Fabrication Of Nanostructured Surfaces Research Articles

Surface engineering by rogue wave induced by energetic carbon clusters

Swift heavy ions are effective in nanostructuring material surfaces. The irradiation of lanthanum fluoride with 30 MeV C60 leads to the creation of surface nanohillocks of size larger than the ones produced by monoatomic heavy ions. The generation of the observed nano-sized hillocks is described here by a new approach that is based on ion-induced intensive electronic excitations that create localized rogue waves. Consequently, the induced nonlinear ion-acoustic rogue waves are considered a hallmark of nanohillock formation. Plasma hydrodynamic equations produce a relationship between normalised electron number density and crystal lattice spacing. Similarities to the hillock profile suggest the crucial primary role of electron density in the fabrication of surface nanostructures.

Grain Orientation, Angle of Incidence, and Beam Polarization Effects on Ultraviolet 300 ps‐Laser‐Induced Nanostructures on 316L Stainless Steel

AbstractLaser‐induced periodic surface structures (LIPSS) represent a unique route for functionalizing materials through the fabrication of surface nanostructures. Commercial AISI 316L stainless steel (SS316L) surfaces are laser treated by ultraviolet 300 ps laser pulses in a laser line scanning (LLS) approach. Processing parameters are optimized (pulse energy of 2.08 µJ, pulse repetition frequency of 300 kHz, and suitable laser scan and sample displacement rates) for the generation of low spatial frequency LIPSS over a large 25 × 25 mm2 area. Different angles of incidence of the laser radiation (0°, 30°, and 45°) and different linear laser beam polarizations (s and p) produce a plethora of rippled surface morphologies at distinct grains. Scanning electron microscopy and 2D Fourier transforms, together with calculations of the optical energy deposited at the treated surfaces using Sipe's first‐principles electromagnetic scattering theory, are used to study and analyze in detail these surface morphologies. Combined with electron backscattering diffraction, analyses allow associating site‐selectively various laser‐induced‐surface morphologies with the underlying crystalline grain orientation. Resulting grain orientation maps reveal a strong impact of the grain crystallographic orientation on LIPSS formation and point toward possible strategies, like multi‐step processes, for improving the manufacturing of LIPSS and their areal coverage of polycrystalline technical materials.

A Microshutter for the Nanofabrication of Plasmonic Metal Alloys with Single Nanoparticle Composition Control.

Alloying offers an increasingly important handle in nanomaterials design in addition to the already widely explored size and geometry of nanostructures of interest. As the key trait, the mixing of elements at the atomic level enables nanomaterials with physical or chemical properties that cannot be obtained by a single element alone, and subtle compositional variations can significantly impact these properties. Alongside the great potential of alloying, the experimental scrutiny of its impact on nanomaterial function is a challenge because the parameter space that encompasses nanostructure size, geometry, chemical composition, and structural atomic-level differences among individuals is vast and requires unrealistically large sample sets if statistically relevant and systematic data are to be obtained. To address this challenge, we have developed a microshutter device for spatially highly resolved physical vapor deposition in the lithography-based fabrication of nanostructured surfaces. As we demonstrate, it enables establishing compositional gradients across a surface with single nanostructure resolution in terms of alloy composition, which subsequently can be probed in a single experiment. As a showcase, we have nanofabricated arrays of AuAg, AuPd, and AgPd alloy nanoparticles with compositions systematically controlled at the level of single particle rows, as verified by energy dispersive X-ray and single particle plasmonic nanospectroscopy measurements, which we also compared to finite-difference time-domain simulations. Finally, motivated by their application in state-of-the-art plasmonic hydrogen sensors, we investigated PdAu alloy gradient arrays for their hydrogen sorption properties. We found distinctly composition-dependent kinetics and hysteresis and revealed a composition-dependent contribution of a single nanoparticle response to the ensemble average, which highlights the importance of alloy composition screening in single experiments with single nanoparticle resolution, as offered by the microshutter nanofabrication approach.

