bilayers of yttrium iron garnet (Y3Fe5O12,YIG)/Pt: the time-resolved longitudinal spin Seebeck (TRLSSE) effect microscope. We detect the local, in-plane magnetic orientation within the YIG by focusing a picosecond laser to generate thermally-driven spin current from the YIG into the Pt by the spin Seebeck effect, and then use the inverse spin Hall effect in the Pt to transduce this spin current to an output voltage. To establish the time resolut…
Ultrathin (111)-oriented polar iron oxide films were grown on a Pt(111) single crystal either by the reactive deposition of iron or oxidation of metallic iron monolayers. These films were characterized using low energy electron diffraction, scanning tunneling microscopy and conversion electron Mossbauer spectroscopy. The reactive deposition of Fe led to the island growth of Fe3O4, in which the electronic and magnetic properties of the bulk material were modulated by superparamagnetic size effects for thicknesses below 2 nm, revealing specific surface and interface features. In contrast, the ox…
Semiconducting oxides with reducible cations are ideal platforms for various functional applications in nanoelectronics and catalysts. Here we report an ultrathin monolayer alpha-MoO3 where tunable electronic properties and different gas adsorbing behaviors upon introducing the oxygen vacancies (VO). The unique property of alpha-MoO3 is that it contains three different types of oxygen atoms occupying three Wyckoff sites that are absent in other low-dimensional oxides and provides rich electronic hybridized states. The presence of VO triggers intermediate state in the gap at ~0.59 eV below the …
We report a first-principles calculation that models the effect of iron (Fe) atoms on the adsorption of a tungsten (W) atom on W(100) surfaces. The adsorption of a W atom on a clean W(100) surface is compared with that of a W atom on a W(100) surface covered with a monolayer of Fe atoms. The total energy of the system is computed as the function of the height of the W adatom. Our result shows that the W atom first adsorbs on top of the Fe monolayer. Then the W atom can replace one of the Fe atoms through a path with a moderate energy barrier and reduce its energy further. This intermediate sit…
The ability to precisely control the electronic coupling/decoupling of adsorbates from surfaces is an essential goal. It isimportant for fundamental studies not only in surface science but alsoin several applied domains including, for example, miniaturizedmolecular electronic or for the development of various devices suchas nanoscale biosensors or photovoltaic cells. Here, we provide atomic-scale experimental and theoretical investigations of a semi-insulatinglayer grown on a silicon surface via its epitaxy with CaF2. We showthat, following the formation of a wetting layer, the ensuing organiz…
We report on the self-organized growth of a regular array of Fe nanoclusters on a nanopatterned magnetite surface. Under oxidizing preparation conditions the (111) surface of magnetite exhibits a regular superstructure with three-fold symmetry and a 42 A periodicity. This superstructure represents an oxygen terminated (111) surface, which is reconstructed to form a periodically strained surface. This strain patterned surface has been used as a template for the growth of an ultrathin metal film. A Fe film of 0.5 A thickness was deposited on the substrate at room temperature. Fe nanoclusters are…
The observation of intense visible fluorescence from silver and iron nanoparticles in different solution phases and surface capping is reported here. Metallic silver and iron nanoparticles were obtained by exploding pure silver and iron wires in pure water. Bovine serum albumin protein adsorption on the silver nanoparticles showed an enhanced fluorescence. The presence of poly-vinyl pyrrolidone polymer in the exploding medium resulted in a stabilized growth of iron nanoparticles with enhanced fluorescence intensity. The fluorescence was found to be surface /interface dependant. The fluorescenc…
The segregation behavior of Cr in dilute Fe-Cr alloys is known to be anomalous since the main barrier for surface segregation of Cr in these alloys arises not from the topmost surface layer but from the subsurface layer where the solution energy of Cr is much more endothermic as compared to the topmost surface layer. The Fe-Cr alloys are candidate structural materials for the new generation of nuclear reactors. The surfaces of these alloys will be exposed to hydrogen or its isotopes in these reactors, and although hydrogen is soluble neither in Fe nor in Fe-Cr alloys, it is known that the adso…
We have investigated recrystallization of amorphous Yttrium Iron Garnet (YIG) by annealing in oxygen atmosphere. Our findings show that well below the melting temperature the material transforms into a fully epitaxial layer with exceptional quality, both structural and magnetic.\\ In ferromagnetic resonance (FMR) ultra low damping and extremely narrow linewidth can be observed. For a 56 nm thick layer a damping constant of $α$=(6.63$\pm$1.50)$\cdot$10$^{-5}$ is found and the linewidth at 9.6 GHz is as small as 1.30$\pm$0.05 Oe which are the lowest values for PLD grown thin films reported so fa…
Transition metal ferromagnetic films with perpendicular magnetic anisotropy (PMA) have ferromagnetic resonance (FMR) linewidths that are one order of magnitude larger than soft magnetic materials, such as pure iron (Fe) and permalloy (NiFe) thin films. A broadband FMR setup has been used to investigate the origin of the enhanced linewidth in Ni$|$Co multilayer films with PMA. The FMR linewidth depends linearly on frequency for perpendicular applied fields and increases significantly when the magnetization is rotated into the film plane. Irradiation of the film with Helium ions decreases the PM…
Thin Yttrium Iron Garnet (YIG) is a promising material for integrated magnonics. In order to introduce YIG into nanofabrication processes it is necessary to fabricate very thin YIG films with a thickness well below 100 nm while retaining the extraordinary magnetic properties of the material, especially its long magnon lifetime and spin wave propagation length. Here, we give a brief introduction into the topic and we review and discuss the various results published over the last decade in this area. Especially for ultrathin films it turns out that pulsed layer deposition and sputtering are the …
The atomic interaction and magnetic properties of ultrathin Fe films grown on cleaved and polished MgO(100) surfaces were studied by conversion electron Mössbauer spectroscopy (CEMS) in broad temperature range. Fe with different layer thickness was deposited on MgO substrates. The layers were formed on polished and cleaved substrate surfaces at RT. The analysis of the spectra showed no Fe-O$^{2-}$ interaction in MgO/Fe interface. Iron layers showed different magnetic anisotropy depending on their thickness.
