Functional pattern engineering in glancing angle deposition thin films

We present a new method for making functional patterns in thin films consisting of highly ordered arrays of complex, submicrometer structures, deposited at oblique flux incidence angles using the glancing angle deposition technique. By performing physical vapor deposition on direct write seed layers with intentional point and line lattice defects, we are able to generate embedded air-filled linear and planar patterns in the films in a single-step transfer approach with no need for conventional postdeposition micromachining. The uniformity and porosity of the thin films is fully maintained, with minimal impact on the film morphology adjacent to the patterns. This ability to engineer air-filled patterns is crucial to several promising thin-film applications, including photonic band gap crystals and microfluidics.     

Interface strength of structured nanocolumns grown by glancing angle deposition

In order to investigate the mechanics of interfacial fracture in structured nano-elements grown by glancing angle deposition (GLAD), fracture experiments were conducted on oblique Ti nanocolumns grown on a Si substrate using a micro-brick specimen. Two types of specimens, a Forward specimen (loading with the column tilt direction) and a Reverse specimen (loading against the column tilt), were prepared to clarify the effect of an asymmetric nanostructure on the interface strength. The specimens fractured at the interface or near the interface between the Ti nanocolumns and the Si substrate for both specimens. The critical force and displacement at fracture in the Forward specimens were about 2.0 times and 1.6 times as large as those in the Reverse specimens, respectively, showing clear anisotropy in the interface strength. The local stress distribution along the interface in the single nanocolumn at fracture was analyzed by finite element analysis. While the stress singularity in the Reverse specimen was greater than that in the Forward specimen, the normal stresses in a region 1–3 nm near the interface edge were almost identical regardless of the loading direction, suggesting that intensified stress in the nanoscale region dominated fracture.     

Nanostructured tungsten and tungsten trioxide films prepared by glancing angle deposition

Nanostructured tungsten (W) and tungsten trioxide (WO₃) films were prepared by glancing angle deposition using pulsed direct current magnetron sputtering at room temperature with continuous substrate rotation. The chemical compositions of the nanostructured films were characterized by X-ray photoelectron spectroscopy, and the film structures and morphologies were investigated using X-ray diffraction and high resolution scanning electron microscopy. Both as-deposited and air annealed tungsten trioxide films exhibit nanostructured morphologies with an extremely high surface area, which may potentially increase the sensitivity of chemiresistive WO₃ gas sensors. Metallic W nanorods formed by sputtering in a pure Ar plasma at room temperature crystallized into a predominantly simple cubic β-phase with <100> texture although evidence was found for other random grain orientations near the film/substrate interface. Subsequent annealing at 500 °C in air transformed the nanorods into polycrystalline triclinic/monoclinic WO₃ structure and the nanorod morphology was retained. Substoichiometric WO₃ films grown in an Ar/O₂ plasma at room temperature had an amorphous structure and also exhibited nanorod morphology. Post-deposition annealing at 500 °C in air induced crystallization to a polycrystalline triclinic/monoclinic WO₃ phase and also caused a morphological change from nanorods into a nanoporous network.     

Growth and properties of the CuInS2 thin films produced by glancing angle deposition

We use the glancing angle deposition technique (GLAD) to grow CuInS₂ thin films by a vacuum thermal method onto glass substrates. During deposition, the substrate temperature was maintained at 200 °C. Due to shadowing effect the oblique angle deposition technique can produce nanorods tilted toward the incident deposition flux. The evaporated atoms arrive at the growing interface at a fixed angle θ measured from the substrate normal. The substrate is rotated with rotational speed ω fixed at 0.033 rev s^− 1. We show that the use of this growth technique leads to an improvement in the optical properties of the films. Indeed high absorption coefficients (10⁵–3.10⁵ cm^− 1) in the visible range and near-IR spectral range are reached. In the case of the absence of the substrate rotation, scanning electron microscopy pictures show that the structure of the resulting film consists of nanocolumns that are progressively inclined towards the evaporation source as the incident angle was increased. If a rapid azimuthal rotation accompanies the substrate tilt, the resulting nanostructure is composed of an array of pillars normal to the substrate. The surface morphology show an improvement without presence of secondary phases for higher incident angles (θ > 60°).     