Cation-dependent assembly of hexagonal DNA origami lattices on SiO2 surfaces.

DNA origami nanostructures have emerged as functional materials for applications in various areas of science and technology. In particular, the transfer of the DNA origami shape into inorganic materials using established silicon lithography methods holds great promise for the fabrication of nanostructured surfaces for nanoelectronics and nanophotonics. Using ordered DNA origami lattices directly assembled on the oxidized silicon surface instead of single nanostructures would enable the fabrication of functional nanopatterned surfaces with macroscopic dimensions. Here, we thus investigate the assembly of hexagonal DNA lattices from DNA origami triangles on RCA-cleaned silicon wafers with hydroxylated surface oxide by time-lapse atomic force microscopy (AFM). Lattice assembly on the SiO2 surface is achieved by a competition of monovalent and divalent cations at elevated temperatures. Ca2+ is found to be superior to Mg2+ in promoting the assembly of ordered lattices, while the presence of Mg2+ rather results in DNA origami aggregation and multilayer formation at the comparably high Na+ concentrations of 200 to 600 mM. Furthermore, Na+ concentration and temperature have a similar effect on lattice order, so that a reduction of temperature can be compensated to some extent by an increase in Na+ concentration. However, even under optimized conditions, the DNA origami lattices assembled on the SiO2 surface exhibit a lower degree of order than equivalent lattices assembled on mica, which is attributed to a higher desorption rate of the DNA origami nanostructures. Even though this high desorption rate also complicates any post-assembly treatment, the formed DNA origami lattices could successfully be transferred into the dry state, which is an important prerequisite for further processing steps.

ICAR ATRP-induced surface self-assembly in the fabrication of the surface nanostructures

Polymerization induced surface self-assembly (PISSA) technology is a state-of-the-art method in the fabrication of the hierarchical surface nanostructures. Previously, we demonstrated that reversible addition−fragmentation chain transfer (RAFT) polymerization-based PISSA could be used to construct hierarchical surface nanostructures on the silica particles. Atom transfer radical polymerization (ATRP) has many advantages, especially in the synthesis of the macroinitiator. In this research initiators for continuous activator regeneration (ICAR) ATRP-induced PISSA approach is used to fabricate surface nanostructures. Poly(ethylene glycol) (PEG) macroinitiator and poly(oligo(ethylene glycol) monomethyl ether methacrylate-co-2-(2-bromoisobutyrnyloxy) ethyl methacrylate) (P(OEGMA-co-BIEM)) polymer brush macroinitiator on silica particles are used to initiate ATRP of styrene in methanol/water mixture. With the chain extensions, POEGMA-g-PS graft copolymer brushes and “free” PEG-b-PS block copolymer chains make surface coassembly into surface nanostructures. With an increase in monomer feeding ratio, the surface morphology gradually changes from small-sized spherical surface micelles (s-micelles), to big-sized s-micelles, and to asymmetric layered structures. Kinetics studies indicate that with an increase in monomer conversion there is a transition from homogeneous to heterogeneous polymerization.

Broadband Enhancement of Anti-reflectivity for a High Angle of Incidence Using Nanocone Geometry.

The broadband antireflective (AR) effect for wide incident angles has a significant effect on the photoconversion efficiency of photovoltaics and visibility of large-format display panels. The fabrication of surface nanostructures has continued to attract research interest as an effective way to provide such optical performance. However, the effects of different nanostructure geometries are not fully understood, especially for wide-angle AR effects. In this work, we conduct a systematic analysis of the effect of periodic nanostructures such as nanocones (NCs) and inverted nanocones (INCs) on anti-reflectivity at high angles of incidence (AOIs) in terms of light scattering, guided-mode resonance (GMR), and internal reflections. NCs provide good coupling of light scattering and GMR because of their protruding geometry; hence, reduced reflectance can be obtained in the short wavelength region. Further, NCs exhibit relatively weaker GMR intensities and internal reflections, resulting in low reflectance in the long wavelength region. Therefore, NCs offer a superior broadband AR effect for high AOIs compared with INCs. Based on this analysis, we demonstrate an extremely low average reflectance (5.4%) compared to that of the bare substrate (34.7%) for the entire visible range at an AOI of 75° by fabricating NCs on both sides of the substrate.

