Surface nanopatterning by ion beam irradiation: compositional effects.

Surface nanopatterning induced by ion beam irradiation (IBI) has emerged as an effective nanostructuring technique since it induces patterns on large areas of a wide variety of materials, in short time, and at low cost. Nowadays, two main subfields can be distinguished within IBI nanopatterning depending on the irrelevant or relevant role played by the surface composition. In this review, we give an up-dated account of the progress reached when surface composition plays a relevant role, with a main focus on IBI surface patterning with simultaneous co-deposition of foreign atoms. In addition, we also review the advances in IBI of compound surfaces as well as IBI systems where the ion employed is not a noble gas species. In particular, for the IBI with concurrent metal co-deposition, we detail the chronological evolution of these studies because it helps us to clarify some contradictory early reports. We describe the main patterns obtained with this technique as a function of the foreign atom deposition pathway, also focusing in those systematic studies that have contributed to identify the main mechanisms leading to the surface pattern formation and development. Likewise, we explain the main theoretical models aimed at describing these nanopattern formation processes. Finally, we address two main special features of the patterns induced by this technique, namely, the enhanced pattern ordering and the possibility to produce both morphological and chemical patterns.

Radio- and nano-chemistry of aqueous Ga(iii) ions anchored onto graphene oxide-modified complexes.

The gallium-68 radiolabelling of new functional graphene oxide composites is reported herein along with kinetic stability investigations of the radio-nanohybrids under different environments and insights into their surface characteristics by SEM and XPS. The present work highlights the potential of graphene oxides as nanocarriers for small molecules such as bis(thiosemicarbazonato) complexes to act as multifunctional platforms for rapid and effective radioimaging agent incorporation.

Superparamagnetic nanosorbent for water purification: Assessment of the adsorptive removal of lead and methyl orange from aqueous solutions.

The present study describes the preparation of 50.3 nm superparamagnetic nanosorbents with high surface area for the adsorptive removal of lead and methyl orange from water. This material is based on the surface modification of iron oxide superparamagnetic nanoparticles with a double-shell coating of mesoporous silica whose porosity was increased up to 570 m2/g by the addition of a porogenic material and its calcination. The adsorptive performance of the nanosorbent was evaluated as a function of several parameters (e.g. solution pH, pollutant initial concentration, and contact time), concluding that pHs around 5 are needed to avoid precipitation of Pb2+ as Pb(OH)2 and the equilibrium adsorption capacity is reached after 2 h in all cases. The experimental data on the adsorption capacity of lead and methyl orange onto the nanosorbent were fit to a pseudo-second order kinetic model and Langmuir isotherm model. The maximum adsorption capacity value increases from 35 up to 50 mg/gNS for lead removal with increasing nanosorbent surface area. Contrary, for methyl orange the maximum adsorption goes up to 240 mg/gNS, indicating a larger nanosorbent surface affinity for the organic matter that is able to diffuse through the silica pores as probed by the intraparticle diffusion model. In addition, we found an good reusability (100% recovering after 4 sorption/desorption cycles for methyl orange removal), which makes of this magnetic nanosorbent suitable for remediation technologies.

Direct Patterning of p-Type-Doped Few-layer WSe2 Nanoelectronic Devices by Oxidation Scanning Probe Lithography.

Direct, robust, and high-resolution patterning methods are needed to downscale the lateral size of two-dimensional materials to observe new properties and optimize the overall processing of these materials. In this work, we report a fabrication process where the initial microchannel of a few-layer WSe2 field-effect transistor is treated by oxygen plasma to form a self-limited oxide layer on top of the flake. This thin oxide layer has a double role here. First, it induces the so-called p-doping effect in the device. Second, it enables the fabrication of oxide nanoribbons with controlled width and depth by oxidation scanning probe lithography (o-SPL). After the removal of the oxides by deionized H2O etching, a nanoribbon-based field-effect transistor is produced. Oxidation SPL is a direct writing technique that minimizes the use of resists and lithographic steps. We have applied this process to fabricate a 5 nm thick WSe2 field-effect transistor, where the channel consists in an array of 5 parallel 350 nm half-pitch nanoribbons. The electrical measurements show that the device presents an improved conduction level compared to the starting thin-layer transistor and a positive threshold voltage shift associated to the p-doping treatment. The method enables to pattern devices with sub-50 nm feature sizes. We have patterned an array of 10 oxide nanowires with 36 nm half-pitch by oxidation SPL.