Layer uniformity of glancing angle deposition

Some results of an investigation on the layer thickness uniformity of glancing angle deposition are presented. A zirconia monolayer has been deposited by glancing angle deposition to analyze the layer thickness uniformity. The experimental results indicate that the thickness variation over the substrate is less than 0.1%, which is considered as good uniformity. It is found that the non-uniformity of experimental results is larger than that of the theoretical results.     

Nanospring pressure sensors grown by glancing angle deposition

Arrays of Cr zigzag nanosprings and slanted nanorods, 15-55 nm and 40-80-nm-wide, respectively, were grown on SiO2/Si substrates by glancing angle deposition. The arrays exhibit a reversible change in resistivity upon loading and unloading, by 50% for nanosprings and 5% for nanorods, indicating their potential as pressure sensors. The resistivity drop is due to a compression of nanosprings (by a measured 19% for an applied external force of 10(-10) N per spring), which causes them to physically touch their neighbors, providing a path for electric current to flow between nanosprings. Repeated loading and unloading at large loads (> or =1 MPa) results in irreversible plastic deformation and a degradation of the pressure sensitivity.     

Film morphology modification in ion-assisted glancing angle deposition

Porous structured films grown with the glancing angle deposition technique have been widely studied for thin film optical device applications. We report the use of ion assistance to modify the structural and optical properties of porous silicon dioxide and titanium dioxide columnar thin films grown at deposition angles of 70° and 85°. Optical characterization studies show that tilted columnar structures will undergo an increase in tilt angle and film density with increasing ion dose. These two trends contrast with unassisted films where film density and column tilt angle are primarily controlled by the deposition angle. Thus, a regime of film structures simultaneously exhibiting high film density and large column tilt angle is enabled by incorporating an ion-assisted process. The phisweep substrate motion algorithm for minimizing columnar anisotropy used in conjunction with ion-assisted deposition provides additional control over film morphology and expands the utility of this modified fabrication process.     

Porous broadband antireflection coating by glancing angle deposition

We deposited graded-index SiO2 films using glancing angle deposition to produce high-transmission antireflection coatings on glass. Because of the accurate control over the thin-film microstructure provided by this technique, we were able to create graded densities with a Gaussian profile resulting in transmission values greater than 99.9% for a single-layer interface with bandwidths up to 460 nm. The graded-index layer also provides low reflectance at nonnormal angles of incidence with transmission values degrading little for incidence angles up to 30 degrees.     

Roughness of glancing angle deposited titanium thin films: an experimental and computational study

The characterization of roughness at the nanoscale by the means of atomic force microscopy (AFM) was performed on high aspect ratio glancing angle deposited titanium thin films. With the use of scanning electron microscopy as well as x-ray photoelectron spectroscopy, it was shown that the AFM measurements gave rise to incorrect roughness values for the films consisting of the highest aspect ratio structures. By correcting for this experimental artefact, the difference between the saturated roughness value of a film grown with conventional physical vapour deposition and films grown with a glancing angle of deposition was shown to behave as a power law function of the deposition angle, with a saturated roughness exponent of κ?=?7.1?±?0.2. This power law scaling was confirmed by three-dimensional molecular dynamics simulations of glancing angle deposition, where the saturated roughness exponent was calculated to κ?=?6.7?±?0.4.     

纳米结构的倾斜角度沉积及性能优化

纳米材料发展的关键是纳米结构的制备、形貌调控和性能优化.倾斜角度沉积是以较大的角度(大于75°)倾斜入射沉积薄膜,通过控制沉积参数,得到具有特殊形貌纳米结构的方法,具有适用范围广,操作便捷,制备的薄膜面积大、纯度高、结构规整等特点,是一种理想的制备纳米材料的方法.本文介绍了采用倾斜角度沉积技术制备氧化铪抗反射薄膜和银基表面增强拉曼基底,详细分析了该方法的参数调控对纳米结构的形貌和性能的影响,并指出将倾斜角度沉积与其他先进技术相结合(以原子层沉积为例),可进一步优化纳米结构的性能,提高倾斜角度沉积的使用范围.     