Theoretical solvent selection for nanostructured surface fabrication of reusable and colourimetric visual-eye sensor strips with rhodamine derivative-encapsulated polymeric membranes for highly sensitive and selective detection of Hg2+

Homogenous electrospinnable solutions were prepared through theoretical solvent selection using the high solubility parameters of rhodamine derivatives (rhodamine B hydrazide, RBH and rhodamine 6G hydrazide, R6GH) and poly(methylmethacrylate) (PMMA). Results of the systematic method showed that the best solvent for the Hg2+-sensing membranes was ethanol/tetrahydrofuran at 0.6/0.4 (v/v). PMMA/RBH and PMMA/R6GH membranes were fabricated using electrospinning. The optimal PMMA concentration was 11 wt%. The PMMA/RBH and PMMA/R6GH membranes possessed a nanostructured smooth surface with a high surface area of ultra-fine narrow nanofibres (about 2.5 μm in diameter). Given their high surface area with narrow-diameter fibres, the PMMA/RBH and PMMA/R6GH electrospun membranes showed high selectivity and sensitivity fluorescent sensing of Hg2+ ion with low detection limit (ranges of 0.8–1.099 and 3.6–4.3 ppb, respectively) than the sensor-encapsulated polymeric membranes prepared by spinning technique. The sensing membranes provided a vibrant colourimetric response unique to Hg2+ ions (white-pink) over other potential interfering metal cations that were observed within 30 s by the visual eye. Furthermore, the membranes were effective for reuse up to four times with a high fluorescence intensity. Therefore, PMMA/RBH and PMMA/R6GH can be used as portable colourimetric visual-eye and fluorescent sensors for the easy real-time monitoring of Hg2+ ions in dietary and environment sources.

Nanoparticles and Nanostructured Surface Fabrication for Innovative Cranial and Maxillofacial Surgery.

A novel strategy to improve the success of soft and hard tissue integration of titanium implants is the use of nanoparticles coatings made from basically any type of biocompatible substance, which can advantageously enhance the properties of the material, as compared to its similar bulk material. So, most of the physical methods approaches involve the compaction of nanoparticles versus micron-level particles to yield surfaces with nanoscale grain boundaries, simultaneously preserving the chemistry of the surface among different topographies. At the same time, nanoparticles have been known as one of the most effective antibacterial agents and can be used as effective growth inhibitors of various microorganisms as an alternative to antibiotics. In this paper, based on literature research, we present a comprehensive review of the mechanical, physical, and chemical methods for creating nano-structured titanium surfaces along with the main nanoparticles used for the surface modification of titanium implants, the fabrication methods, their main features, and the purpose of use. We also present two patented solutions which involve nanoparticles to be used in cranioplasty, i.e., a cranial endoprosthesis with a sliding system to repair the traumatic defects of the skull, and a cranial implant based on titanium mesh with osteointegrating structures and functional nanoparticles. The main outcomes of the patented solutions are: (a) a novel geometry of the implant that allow both flexible adaptation of the implant to the specific anatomy of the patient and the promotion of regeneration of the bone tissue; (b) porous structure and favorable geometry for the absorption of impregnated active substances and cells proliferation; (c) the new implant model fit 100% on the structure of the cranial defect without inducing mechanical stress; (d) allows all kinds of radiological examinations and rapid osteointegration, along with the patient recover in a shorter time.

