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.

Coalescence, crystallographic orientation and luminescence of ZnO nanowires grown on Si(001) by chemical vapour transport.

We analyse the morphological, structural and luminescence properties of self-assembled ZnO nanowires grown by chemical vapour transport on Si(001). The examination of nanowire ensembles by scanning electron microscopy reveals that a non-negligible fraction of nanowires merge together forming coalesced aggregates during growth. We show that the coalescence degree can be unambiguously quantified by a statistical analysis of the cross-sectional shape of the nanowires. The examination of the structural properties by x-ray diffraction evidences that the nanowires crystallize in the wurtzite phase, elongate along the c-axis, and are randomly oriented in plane. The luminescence of the ZnO nanowires, investigated by photoluminescence and cathodoluminescence spectroscopy, is characterized by two bands, the near-band-edge emission and the characteristic defect-related green luminescence of ZnO. The cross-correlation of scanning electron micrographs and monochromatic cathodoluminescence intensity maps reveals that: (i) coalescence joints act as a source of non-radiative recombination, and (ii) the luminescence of ZnO nanowires is inhomogeneously distributed at the single nanowire level. Specifically, the near-band-edge emission arises from the nanowire cores, while the defect-related green luminescence originates from the volume close to the nanowire sidewalls. Two-dimensional simulations of the optical guided modes supported by ZnO nanowires allow us to exclude waveguiding effects as the underlying reason for the luminescence inhomogeneities. We thus attribute this observation to the formation of a core-shell structure in which the shell is characterized by a high concentration of green-emitting radiative point defects as compared to the core.

Plasmonic coupling in closed-packed ordered gallium nanoparticles.

Plasmonic gallium (Ga) nanoparticles (NPs) are well known to exhibit good performance in numerous applications such as surface enhanced fluorescence and Raman spectroscopy or biosensing. However, to reach the optimal optical performance, the strength of the localized surface plasmon resonances (LSPRs) must be enhanced particularly by suitable narrowing the NP size distribution among other factors. With this purpose, our last work demonstrated the production of hexagonal ordered arrays of Ga NPs by using templates of aluminium (Al) shallow pit arrays, whose LSPRs were observed in the VIS region. The quantitative analysis of the optical properties by spectroscopic ellipsometry confirmed an outstanding improvement of the LSPR intensity and full width at half maximum (FWHM) due to the imposed ordering. Here, by engineering the template dimensions, and therefore by tuning Ga NPs size, we expand the LSPRs of the Ga NPs to cover a wider range of the electromagnetic spectrum from the UV to the IR regions. More interestingly, the factors that cause this optical performance improvement are studied with the universal plasmon ruler equation, supported with discrete dipole approximation simulations. The results allow us to conclude that the plasmonic coupling between NPs originated in the ordered systems is the main cause for the optimized optical response.

Spectrally broad plasmonic absorption in Ga and In nanoparticle hybrids.

In this work, we use Joule-effect thermal evaporation to produce hybrid structures made of Ga and In nanoparticles (NPs) on Si (100) substrates. Taking advantage of the protective oxide shell, In NPs can be used as a template for a second deposition step without structural changes, enabling the hybridization of NPs of materials. These complex structures of mixed NPs present a spectrally broad plasmonic absorption that can be optically tuned with a wide range of photon energies from UV to IR regions with a full width at half maximum range of ∼400 to 800 nm. The results suggest that the localized surface plasmon resonance (LSPR) of the hybrid NPs is mainly due to the plasmonic coupling of the in-plane modes. Furthermore, different scenarios studied by discrete dipole approximation simulations show that the interconnection between NPs is extremely sensitive to the size and the local arrangement of the nanostructures. This kind of broadening and tunable LSPR may have interest for energy transfer applications, biosensing platforms and solar cells.

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.

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.

Analysis of Zinc Nitride Resistive Indicators under Different Relative Humidity Conditions.

