Nanostructured Au(111)/Oxide epitaxial heterostructures with tailoring plasmonic response by a one-step strategy

In this work, we present a strategy for developing epitaxial incommensurate nanostructured Au/oxide heterostructures with tunable plasmonic response. Previously, high-quality single-phase and single-oriented alfa-Fe2O3(0001) thin films were achieved, which have been used as a template for noble-metal epitaxial deposition. The complex systems have been grown by pulsed laser deposition on two different types of oxide substrates: alfa-Al2O3(0001) and SrTiO3(111). A one-step procedure has been achieved tailoring the isolated character and the morphological features of Au nanostructures through the substrate temperature during Au growth, without altering the structural characteristics of the hematite layer that is identified as a single iron oxide phase. The epitaxial character and the lattice coupling of Au/oxide bilayers are mediated through the sort of oxide substrate. Single-oriented Au(111) islands are disposed with a rotation of 30° between their crystallographic axes and those of alfa-Fe2O3(0001). The Au(111) and SrTiO3(111) lattices are collinear, while a rotation of 30° happens with respect to the alfa-Al2O3(0001) lattice. The crystallographic domain size and crystalline order of the hematite structure and the Au nanostructured layer are dependent on the substrate type and the Au growth temperature, respectively. Besides, the functional character of the complex systems has been tested. The localized surface plasmons related to Au nanostructures are excited and controlled through the fabrication parameters, tuning the optical resonance with the degree of Au nanostructuring.This work was supported by the Ministerio Español de Ciencia, Innovación y Universidades (MCIU), and the Consejo Superior de Investigaciones Cientificas (CSIC) through the project PIE-2010 6 OE 013. J.L.-S. and E.E. acknowledge the FPI fellowship and the Torres Quevedo contract (ref: PTQ-14-07289). The ESRF, MCIU, and CSIC are acknowledged for the provision of synchrotron radiation facilities. The authors thank Dr M.A. García for the useful discussion about the plasmonic results and Carlos Beltrán for technical support during the experiments at the BM25 beamline at The ESRF

Femtosecond laser thinning for resistivity control of tungsten ditelluride thin-films synthesized from sol-gel deposited tungsten oxide

In this work we present a route for fabricating WTe2 thin-films together with femtosecond laser post processing, enabling to finely control the conductivity. First, we produce amorphous films of WO3 on Si by spin-coating a sol-gel precursor followed by a consolidating annealing and a reduction process in partial H2 atmosphere, leading to porous metallic tungsten cluster layers. To achieve WTe2, the films were exposed to the chalcogen vapours by isothermal closed space vapor transport. The formation of a tungsten ditelluride film composed of piled crystals could be confirmed and a gradient of surface rich Te identified through hard X-ray photoelectron spectroscopy. Finally, it is demonstrated that resistivity can be changed from 0.2 mΩ.m to 1 mΩ.m, while keeping the material characteristics. An anisotropic conductivity can be induced by direct selective thinning with fs laser writing (350 fs pulse duration, 515 nm laser wavelength) of 1D stripes. The obtained results, demonstrate that laser processing is a promising thin-film post-processing technique that can be applied to 2D transition metal dichalcogenide thin filmsPID2020–112770RB-C22, S2018/NMT-4291 TEC2SPACE, CSIC13-4E-179

Double-cell superstructure and vacancy ordering in tensile-strained metallic thin films of P r0.50 C a0.50Co O3 on LaAl O3