Size-selective breaking of the core-shell structure of gallium nanoparticles.

Core-shell gallium nanoparticles (Ga NPs) have recently been proposed as an ultraviolet plasmonic material for different applications but only at room temperature. Here, the thermal stability as a function of the size of the NPs is reported over a wide range of temperatures. We analyze the chemical and structural properties of the oxide shell by x-ray photoelectron spectroscopy and atomic force microscopy. We demonstrate the inverse dependence of the shell breaking temperature with the size of the NPs. Spectroscopic ellipsometry is used for tracking the rupture and its mechanism is systematically investigated by scanning electron microscopy, grazing incidence x-ray diffraction and cathodoluminescence. Taking advantage of the thermal stability of the NPs, we perform complete oxidations that lead to homogenous gallium oxide NPs. Thus, this study set the physical limits of Ga NPs to last at high temperatures, and opens up the possibility to achieve totally oxidized NPs while keeping their sphericity.

Surface morphology of molybdenum silicide films upon low-energy ion beam sputtering.

The surface morphology of molybdenum silicide (Mo x Si1-x ) films has been studied after low-energy Ar+ ion beam sputtering (IBS) to explore eventual pattern formation on compound targets and, simultaneously, gather information about the mechanisms behind silicide-assisted nanopatterning of silicon surfaces by IBS. For this purpose, Mo x Si1-x films with compositions below, equal and above the MoSi2 stoichiometry (x = 0.33) have been produced by magnetron sputtering, as assessed by Rutherford backscattering spectrometry (RBS). The surface morphology of silicon and silicide films before and after IBS has been imaged by atomic force microscopy (AFM), comprising conditions where typical nanodot or ripple patterns emerge on the former. In the case of irradiated Mo x Si1-x surfaces, AFM shows a marked surface smoothing at normal incidence with and without additional Mo incorporation (the former results in nanodot patterns on Si). The morphological analysis also provides no evidence of ion-induced phase separation in irradiated Mo x Si1-x . Contrary to silicon, Mo x Si1-x surfaces also do not display ripple formation for (impurity free) oblique irradiations, except at grazing incidence conditions where parallel ripples emerge in a more evident fashion than in the Si counterpart. By means of RBS, irradiated Mo x Si1-x films with 1 keV Ar+ at normal incidence have also been used to measure experimentally the (absolute) sputtering yield and rate of Si and Mo x Si1-x materials. The analysis reveals that, under the present working conditions, the erosion rate of silicides is larger than for silicon, supporting simulations from the TRIDYN code. This finding questions the shielding effect from silicide regions as roughening mechanism in metal-assisted nanopatterning of silicon. On the contrary, the results highlight the relevance of in situ silicide formation. Ripple formation on Mo x Si1-x under grazing incidence is also attributed to the dominance of sputtering effects under this geometry. In conclusion, our work provides some insights into the complex morphological evolution of compound surfaces and solid experimental evidences regarding the mechanisms behind silicide-assisted nanopatterning.

Concurrent segregation and erosion effects in medium-energy iron beam patterning of silicon surfaces.

We have bombarded crystalline silicon targets with a 40 keV Fe+ ion beam at different incidence angles. The resulting surfaces have been characterized by atomic force, current-sensing and magnetic force microscopies, scanning electron microscopy, and x-ray photoelectron spectroscopy. We have found that there is a threshold angle smaller than 40° for the formation of ripple patterns, which is definitely lower than those frequently reported for noble gas ion beams. We compare our observations with estimates of the value of the critical angle and of additional basic properties of the patterning process, which are based on a continuum model whose parameters are obtained from binary collision simulations. We have further studied experimentally the ripple structures and measured how the surface slopes change with the ion incidence angle. We explore in particular detail the fluence dependence of the pattern for an incidence angle value (40°) close to the threshold. Initially, rimmed holes appear randomly scattered on the surface, which evolve into large, bug-like structures. Further increasing the ion fluence induces a smooth, rippled background morphology. By means of microscopy techniques, a correlation between the morphology of these structures and their metal content can be unambiguously established.

Tunable plasmonic resonance of gallium nanoparticles by thermal oxidation at low temperaturas.