Nanopillared Chitosan/Gelatin Films: A Biomimetic Approach for Improved Osteogenesis

Biomimicry strategies, inspired from natural organization of living organisms, are being widely used in the design of nanobiomaterials. Particularly, nonlithographic techniques have shown immense potential in the facile fabrication of nanostructured surfaces at large-scale production. Orthopedic biomaterials or coatings possessing extracellular matrix-like nanoscale features induce desirable interactions between the bone tissue and implant surface, also known as osseointegration. In this study, nanopillared chitosan/gelatin (C/G) films were fabricated using nanoporous anodic alumina molds, and their antibacterial properties as well as osteogenesis potential were analyzed by comparing to the flat C/G films and tissue culture polystyrene as controls. In vitro analysis of the expression of RUNX2, osteopontion, and osteocalcin genes for mesenchymal stem cells as well as osteoblast-like Saos-2 cells was found to be increased for the cells grown on nano C/G films, indicating early-stage osteogenic differentiation. Moreover, the mineralization tests (quantitative calcium analysis and alizarin red staining) showed that nanotopography significantly enhanced the mineralization capacity of both cell lines. This work may provide a new perspective of biomimetic surface topography fabrication for orthopedic implant coatings with superior osteogenic differentiation capacity and fast bone regeneration potential.

Surface Nanostructure Formation and Atomic-Scale Templates for Nanodevices.

The holy grail in nanoelectronics is the construction of nanodevices with high density, low cost, and high performance per device and per integrated circuit. One approach is the fabrication of surface nanostructures and atomic-scale templates via the autonomous assembly of atoms and/or molecules on well-defined surfaces. To steer the atomic or molecular growth processes and create a wide range of surface nanostructures with desired properties, a comprehensive understanding of the mechanisms that control the surface self-assembly processes is required. The capability to manipulate the nanodevices at the submolecular level with good controllability is also of paramount importance. This review highlights some key recent developments in the fabrication of low-dimensional nanostructures based on supramolecular self-assembly on predefined surfaces, with particular emphasis on the rapidly expanding field of two-dimensional materials. Special attention is also given to the latest progress in single-molecule manipulation for future device applications.

Flexible foils formed by a prolonged electron beam irradiation in scanning electron microscope

The ubiquitous presence of hydrocarbon contamination on solid surfaces alters their inherent physical properties and complicates the surface analyses. An irradiation of sample surface with electron beam can lead to the chemical transformation of the hydrocarbon layer to carbon films, which are flexible and capable of acting as a barrier for chemical etching of an underlying material. The growth of these foils is limited by supply of hydrocarbons to the writing beam position rather than the electron dose or electron beam current. The prepared films can find their applications in fabrication of surface nanostructures without a need of an electron sensitive resist material.

Surface bioactivation through the nanostructured layer on titanium modified by facile HPT treatment

Facile fabrication of nanostructured surface is of great importance for the use of titanium (Ti) implants in biomedical field. In this study, a low-cost and easy-to-operate method called HPT (hydrothermal & pressure) here has been developed and used to fabricate the expected nanostructured surface on Ti substrates. The effects of experimental parameters on the morphology of Ti surface were investigated and characterized. The results indicated that by altering the hydrothermal pressure, NaOH concentration and treating time, surface nanostructure like nanopetals or nanoflakes could be formed on the surface of Ti substrates. The orthogonal experiments were conducted to demonstrate the optimized operation conditions. A formation mechanism of the nanostructured titanate layer was proposed, revealing that the nanostructured layer could be formed via a special upward and downward co-growth manner. In vitro cell culture showed that the HPT treated Ti substrates, especially the T-10 sample, could greatly enhance the cell-material interactions, i.e. the cell proliferation and differentiation, focal protein adhesion, and osteogenic factor expression. The HPT method paves a new way to modify the surface of Ti implants with better bioactivity and promising prospect for future biomedical applications.

