The diffusion of Ga2O3 into the surface of single crystal[001] rutile leads to the insertion of β-gallia subunits along {210} planes of the parent rutile structure. These linear defects introduce hexagonally shaped tunnels, approximately 2.5 å in diameter, normal to the]001] surface. Because these tunnels may serve as highly reactive sites for the attachment of macromolecules, we are exploring the application of these linear defects for creating nanostructures. The current work investigates the kinetics of defect formation and the factors that affect defect periodicity and orientation. Gallium oxide was applied to the surfaces of [001]-oriented TiO2 single-crystal substrates via a sol-gel spin-coating process using a gallium-containing precursor. Thermal treatments were systematically varied to obtain different defect surface structures. Defect orientation and the surface concentration of rows of defects were characterized via tapping mode atomic force microscopy.

Experimental studies of low-energy (≤ 2000 eV) Ar+ ion beam erosion of Si surfaces under normal and oblique ion incidence with simultaneous sample rotation at room temperature show a variety of topographies. At oblique ion incidence, between 70° and 80° with respect to surface normal, dot patterns evolve (dot size ∼ 30 nm) with a remarkably high degree of ordering comparable to dot nanostructures reported for different III/V compound semiconductors. The mean size and ordering of these nanostructures can be adjusted by various process parameters like ion beam energy and erosion time, respectively. Scanning force microscopy (AFM) has been used to characterize the evolution of the surface topography.

Nano structure formations on Au surfaces by 20 keV Ar gas cluster ion beam (GCIB) irradiation at an oblique incidence were studied. When the incident angle was close to 0° from the surface normal of Au targets, the Au surface was smoothed due to the lateral sputtering effects and there were no structure formations on the surfaces. However, ripples were formed on Au surfaces at incident angle of 60° without sample rotation. When the Au samples were irradiated with Ar-GCIB at 60° with sample rotation, cone like structures with 50nm in diameters were fabricated and the surface roughness had a maximum value. However, the surface roughness suddenly decreased over incident angle of 60°. Even though the surface roughness was the same in the cases with and without sample rotations at 85° incidence, ripple structures were formed parallel to the incoming GCIB directions when there was no rotation. The incident angle dependence of the sputtering depth decreased following cosθ dependence. Very efficient surface smoothing without removing materials were realized with oblique incidence.

We present novel results showing that the application of a rapid spatio-temporal surface modulation in-situ with film deposition directs the assembly of ordered nanostructures. Co nanoclusters of approximately 50 nm in size were assembled into one-dimensionally ordered arrays spaced 400 nm apart on Si (100) substrates during film growth of a 0.5 nm thick film. This ordered arrangement was achieved under e-beam evaporation of Co with simultaneous two-beam pulsed laser interference irradiation. The ordering length scale was consistent with the theoretical two-beam fringe spacing. For a thicker Co film, the particles were irregularly shaped, like that of a rapidly solidified liquid-like structure. From this evidence, the mechanism for ordering is partly attributed to thermal effects due to the spatially periodic laser interference heating of the cobalt nanoparticles. This dynamic in-situ process, without the need of any pre-or post-patterning of the substrate or film, is promising as an economical and simple approach to assemble ordered nanostructured films. The author can be reached via e-mail at ramkik@wuphys.wustl.edu

We have demonstrated the direct formation of elongated Ag particles with a quasi-parallel major axis on SiO2 template layer by using dynamic oblique deposition (DOD). The peculiar nanomorphology of the particles and template is physically self-organized owing to the self-shadowing in the oblique vacuum deposition. The resulting films exhibit anisotropic optical absorption due to plasma resonance sensitive to the shape of the Ag particles on the template. Since our method can be applied to any combination of thin film materials, it is useful for enabling the plasmon-mediated optical phenomena and to apply them for the development of various photonic devices such as thin film polarizers.

We investigate the formation of (In, Ga)As self assembled quantum structures grown on different orientations of a GaAs substrate along one side of the stereographic triangle between (100) and (111)A surfaces. The samples were grown by Molecular Beam Epitaxy, monitored by Reflection High-Energy Electron Diffraction during the growth and characterized by in-situ Scanning Tunneling Microscopy and Atomic Force Microscopy. A systematic transition from zero dimensional (In, Ga)As quantum dots to one dimensional quantum wires was observed as the substrate was varied along the side of the triangle within 25° miscut from the (100) toward (111)A, which includes several high index surfaces. We propose an explanation for the role of the substrate in determining the type of the nanostructure that is formed.