The Pr-based cobaltate Pr0.5Ca0.5CoO3 (PCCO) presents in bulk form a singular simultaneous valence and spin-state transition that turns the metallic state into insulator, and displays a large and ultrafast photoresponse in the insulating phase. Epitaxial thin films of PCCO have been grown by deposition on LaAlO3(001) (LAO) substrate, chosen to minimize the mismatch with the film. The films grow epitaxially with two times the substrate periodicity (2a0×2a0×2a0) and the long perovskite axis perpendicular to the surface. We report a reduction of the structural symmetry from Pnma (bulk) to P212121 (film). The P212121 symmetry revealed by synchrotron x ray remains at low temperatures. These PCCO films are metallic, and ferromagnetic below TC=170K, confirming the stabilization of excited Co3+ spin states and the suppression of the concurrent Co spin-state, valence, and metal-insulator transitions. Z-contrast imaging and electron-energy-loss spectroscopy elemental maps reveal long-range ordered oxygen vacancy planes unexpectedly stacking parallel to the interface, in spite of the tensile character of the PCCO/LAO heterostructure. In contrast to the general tendency reported for strained La0.5Sr0.5CoO3-d (LSCO) films, we show that a nominal tensile strain can be also compatible with the presence of alternating O vacancy planes parallel to the interface, instead of perpendicular to it. That occurs thanks to the double cell of the film and the formation of the (1/2, 1/2, 1/2) superstructure studied in this work. These results expand the possibilities of controlling interfacial physical properties via engineering of ordered oxygen-defect structures in strongly correlated oxides

Improving the co and ch4 gas sensor response at room temperature of alpha-fe2o3(0001) epitaxial thin films grown on srtio3(111) incorporating au(111) islands

In this work, the functional character of complex -Fe2O3(0001)/SrTiO3(111) and Au(111) islands/ -Fe2O3(0001)/SrTiO3(111) heterostructures has been proven as gas sensors at room temperature. Epitaxial Au islands and -Fe2O3 thin film are grown by pulsed laser deposition on SrTiO3(111) substrates. Intrinsic parameters such as the composition, particle size and epitaxial character are investigated for their influence on the gas sensing response. Both Au and -Fe2O3 layer show an island-type growth with an average particle size of 40 and 62 nm, respectively. The epitaxial and incommensurate growth is evidenced, confirming a rotation of 30 between the in-plane crystallographic axes of -Fe2O3(0001) structure and those of SrTiO3(111) substrate and between the in-plane crystallographic axes of Au(111) and those of -Fe2O3(0001) structure. -Fe2O3 is the only phase of iron oxide identified before and after its functionalization with Au nanoparticles. In addition, its structural characteristics are also preserved after Au deposition, with minor changes at short-range order. Conductance measurements of Au(111)/ -Fe2O3(0001)/SrTiO3(111) system show that the incorporation of epitaxial Au islands on top of the -Fe2O3(0001) layer induces an enhancement of the gas-sensing activity of around 25% under CO and 35% under CH4 gas exposure, in comparison to a bare -Fe2O3(0001) layer grown on SrTiO3(111) substrates. In addition, the response of the heterostructures to CO gas exposure is around 5–10% higher than to CH4 gas in each case.This work has been supported by the Ministerio Español de Ciencia e Innovación (MICINN) and the Consejo Superior de Investigaciones Cientificas (CSIC) through the projects PIE-2010-OE-013- 200014, PIE 2021-60-E-030 and RTI2018-095303-A-C52. The ESRF, MICINN and CSIC are acknowledged for the provision of synchrotron radiation facilities. A.S. acknowledges financial support from Comunidad de Madrid for an “Atracción de Talento Investigador” Contract (2017-t2/IND5395)

Competition between covalent and non-covalent grafting of fluorescein isothiocyanate on double-walled carbon nanotubes: a quantitative approach

The functionalization of carbon nanotubes with fluorescent molecules is a standard procedure in many toxicity studies aiming at knowing their distribution within cells or whole organisms. Nevertheless, there is a lack of knowledge concerning the efficiency of the grafting processes, and more specifically concerning the question of the competition between covalent and non-covalent grafting. In this work, we investigated the grafting process of the fluorescein isothiocyanate (FITC) onto double-walled carbon nanotubes (DWNTs) using X-ray photoelectron spectroscopy, inelastic neutron scattering spectroscopy and computational simulations.We demonstrated that both covalent and non-covalent grafting occurred during the functionalization with the FITC. Moreover, we showed that a significant fraction of the fluorophore remained simply adsorbed onto the DWNTs despite thorough washing steps, which raises concerning questions about the use of this fluorophore in some toxicity studies and its possible ability to mislead their conclusions