Silicon nanorods prepared by glancing angle catalytic chemical vapor deposition

Vertically oriented amorphous and microcrystalline Si nanorods grown on different substrates were successfully obtained by Cat CVD with the glancing angle incident silane flux at low temperatures. The influences of the substrate type, substrate temperature, post treatment and hydrogen dilution on the microstructure of Si nanorods were investigated. The density and diameter of nanorods are varying with the substrates. The hydrogen dilution of silane dominates the crystallization of Si nanorods rather than high substrate temperature at 550 °C and annealing at 900 °C in nitrogen for 6 h. The crystallized Si nanorods with crystalline volume fraction, Xc, of 0.55 were achieved under a low substrate temperature of 140 °C.     

Vapor deposited sculptured nano-porous titania films by glancing angle deposition for efficiency enhancement in dye-sensitized solar cells

Sculptured porous titania films as photoanode in dye-sensitized solar cell (DSSC) were prepared using an electron-beam evaporation system with glancing angle deposition (GLAD) method. By controlling the substrate rotation rate and the incident angle of evaporant, titania films of various thicknesses were prepared on ITO glasses. The as-deposited nano-porous films are comprised of helical nano-columns and assembled in an orderly manner with gaps or pores in between, which offer large internal surface area for dye adsorption and direct electron transfer path. There is a positive correlation between the film thickness, film effective surface area, amount of absorbed dye and cell efficiency. The nano-porous films provide a synergistic effect of high surface area, effective route for electron transfer, tight interfaces, and enhanced light trapping, which are all beneficial for higher cell efficiency. The DSSC consisting of a 6 μm titania film, deposited at substrate rotating rate 0.17 rpm and incident angle 73°, gave a cell efficiency of 6.1%.     

The structure of Ta nanopillars grown by glancing angle deposition

Regular arrays of Ta nanopillars, 200 nm wide and 500 nm tall, were grown on SiO₂ nanosphere patterns by glancing angle sputter deposition (GLAD). Plan-view and cross-sectional scanning electron microscopy analyses show dramatic changes in the structure and morphology of individual nanopillars as a function of growth temperature T_s ranging from 200 to 700 °C. At low temperatures, T_s ≤ 300 °C, single nanopillars develop on each sphere and branch into subpillars near the pillar top. In contrast, T_s ≥ 500 °C leads to branching during the nucleation stage at the pillar bottom. The top branching at low T_s is associated with surface mounds on a growing pillar that, due to atomic shadowing, develop into separated subpillars. At high T_s, the branching occurs during the nucleation stage where multiple nuclei on a single SiO₂ sphere develop into subpillars during a competitive growth mode which, in turn, leads to intercolumnar competition and the extinction of some nanopillars.     

Indium tin oxide nanowhisker morphology control by vapour-liquid-solid glancing angle deposition

A new growth technique for indium tin oxide nanowhiskers with increased control over feature size and spacing is reported. The technique is based on a unique combination of self-catalysed vapour-liquid-solid (VLS) growth and glancing angle deposition (GLAD). This VLS-GLAD technique provides enhanced control over nanowhisker morphology as the effect of typical VLS growth parameters (e.g.?flux rate, temperature) is amplified at large deposition angles characteristic of GLAD. Spatial modulation of the collimated growth flux controls trunk width, number and orientation of branches, and overall nanowhisker density. Here we report the influence of growth conditions (including deposition angle, flux rate, nominal pitch and substrate temperature) on nanowhisker morphology, with specific focus on the effect of large deposition angles. Sheet resistance and transmission of the films were measured to characterize their performance as transparent conductive oxides. Hybrid nanostructured films grown in this study include high surface area nanowhiskers protruding from a conductive film, ideal for transparent conductive electrode applications.     