Self-formed nanopatterns on Si (001) substrates fabricated by ion beam sputter etching were investigated by atomic force microscopy (AFM). The ion beam sputtering was performed with an Ar+ ion beam produced from a Kaufman type ion gun. In order to fabricate the periodic nanoscale patterns on Si surface, the effects of sputter parameters such as ion energy, flux, incident angle and etching time on surface morphology was investigated. As a result, nanometer scale ripples and 3-dimensioal nanodots were formed uniformly after ion beam sputtering. The surface morphology of Si was significantly dependent on incident angle and ion beam flux.

We get size-controlled nanocrystalline silicon (nc-Si) from a-SiNx/a-Si:H/a-SiNx sandwich structures by thermal annealing. Transmission electron microscope analyses show that the mean size and the grain size distribution (GSD) of the nc-Si are controlled by the annealing conditions and the a-Si sublayer thickness. We build a theoretical model of constrained crystallization which can well interpret the phenomena of the growth halt of nc-Si and higher crystallization temperature for the thinner a-Si sublayer. The experimental results indicate that constrained crystallization method is promising to achieve uniform and high density nc-Si array either by thermal annealing or by laser annealing. Based on this investigation we employ the method of laser interference crystallization (LIC) to fabricate nanocrystal Si with the two-dimensional (2D) patterned distribution within 10 nm thick a-Si:H single layer. Si nano-crystallites are selectively located in the discal regions within the initial a-Si:H layer. The present method is promising to fabricate various patterned nc-Si arrays for device applications simply by changing the geometry of the mask.

TiO2 photocatalysts have a strong oxidation ability for organic compounds under UV irradiation. The surfaces of polyimide and polymethyl methacrylate (PMMA) were photocatalytically machined using a porous TiO2 wire prepared by phase separation and selective leaching with elongation. After UV irradiation, these surfaces were decomposed along the length of the TiO2 wire. Such surface decomposition depended on the irradiation angle of UV light and irradiation time. The machining rate of PMMA was higher than that of the polyimide.

We have measured the temperature and ion flux dependence of the ripple wavelength on a Cu(001) surface during low energy ion sputtering. We analyze these results in terms of a linear instability model and identify different experimentally observed behavior with different mechanisms of relaxation and surface defect kinetics. In a high temperature regime, diffusing species on the surface are mainly thermally induced while in a lower temperature range, the diffusing species are ion beam induced. At even lower temperature, thermal diffusion is deactivated and the surface relaxes through an athermal mechanism. We define a transition between different defects formation kinetics in temperature and flux phase space and discuss how the defect kinetics model can be extended to different materials system.

Photocatalysis of oblique columnar TiO2 thin films has been investigated as a function of thickness using photobleaching of methylene blue (MB). The degradation rate of MB depends on the thickness of the films, although no significant differences in the columnar morphology, crystallinity and optical absorption are found. The relation between the degradation rate and the thickness is well described by a simple model, in which the degradation rate at a certain depth is proportional to the intensity of ultra violet (UV) light. The photocatalytic active thickness is estimated at approximately 200 nm. Thus the interior surface of the oblique columnar TiO2 thin films works well as photocatalyst.

Czochralski silicon wafers which are treated by hydrogen plasma at ca. 260 °C are structured at the surface due to the high reactivity of atomic hydrogen. “Nanopatterned” (np) Si layers with average structure diameters below 100 nm are created. The thickness of the np-Si layer is on the order of 100 nm. The morphology of np-Si layers depend on the applied plasma power and the exposure time. The formation of np-Si layers is discussed in the frame of a combined etching/ redeposition mechanism. Annealing at T ≥ 800 °C causes a reconstruction of np-Si layers and the appearance of tensile stress in the wafers up to a depth of several micrometers.

We have implemented and investigated numerically a new process to fabricate self-organized metal networks and lines on non-metallic substrates. We have deposited a thin film of Cu on silicon and glass substrates and etched the film by a 1 keV-energy Ar beam. Due to the kinetic mechanism known as sputter instability, nanosize metal patterns self-organize on the substrate at the stage when the etched surface reaches the metal/substrate interface. By numerical simulations, we have investigated the mechanism and control factors for the process.

We provide an overview of a novel self-assembly process that occurrs during GeSi/Si(001) strain-layer heteroepitaxy under conditions of limited adatom mobility. Suppression of copious surface diffusion leads to limited three-dimensional roughening in the form of pits that partially consume a thick, metastable wetting layer. The material ejected from the pits accumulates alongside, eventually forming a symmetric quantum dot molecule consisting of four islands bound to a {105}-faceted pit. These structures, which are of interest in nanologic applications, appear to arise from an intrinsic strain-relief mechanism in a relatively narrow regime of deposition conditions. An additional degree of morphological control is obtained by annealing films containing pits, before they evolve to full quantum dot molecules. Annealing promotes a one-dimensional growth instability leading to the formation of highly anisotropic grooves, bounded by long, wire-like islands. Finally, we show that patterns created in the Si substrate using a focused ion beam can control the location of quantum dot molecules, which is an additional critical step towards being able to use these structures for computing.