Plasma sputtering depositions with colloidal masks for fabrication of nanostructured surfaces with enhanced photocatalytic activity

Titanium oxide/silicon oxide (TiO2/SiO2) 2D patterns were obtained by magnetron sputtering depositions of Ti on close-packed and size-reduced colloidal masks on Si and quartz substrates, followed by mask lift-off and ending with thermal oxidation. The physical processes involved in growing 2D Ti patterns and their oxidation are analyzed. For the magnetron sputtering deposition, two regimes are considered: the low-pressure regime when the flux of sputtered atoms is anisotropic, and the high-pressure regime, when the flux of sputtered atoms is isotropic due to frequent collisions. Moreover, magnetron sputtering operation modes, such as dc sputtering and high power impulse sputtering, are compared. The changes in pattern size and morphology determined by the oxidation of the Ti patterns and Si substrate are analyzed. The hydrophilicity induced by UV-light irradiation and the visible-light photocatalytic activity towards the degradation of the methylene blue of the fabricated TiO2/SiO2 patterns were considerably higher when compared to the performances of uniform TiO2 films.

Surfactants adsorption on crossing stripes and steps.

Using coarse-grained dissipative particle dynamics (DPD) simulations, we systematically study the effect of surface heterogeneity on surfactant adsorption. Here we investigate the adsorption and aggregation of surfactants on hydrophobic stripes crossing each other perpendicularly (i.e., crossing stripes) and on hydrophobic steps. The results are compared with those obtained for isolated stripes. We find that on crossing stripes of moderate stripe widths (e.g., L = 0.61LS, 1.22LS and 1.83LS, where LS is the length of one surfactant molecule) the crossing region hinders the formation of defect-free adsorbed surfactant structures. By increasing the stripe width and/or by increasing the length of one of the two perpendicularly crossing stripes (i.e., lowering the surface density of defects/intersections), the crossing region is found to have a weaker effect on the features of the adsorbed structures. Regarding surfactant adsorption on steps, our simulation results show that the self-assembled aggregates can be stretched along the step corner, and the resultant elastic deformation can hinder adsorption. This qualitative observation can facilitate a description of surfactant adsorption that takes into consideration also the deformation of the self-assembled film. As suggested by such a general model, increasing the convex angle of the step, increasing the size of the surfactant head groups, and changing other physical parameters can reduce the elastic energy penalty, and yield larger amounts of surfactants adsorbed. The results presented could assist in understanding and sometimes predicting surfactant adsorption on heterogeneous surfaces, suggest methods to formulate surfactant mixtures to control surface coverage on heterogeneous surfaces, and perhaps facilitate new methods for the fabrication of nano-structured surfaces.

Influence of ligands in metal nanoparticle electrophoresis for the fabrication of biofunctional coatings

Electrophoretic deposition of colloidal nanoparticles shows great promise for the fabrication of nanostructured surfaces, especially relevant for the surface modification of three dimensional medical implants. Here, the role of small and bulky, chemisorbent and physisorbent ligands on metal (gold, platinum) nanoparticle deposition dynamics are systematically investigated. To be able to compare ligand-coated to ligand-free nanoparticles, pulsed laser ablation in liquid is employed as nanoparticle fabrication method. Nanoparticles’ electrophoretic properties are assessed via zeta potential measurements and nanoparticle tracking analysis, while online-UV–vis spectroscopy provides information about the deposition dynamics. Electron micrographs and contact angle measurements are employed to characterize the deposit. We show that ligand-free nanoparticles feature a high electrophoretic mobility and linear deposition kinetics, representing an excellent model material for controlled electrophoretic deposition. In contrast, the electrophoretic mobility of surface-modified nanoparticles is altered due to the surrounding ligand layer, resulting in less efficient deposition. Notably, electrophoretic mobility is not solely governed by the ligand's charge and does not correlate to the zeta potential values directly. Finally, bioactive nanotopographies with tunable wettability were created when depositing nanoparticles functionalized with cell-penetrating peptides. These peptide-nanoparticle bioconjugates have great potential to be used for mediating delivery via an implant surface such as a neural electrode.