The effect of the oxidation of gallium nanoparticles (Ga NPs) on their plasmonic properties is investigated. Discrete dipole approximation has been used to study the wavelength of the out-of-plane localized surface plasmon resonance in hemispherical Ga NPs, deposited on silicon substrates, with oxide shell (Ga2O3) of different thickness. Thermal oxidation treatments, varying temperature and time, were carried out in order to increase experimentally the Ga2O3 shell thickness in the NPs. The optical, structural and chemical properties of the oxidized NPs have been studied by spectroscopic ellipsometry, scanning electron microscopy, grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy. A clear redshift of the peak wavelength is observed, barely affecting the intensity of the plasmon resonance. A controllable increase of the Ga2O3 thickness as a consequence of the thermal annealing is achieved. In addition, simulations together with ellipsometry results have been used to determine the oxidation rate, whose kinetics is governed by a logarithmic dependence. These results support the tunable properties of the plasmon resonance wavelength in Ga NPs by thermal oxidation at low temperatures without significant reduction of the plasmon resonance intensity.

Core@shell, Au@TiOx nanoparticles by gas phase synthesis.

Herein, gas phase synthesis and characterization of multifunctional core@shell, Au@TiOx nanoparticles have been reported. The nanoparticles were produced via a one-step process using a multiple-ion cluster source under a controlled environment that guaranteed the purity of the nanoparticles. The growth of the Au cores (6 nm diameter) is stopped when they pass through the Ti plasma where they are covered by an ultra-thin (1 nm thick) and homogeneous titanium shell that is oxidized in-flight before the soft-landing of the nanoparticles. The Au cores were found to be highly crystalline with icosahedral (44%) and decahedral (66%) structures, whereas the shell, mainly composed of TiO2 (79%), was not ordered. The highly electrical insulating behaviour of the titanium oxide shell was confirmed by the charging effect produced during X-ray photoemission spectroscopy.

Self-organised silicide nanodot patterning by medium-energy ion beam sputtering of Si(100): local correlation between the morphology and metal content.

We have produced self-organised silicide nanodot patterns by medium-energy ion beam sputtering (IBS) of silicon targets with a simultaneous and isotropic molybdenum supply. Atomic force microscopy (AFM) studies show that these patterns are qualitatively similar to those produced thus far at low ion energies. We have determined the relevance of the ion species on the pattern ordering and properties. For the higher ordered patterns produced by Xe(+) ions, the pattern wavelength depends linearly on the ion energy. The dot nanostructures are silicide-rich as assessed by x-ray photoelectron spectroscopy (XPS) and emerge in height due to their lower sputtering yield, as observed by electron microscopy. Remarkably, a long wavelength corrugation is observed on the surface which is correlated with both the Mo content and the dot pattern properties. Thus, as assessed by electron microscopy, the protrusions are Mo-rich with higher and more spaced dots on their surface whereas the valleys are Mo-poor with smaller dots that are closer to each other. These findings indicate that there is a correlation between the local metal content of the surface and the nanodot pattern properties both at the nanodot and the large corrugation scales. These results contribute to advancing the understanding of this interesting nanofabrication method and aid in developing a comprehensive theory of nanodot pattern formation and evolution.

Adsorption and Coupling of 4-aminophenol on Pt(111) surfaces.

We have deposited 4-aminophenol on Pt(111) surfaces in ultra-high vacuum and studied the strength of its adsorption through a combination of STM, LEED, XPS and ab initio calculations. Although an ordered (2√3×2√3)R30° phase appears, we have observed that molecule-substrate interaction dominates the adsorption geometry and properties of the system. At RT the high catalytic activity of Pt induces aminophenol to lose the H atom from the hydroxyl group, and a proportion of the molecules lose the complete hydroxyl group. After annealing above 420K, all deposited aminophenol molecules have lost the OH moiety and some hydrogen atoms from the amino groups. At this temperature, short single-molecule oligomer chains can be observed. These chains are the product of a new reaction that proceeds via the coupling of radical species that is favoured by surface diffusion.

Influence of metal co-deposition on silicon nanodot patterning dynamics during ion-beam sputtering.