Multi-phase structured silicon carbon nitride thin films prepared by hot-wire chemical vapour deposition

In this work, Silicon Carbon Nitride (Si-C-N) thin films were deposited by Hot Wire Chemical Vapour Deposition (HWCVD) technique from a gas mixture of silane (SiH₄), methane (CH₄) and nitrogen (N₂). Six sets of Si-C-N thin films were produced and studied. The component gas flow rate ratio (SiH₄:CH₄:N₂) was kept constant for all film samples. The total gas flow-rate (SiH₄ + CH₄ + N₂) was changed for each set of films resulting in different total gas pressure which represented the deposition pressure for each of these films ranging from 40 to 100 Pa. The effects of deposition pressure on the chemical bonding, elemental composition and optical properties of the Si-C-N were studied using Fourier transform infrared (FTIR) spectroscopy, Auger Electron Spectroscopy (AES) and optical transmission spectroscopy respectively. This work shows that the films are silicon rich and multi-phase in structure showing significant presence of hydrogenated amorphous silicon (a-Si:H) phase, amorphous silicon carbide (a-SiC), and amorphous silicon nitride (a-SiN) phases with Si-C being the most dominant. Below 85 Pa, carbon content is low, and the films are more a-Si:H like. At 85 Pa and above, the films become more Si-C like as carbon content is much higher and carbon incorporation influences the optical properties of the films. The properties clearly indicated that the films underwent a transition between two dominant phases and were dependent on pressure.     

The dependence of the texture of tellurium thin films on vacuum deposition angle

Vacuum-deposited tellurium thin films can show substantially different surface morphologies depending on the angle with which the vapor stream impinges on the substrate surface. These tellurium thin films have a tendency to grow as acicular crystallites but as the deposition angle is increased so that the vapor stream becomes tangetial to the substrate surface the spacing between crystallites increase and approaches, at stream angles of approximately 80° from the normal, dimensions roughly once or twice the average wavelength of visible light. Such films may have application in solar energy collector systems because of the high absorptivity of sunlight shown by such films. Mechanisms which describe the tendency for crystallite spacing to increase with increasing angle are discussed.     

Optimization of periodic column growth in glancing angle deposition for photonic crystal fabrication

We investigate the growth of periodically aligned silicon microstructures for the fabrication of square spiral photonic crystals using the glancing angle deposition phi-sweep process. We report the optimization of the phi-sweep offset angle for fabrication of microstructures with more precise geometry. The effects of varying the sweep offset angle of the phi-sweep process are studied for films deposited onto a square lattice array of growth seeds. To represent one growth segment of the phi-sweep process, we fabricate 15?nm silicon thin films using several azimuthal substrate offsets from 0° to 45° at a vapor incidence angle of 85°. We also deposit silicon square spirals on square lattice arrays with the phi-sweep method, using various sweep offset angles from γ = 0° to 45°. We find that using an offset angle of γ = 26.5° optimizes the shadowing geometry, which minimizes anisotropic broadening, producing greater quality photonic crystal structures. From normal incidence reflection spectroscopy, a maximum full width at half-maximum of 273 ± 3?nm and a relative peak width (Δλ/λ) of 16.1 ± 0.1% were found for a sweep offset angle of γ = 26.5°.     

Localized surface plasmon resonance biosensor using silver nanostructures fabricated by glancing angle deposition

Glancing angle deposition was used to produce approximately 150-nm-thick silver nanoparticle films, which were evaluated as localized surface plasmon resonance (LSPR) biosensors. The films have a strong extinction peak around 368 nm in air due to LSPR. As the refractive index of the surrounding environment is increased, the extinction peak red-shifts with a linear dependence. The films were functionalized with 11-amino-1-undecanethiol and rabbit immunoglobulin G (rIgG) to allow for the detection of anti-rIgG binding. Binding of biomolecules to the nanoparticle surface increases the local refractive index and results in a red-shifting of the extinction peak. The wavelength shift at varying concentrations of anti-rIgG was measured and fit to the Langmuir isotherm. This yielded approximate values for the saturation response, Delta lambda max = 29.4 +/- 0.7 nm, and the surface confined binding constant, Ka = (2.7 +/- 0.3) x 10(6) M(-1). The response to nonspecific binding was also investigated.     

Ion-beam-assisted deposition of thin films

Some effects on the properties of electron-beam evaporated thin films produced by ion bombardment of the growing film are reported. Substantial increases in the packing densities of SiO2 , TiO2 , and ZrO2 films have been produced as measured by the reduction in the adsorption of moisture when the films are exposed to a humid atmosphere. In a ZrO2-SiO2 multilayer interference filter, changes in the wavelength of the peak transmittance on exposure to the atmosphere have been reduced from 8 nm for films deposited without ion bombardment to <1 nm for ion-beam-assisted films.