Femtosecond Ablation of Silicon in Acetone: Tunable Photoluminescence from Generated Nanoparticles and Fabrication of Surface Nanostructures

Silicon (Si) nanoparticles (NPs) and self-organized high spatial frequency laser (HSFL) induced periodic surface structures were fabricated by means of femtosecond ablation of bulk Si target in acetone. The ablation was performed with ∼40 fs (fwhm) pulses and different input energies of ∼500, ∼200, ∼150, ∼100, ∼50, and ∼10 μJ. Fabricated NPs and nanostructures (NSs) were characterized by UV–visible absorption spectroscopy, photoluminescence (PL) spectroscopy, Raman spectroscopy, transmission electron microscopy, and field emission scanning electron microscopy. The average sizes of the NPs were estimated to be in the 4–135 nm range. From the PL studies of Si NPs of different sizes, we have observed a size-dependent shift toward blue spectral region. We could tune the observed PL peak in the spectral range of 440–515 nm. The crystalline and amorphous nature of the Si nanoparticles and nanostructures was investigated using selected area electron diffraction and Raman spectra. Complex refractive index, conduc...

Understanding Anisotropic Plasma Etching of Two-Dimensional Polystyrene Opals for Advanced Materials Fabrication

Anisotropic deformation of polystyrene particles in an oxygenated (O2/Ar) plasma is observed for radio frequency (rf) plasma and inductively coupled plasma (ICP). A facile model based on a ratio of completely isotropic and completely anisotropic etching is presented to describe the anisotropy of the etching process and is implemented to determine the height of the spheroid-shaped polystyrene particles. In our systems, we find the plasma etching to be 54% isotropic in the rf plasma and 79% isotropic in the ICP. With this model, the maximum material deposition thickness for nanofabrication with plasma-etched nanosphere lithography or colloid lithography can be predicted. Moreover, the etching of polystyrene particles in an oxygenated plasma is investigated versus the etching time, gas flow, gas composition, temperature, substrate material, and particle size. The results of this study allow precise shape tuning during the fabrication of nanostructured surfaces with size-dependent properties for bionic, medical, and photonic applications.

Optical response of alkali metal atoms confined in nanoporous glass*

We study the influence of optical radiation on adsorption and desorption processes of alkali metal atoms confined in nanoporous glass matrices. Exposure of the sample to near-IR or visible light changes the atomic distribution inside the glass nanopores, forcing the entire system to evolve towards a different state. This effect, due to both atomic photodesorption and confinement, causes the growth and evaporation of metastable nanoparticles. It is shown that, by a proper choice of light characteristics and pore size, these processes can be controlled and tailored, thus opening new perspectives for fabrication of nanostructured surfaces.

Laser Fabrication of Nanostructures on a Pure Aluminum Surface in Air

We report on the fabrication of surface nanoparticles and micro/nanograting structures on bulk pure aluminum in air using a 150 fs, 775 nm femtosecond laser. We investigate the size of the generated surface nanoparticles under irradiation with different femtosecond laser pulses. Smaller nanoparticles can be induced by a larger number of laser pulses and a lower laser fluence. In addition, we observe the formation of micro/nanogratings when the laser focus is scanned across a pure aluminum surface in air. We obtain micro- and nano-grating composite structures on a pure aluminum surface by adjusting the laser fluence and scan velocity. Femtosecond laser surface ablation of bulk pure aluminum in air is potentially a promising technique for efficient fabrication of surface nanostructures.

Rapid fabrication of nanostructured surfaces using nanocoining

A new process for creating high quality ordered arrays of nanofeatures called nanocoining is presented. A diamond die with a structured area of nanofeatures (1600 features in a 20 μm × 20 μm area) is used to physically transfer features to a mold surface. The die is attached to an actuator capable of producing an elliptical tool-path, the dimensions of which are process dependent and enable the die to match velocity with the moving mold during contact to avoid dragging the nanostructured area along the mold surface (smear). Nanocoining process parameters are discussed which enable indents to be indexed precisely to completely cover target areas. Techniques for die alignment and depth control are also required to create large areas (339 mm2) of nanofeatures in short times (∼20 min). Nanocoining experiments were performed at 1 kHz (1000 indents or 1.6 million features per second) on a flat electroless nickel sample. UV curable replicates were then created from the nickel mold and both the mold and replicate were examined in an SEM and AFM.