Silk fibroin (SF) and bovine serum albumin (BSA) thin films were deposited on Si(100) substrate either by colloid casting method or by pulsed laser deposition (PLD). Emphasis is laid on the comparison of nanostructures, which developed during the deposition. AFM diagrams were evaluated to quantify the nanostructures, parallel and perpendicular to the substrate, by the average wavelength of the profilogram (Wa ) and surface roughness (Rrms ), respectively. The film thickness increased with increasing the concentration of colloids or laser deposition time. The value of Wa increased with the film thickness. We note, however, that the value Wa becomes much less sensitive with decreasing the scanning area due to decreasing probability of the abnormally large agglomerates of the nanometric units. Probability of the agglomeration growth as a consequence of the surface adhesion is higher with higher concentration of random coil, followed by β-sheet and α-helix. BSA with smaller primary units and lower probability of agglomeration give more uniform films.

Kinetic limitations related to the Schwoebel-Ehrlich (SE) diffusion barrier are examined in two-(2D) and three-dimensional (3D) growth. It is shown that the realization of step instabilities in 2D growth, possibly caused by the SE barrier, may be hindered by other factors such as step permeability and the relative importance of diffusion and step attachment. Growth shapes of Ag crystallites are also determined that reveal the impact of kinetic limitations. Dramatic changes of growth shape caused by In codeposition suggest that surfactants can modify the 3D SE barrier.

Pulsed laser-induced ablation using diamond-like carbon (DLC) films is reported. Pulsed XeCl excimer laser induced heating revealed that 200-nm DLC films formed by sputtering method had high heat resistivity and structural relaxation was induced by laser heating. SiO2 layers formed on the DLC films were successively removed from the DLC surface by laser heating at 350 mJ/cm2. C-O bond reaction probably occurred and stickiness of SiO2 to carbon was reduced. Laser induced forward transfer of Al/SiO2 was also demonstrated using DLC films with laser heating.

The strain driven self-assembly of faceted Ge nanocrystals during epitaxy on Si(001) to form quantum dots (QDs) is by now well known. We have also recently provided an understanding of the thermodynamic driving force for directed assembly of QDs on bulk Si (extendable to other QD systems) based on local chemical potential and curvature of the surface. Silicon-on-insulator (SOI) produces unique new phenomena. The essential thermodynamic instability of the very thin crystalline layer (called the template layer) resting on an oxide can cause this layer, under appropriate conditions, to dewet, agglomerate, and self-organize into an array of Si nanocrystals. Using low-energy electron microscopy (LEEM), we observe this process and, with the help of first-principles total-energy calculations, we provide a quantitative understanding of this pattern formation. The Si nanocrystal pattern formation can be controlled by lithographic patterning of the SOI prior to the dewetting process. The resulting patterns of electrically isolated Si nanocrystals can in turn be used as a template for growth of nanostructures, such as carbon nanotubes (CNTs). Finally we show that this growth may be controlled by the flow dynamics of the feed gas across the substrate.

It is known that oblique angle deposition (or glancing angle deposition) can create 3D architectures that are otherwise difficult to produce using the conventional lithographic techniques. The technique relies on a self-assembly mechanism originated from a physical shadowing effect during deposition. In this paper we show examples of 3D nanostructures obtained by this oblique angle deposition on a templated substrate with regularly spaced pillar seeds. We show that common to this technique is the phenomenon of side-way growth on the seeds. The side-way growth leads to a fan-like structure at the initial stages of growth if the incident oblique angle is fixed during growth. Simulations based on a steering effect due to the attractive force between the incoming atom and the existing atoms on the surface produce a fanlike structure similar to that observed experimentally. We show that a two-phase substrate rotation scheme during deposition can dramatically reduce this fan-out effect and can lead to uniform and isolated columns.

The Cu <111> columns, which are formed during magnetron sputtering deposition, are faceted on the top and zigzag on sides. Our numerical results of large facet-facet diffusion barriers offer an explanation of the facet dimension. Based on the stacking fault formation energies of various face-centered-cubic metals, we suggest that the zigzag shape of Cu <111> columns is a result of deposition twins. Our molecular dynamics simulations indeed confirm this suggestion. Further, the dynamics simulations reveal the transient role of {100} facets, which facilitate the formation of {111} facets and disappear afterwards.