Large-area van der Waals epitaxy and magnetic characterization of Fe3GeTe2films on graphene

Scalable fabrication of magnetic 2D materials and heterostructures constitutes a crucial step for scaling down current spintronic devices and the development of novel spintronic applications. Here, we report on van der Waals (vdW) epitaxy of the layered magnetic metal Fe3GeTe2 (FGT) - a 2D crystal with highly tunable properties and a high prospect for room temperature ferromagnetism (FM) - directly on graphene by employing molecular beam epitaxy. Morphological and structural characterization confirmed the realization of large-area, continuous FGT/graphene heterostructure films with stable interfaces and good crystalline quality. Furthermore, magneto-transport and x-ray magnetic circular dichroism investigations confirmed a robust out-of-plane FM in the layers, comparable to state-of-the-art exfoliated flakes from bulk crystals. These results are highly relevant for further research on wafer-scale growth of vdW heterostructures combining FGT with other layered crystals such as transition metal dichalcogenides for the realization of multifunctional, atomically thin devices

Characterization of a robust Co-II fluorescent complex deposited intact on HOPG

The new diimine fluorescent ligand ACRI-1 based on a central acridine yellow core is reported along with its coordination complex [Co-2(ACRI-1)(2)] (1), a fluorescent weak ferromagnet. Due to the strong fluorescence of the acridine yellow fluorophore, it is not completely quenched when the ligand is coordinated to Co-II. The magnetic properties of bulk complex 1 and its stability in solution have been studied. Complex 1 has been deposited on highly ordered pyrolitic graphite (HOGP) from solution. The thin films prepared have been characterized by AFM, time-of-flight secondary ion mass spectrometry (TOF-SIMS), grazing incidence X-ray diffraction (GIXRD), X-ray absorption spectroscopy (XAS), X-ray magnetic circular dichroism (XMCD) and theoretical calculations. The data show that the complex is robust and remains intact on the surface of graphite

Investigation of the grafting of fluorophores onto double-walled carbon nanotubes: the influence of the geometry of the molecules

The functionalization of nanoparticles is nowadays a standard procedure for many applications. Carbon nanotubes are no exception, and their functionalization has become an important part of the research effort these past decades. Nevertheless, there is still a lack of knowledge concerning the efficiency of the grafting processes, and more specifically concerning the question of the competition between covalent and non-covalent grafting when functionalized for example with aromatic fluorescent molecules. In a previous article, we investigated the grafting of fluorescein isothiocyanate onto double-walled carbon nanotubes. In order to explore the influence of the geometry of the fluorophore on the efficiency of the grafting processes, this work investigated the grafting of a streptocyanine onto the same carbon nanotubes using a combination of X-ray photoelectron spectroscopy, inelastic neutron scattering spectroscopy and computational simulations. The selected streptocyanine presents a very different geometry compared to FITC. Nevertheless, we show that, as in the case of FITC, both covalent and non-covalent grafting occurred simultaneously and that a comparable fraction of the fluorophore remained simply adsorbed onto the DWNTs despite thorough washings, indicating that the geometry of the streptocyanine did not exhibit the expected influence on the grafting process efficiency

Formation of titanium monoxide (001) single-crystalline thin film induced by ion bombardment of titanium dioxide (110)

© 2015 Macmillan Publishers Limited. All rights reserved. A plethora of technological applications justify why titanium dioxide is probably the most studied oxide, and an optimal exploitation of its properties quite frequently requires a controlled modification of the surface. Low-energy ion bombardment is one of the most extended techniques for this purpose and has been recently used in titanium oxides, among other applications, to favour resistive switching mechanisms or to form transparent conductive layers. Surfaces modified in this way are frequently described as reduced and defective, with a high density of oxygen vacancies. Here we show, at variance with this view, that high ion doses on rutile titanium dioxide (110) induce its transformation into a nanometric and single-crystalline titanium monoxide (001) thin film with rocksalt structure. The discovery of this ability may pave the way to new technical applications of ion bombardment not previously reported, which can be used to fabricate heterostructures and interfaces.Peer Reviewe