We address the impact of metal co-deposition in the nanodot patterning dynamics of Si(100) surfaces under normal-incidence 1 keV Ar(+) ion-beam sputtering (IBS). In particular, the effect of both the metal nature (Fe or Mo) and flux has been studied. Morphological and compositional evolution were followed by atomic force microscopy (AFM) and Rutherford backscattering spectrometry, respectively. For the same type of impurity, the dynamics is faster for a higher co-deposition flux, which also drives to larger asymptotic roughness and wavelength. Mo co-deposition yields rougher surfaces for a lower metal coverage than Fe and, remarkably, higher ordered patterns. X-ray photoelectron spectroscopy reveals the formation of silicide bonds even before pattern onset, stressing the relevant role of the affinity of the co-deposited metals for silicon. Further, current-sensing AFM performed at the initial and asymptotic stages indicates that the nanodot structures are metal-rich, resulting in coupled compositional and morphological patterns. These results are discussed in terms of phase segregation, morphology-driven local flux variations of impurities and silicide formation. This analysis reveals that the underlying (concurrent) mechanisms of pattern formation are complex since many processes can come into play with a different relative weight depending on the specific patterning conditions. From a practical point of view, it is shown that, by proper selection of the process parameters, IBS with metal co-deposition can be used to tune the dynamics and pattern properties and, interestingly, to produce highly ordered arrays.

Control of magnetization reversal by combining shape and magnetocrystalline anisotropy in epitaxial Fe planar nanowires.

This work presents an analysis of the in-plane magnetization reversal mechanisms of Fe nanowires, with widths from 100 nm to 1 microm, fabricated in epitaxial Au(001)/Fe(001)/MgO(001) thin films by means of focused ion and electron beam lithographies, with either positive or negative resist. The experimental results show that the switching mechanisms and hysteresis are almost exclusively functions of the dimensions of the wires and of the Fe intrinsic properties, with minor influence of the specific fabrication route employed upon optimization of nanostructure parameters in terms of crystallinity and morphology, and well defined and reproducible geometry. The reversal processes evolve from wall pinning at low angles between the applied field and the axis of the wires to basically uniform magnetization rotation at high angles. This behaviour can be described in terms of single spin configurations, thus ruling out the formation of multidomain structures even at high angles. The ability to achieve these high quality and well controlled nanowires allowed us to develop an analytical model, based on uniform magnetization configurations considering just the intrinsic Fe properties and the shape and dimensions of the wires. This simple approach provides a very good qualitative and quantitative agreement with the experimental results, thus evidencing the relatively small role of other extrinsic factors in the magnetization processes.

Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles.

Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO(2) matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

Production of nanohole/nanodot patterns on Si(001) by ion beam sputtering with simultaneous metal incorporation.

We have established the conditions for which nanohole and nanodot patterns are produced on Si(001) surfaces by 1 keV Ar(+) ion beam sputtering (IBS) at normal incidence with an alternating cold cathode ion source (ACC-IS). Nanohole patterns are produced within a narrow IBS window for low ion fluxes (<100 µA cm(-2)) and relatively low ion fluences (<10(18) ions cm(-2)) whereas nanodot morphologies are produced above this window. The nanohole pattern is not stable after prolonged irradiation since it evolves to a nanodot morphology. Rutherford backscattering spectrometry (RBS) measurements show that nanohole patterns are produced when the metal content on the irradiated surfaces is higher (within (2.5-3.5 × 10(15)) atoms cm(-2)) than in the case of nanodots (<2.5 × 10(15) atoms cm(-2)). The different metal content is related to the ACC-IS operation, since the set-up provides simultaneous incorporation of Fe and Mo on the target surface from the erosion of the cathodes and sample holder, respectively. The role of metal incorporation on pattern selectivity has been corroborated qualitatively by extending the results obtained with the ACC-IS to a standard Kaufman-type source. In order to gain further information on the metal effects, chemical analysis of the surface has been performed to complement the compositional RBS results, showing for the first time the relevant participation of metal silicides. Further outlook and a discussion regarding the role of metal incorporation are also given.

On the effect of nanocrystallization and disorder on the magnetic properties of Cu-rich, FeMnCu alloys.

We report on the temperature dependencies of the Mössbauer spectra and the AC magnetic susceptibility measured in Cu-rich, FeMnCu samples prepared by mechanically alloying, using, on the one side, Cu and prealloyed FeMn powders and, on the other, pure element Cu, Mn, and Fe powders. From the correlation of the Mössbauer and susceptibility data we conclude about the basic characteristics of the phase distributions present in the different studied samples. Those distributions are a consequence of both the nanostructure induced upon milling and of the different signs of the Mn/Cu (negative) and Fe/Cu (positive) enthalpies of mixing. The proposed phase distributions are significantly different in the samples prepared from different precursors and this fact is analyzed in terms of the disproportion of the precursor FeMn alloy and in those of the favoured Mn/Cu interdiffusion and the hindered Fe/Cu one.