Zinc nitride (Zn3N2) is a metastable material in ambient conditions because of its high reactivity with water molecules. In this work we perform a systematic analysis of the oxidation of Zn3N2 layers grown by RF magnetron sputtering at room temperature. The aging and transformation of the layers toward a ZnO film is explored by means of spectroscopic ellipsometry and scanning electron microscopy for conditions with different relative humidity (RH). Accurate depth profiling by means of elastic recoil detection analysis with a time-of-flight telescope demonstrated the substitutional reaction between O and N and the important effect of the RH in this process. Because of this metastability the resistivity of the layers changes several orders of magnitude. Taking advantage of this principle, we develop electronic indicators and characterize the transformation of their electrical properties as a function of the ambient RH, finding a good correlation between the transformation time and the RH level.

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.

Analysis of the stability of InGaN/GaN multiquantum wells against ion beam intermixing.

Ion-induced damage and intermixing was evaluated in InGaN/GaN multi-quantum wells (MQWs) using 35 keV N(+) implantation at room temperature. In situ ion channeling measurements show that damage builds up with a similar trend for In and Ga atoms, with a high threshold for amorphization. The extended defects induced during the implantation, basal and prismatic stacking faults, are uniformly distributed across the quantum well structure. Despite the extremely high fluences used (up to 4 × 10(16) cm(-2)), the InGaN MQWs exhibit a high stability against ion beam mixing.

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.

Selective ion-induced intermixing and damage in low-dimensional GaN/AlN quantum structures.

Ion-induced intermixing and damage is evaluated in GaN/AlN superlattices of quantum dots (QDs) and quantum wells (QWs) using 100 keV Ar(+) implantation at low temperature (15 K). Despite the similar damage build up at low fluences, a significant increase of the damage accumulation takes place for QDs at high fluences. Elemental depth profiles were fitted with a diffusion model, revealing the higher intermixing efficiency in QD superlattices, significantly higher than for QWs. The scaling of diffusion length with the local fluence and defect concentration is understood on the basis of cascade mixing and migration of defects in the cation sublattice. The selective intermixing/damage of QDs is explained by the promotion of lateral diffusion mechanisms that result in smooth interfaces, as well as by an enhanced diffusivity due to the characteristic strain distribution in QD superlattices.

Independence of interrupted coarsening on initial system order: ion-beam nanopatterning of amorphous versus crystalline silicon targets.

Interrupted coarsening (IC) has recently been identified as an important feature for the dynamics of the typical length-scale in pattern-forming systems on surfaces. In practice, it can be beneficial to improve pattern ordering since it combines a certain degree of defect suppression with a limited increase in the typical pattern wavelength. However, little is known about its robustness with respect to changes in the preparation of the initial system for cases with potential applications. Working in the context of nano-scale pattern formation by ion-beam sputtering (IBS), we prove that IC properties do not depend on sample preparation. Specifically, interface dynamics under IBS is quantitatively compared on virgin amorphous and crystalline silicon surfaces, using 1 keV Ar(+) ions at normal incidence where nanodot pattern formation is triggered by concurrent co-deposition of Fe atoms during processing. Atomic force microscopy shows that dot patterns with similar spatial order and dynamics are obtained in both cases, underscoring the key dynamical role of the amorphous surface layer produced by irradiation. Both systems have been quantitatively described by an effective interface equation. We employ a new procedure based on the linear growth of the initial surface correlations to accurately estimate the equation coefficients. Such a method improves the predictive power of the interface equation with respect to previous studies and leads to a better description of the experimental pattern and its dynamical features.

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.

Tuning the surface morphology in self-organized ion beam nanopatterning of Si(001) via metal incorporation: from holes to dots.

We report on the selective production of self-organized nanohole and nanodot patterns on Si(001) surfaces by ion beam sputtering (IBS) under normal-incidence of 1 keV Ar(+) ions extracted with a cold cathode ion source. For a fixed ion fluence, nanohole patterns are induced for relatively low ion current densities (50-110 µA cm(-2)), evolving towards nanodot patterns for current densities above 190 µA cm(-2). Both patterns display similar characteristics in terms of wavelength, short-range hexagonal order and roughness. Rutherford backscattering spectrometry measurements show that the surface morphology is tuned by the incorporation of metals coming from the ion source and sample surroundings during the IBS process. The metal content measured in nanohole patterns is almost twice that found in nanodot morphologies. Thus, the pattern morphology results from the balance between the dependences of the erosion rate on the ion flux, the local surface topography and composition. These nanostructures have promising applications as growth templates for preferential growth on either hillocks or cavities.