The spin-nematic scenario proposed for the structural instability of iron-based superconductors is studied theoretically within a Ginzburg-Landau approach in epitaxial thin films. The transition temperature and the domains that appear due the interface with the substrate are computed analytically by following a variatonal procedure. It is predicted a cross-over thickness $l_*$ that separates the Kittel regime, in which the size of the domains goes as the square root of the film thickness $l$, from a new ultrathin regime in which the system tends to reach the single-domain state as $l \to 0$. T…
Alkali-metal adsorption on the surface of materials is widely used for in situ surface electron doping, particularly for observing unoccupied band structures by angle-resolved photoemission spectroscopy (ARPES). However, the effects of alkali-metal atoms on the resulting band structures have yet to be fully investigated, owing to difficulties in both experiments and calculations. Here, we combine ARPES measurements on cesium-adsorbed ultrathin bismuth films with first-principles calculations of the electronic charge densities and demonstrate a simple method to evaluate alkali-metal induced ban…
Ligand-Induced Incompatible Curvatures Control Ultrathin Nanoplatelet Polymorphism and Chirality
ARC Centre of Excellence in Exciton Science, School of Chemistry, University of Sydney（悉尼大学化学学院激子科学卓越中心）；The University of Sydney Nano Institute, University of Sydney（悉尼大学纳米研究所）；Univ. Lyon, ENS de Lyon, CNRS, Laboratoire de Chimie（里昂大学，里昂高等师范学校，法国国家科学研究中心，化学实验室）；LadHyX, CNRS, Ecole polytechnique, Institut Polytechnique de Paris（拉迪克斯实验室，法国国家科学研究中心，巴黎综合理工学院，巴黎理工学院）；Univ Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière（里昂大学，克洛德·贝尔纳里昂第一大学，法国国家科学研究中心，光与物质研究所）
Superparamagnetic γ-Fe2O3 nanoparticles (5 nm diameter) were synthesized in water. The bare particles exhibit good colloidal stability at ~ pH 2 because of the strong electrostatic repulsion with a surface charge of +25 mV. The polyacrylic acid (PAA)-coated particles exhibit remarkable colloidal stability at ~ pH 7 with abundant free carboxyl groups as reactive sites for subsequent functionalization. In this work, we used zeta potential analysis, transmission electron microscopy, small angle X-ray scattering, and Inductively coupled plasma mass spectrometry to investigate the adsorption behavi…
Superconductivity (SC) in the Ba-122 family of iron-based compounds can be controlled by aliovalent or isovalent substitutions, applied external pressure, and strain, the combined effects of which are sometimes studied within the same sample. Most often, the result is limited to a shift of the SC dome to different doping values. In a few cases, the maximum SC transition at optimal doping can also be enhanced. In this work, we study the combination of charge doping together with isovalent P substitution and strain by performing ionic gating experiments on BaFe$_2$(As$_{0.8}$P$_{0.2}$)$_2$ ultra…
The step-wise growth of epitaxial Fe on Cu(001)/Si(001), investigated by in-situ polarized neutron reflectometry is presented. A sputter deposition system was integrated into the neutron reflectometer AMOR at the Swiss neutron spallation source SINQ, which enables the analysis of the microstructure and magnetic moments during all deposition steps of the Fe layer. We report on the progressive evolution of the accessible parameters describing the microstructure and the magnetic properties of the Fe film, which reproduce known features and extend our knowledge on the behavior of ultrathin iron fi…
We studied the structural and magnetic properties of \textit{in-situ} grown iron mononitride (FeN) thin films. Initial stages of film growth were trapped utilizing synchrotron based soft x-ray absorption near edge spectroscopy (XANES) at the N $K$-edge and nuclear resonant scattering (NRS). Films were grown using dc-magnetron sputtering, separately at the experimental stations of SXAS beamline (BL01, Indus 2) and NRS beamline (P01, Petra III). It was found that the initial stages of film growth differs from the bulk of it. Ultrathin FeN films, exhibited larger energy separation between the t$_…
Graphene is an ultrathin material, which allows us to control surface phenomena by means of field-effect gating. Among various surface phenomena, photo-oxidation is known to be a facile method to largely control the electronic structure of graphene. In this study, gate controllability of photo-oxidation of graphene is thoroughly examined using a field-effect-transistor configuration. The presence of water molecules enhances gate controllability, which can be explained using water-oxygen co-adsorption picture. In addition, the photo-oxidation reaction evolves from the edge and proceeds towards …
