Microstructural and frictional control of diamond-like carbon films deposited on acrylic rubber by plasma assisted chemical vapor deposition

In this paper we concentrate on the microstructure of diamond-like carbon films prepared by plasma assisted chemical vapor deposition on acrylic rubber. The temperature variation produced by the ion impingement during plasma cleaning and subsequent film deposition was monitored and controlled as a function of bias voltage and treatment time. Its influence during film growth on the appearance of patterns of cracks and wrinkles, caused by the thermal stresses is evaluated. Different growth modes are proposed in order to explain the smaller patch sizes observed at negative variations of temperature. The coefficient of friction (CoF) of the samples is measured using a pin-on-disk tribometer in non-lubricated conditions. Much lower CoF values than unprotected rubber are seen, which can be correlated with the observed patch size.     

Superhydrophobic polymer films via aerosol assisted deposition — Taking a leaf out of nature's book

Aerosol assisted deposition of three sets of polymer films based on commercially available resins was achieved on various substrates. The films were characterised using a range of methods, including water contact and slip angle to determine water repellent properties. The aerosol assisted deposition inside the chemical vapour deposition reactor was unique in generating a highly rough superhydrophobic surface with water contact angles up to 170°. During the deposition process, two of the polymers were cured resulting in the development of high surface morphology. It was observed that the polymer that did not cure did not develop such a rough surface resulting in a lower water contact angle (∼ 99°). The superhydrophobic films had a Cassie-Baxter type wetting with water failing to penetrate the surface porosity, water spraying on the surface would bounce off. These films had exceptionally low slide angles of ca 1-2° from the horizontal.     

The incorporation of preformed metal nanoparticles in zinc oxide thin films using aerosol assisted chemical vapour deposition

The feasibility of Aerosol Assisted Chemical Vapour Deposition (AA-CVD) has been investigated for the growth of zinc oxide (ZnO) films containing preformed metal nanoparticles. The deposition parameters were first established for ZnO thin films, by varying the heating configuration, substrate temperature and deposition time. Films were characterised using Scanning Electron Microscopy and X-Ray Diffraction. As-deposited films, grown at 250 °C, were mostly amorphous and transformed to highly crystalline Wurtzite ZnO at higher substrate temperatures (400-450 °C). A change in the preferential orientation of the films was observed upon changing (i), the substrate temperature or (ii), the heating configuration. Following this, the applicability of the AA-CVD process for the incorporation of preformed nanoparticles (platinum and gold) in ZnO thin films was investigated. It was found that surface agglomeration occurred, such that the ZnO films were capped with an inhomogeneous coverage of the metal. These layers were characterised using Transmission Electron Microscopy and Electron Diffraction. A possible mechanism for the formation of these metal surface clusters is presented.     

Growth of aluminum nitride thin films prepared by plasma-enhanced atomic layer deposition

Aluminum nitride (AlN) thin films were deposited by atomic layer deposition from aluminum chloride (AlCl₃) and an ammonia/hydrogen plasma. The most important role of the ammonia/hydrogen plasma was to act as a reducing agent to extract Cl from AlCl₃, and to form AlN subsequently. The growth rate was saturated at ∼0.042 nm/cycle, and the thickness was proportional to the number of reaction cycles. Repeating this reaction cycle led to precisely controlled growth. The film properties were analyzed using Auger electron spectroscopy, X-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy and time-of-flight elastic recoil detection analysis. The concentration of chlorine and hydrogen impurities was 0.23 and 2.01 at.%, respectively. AlN films showed good anti-oxidation properties when O₂ was annealed at 650 °C for 30 min.     

Characteristics of atomic layer deposition grown HfO2 films after exposure to plasma treatments

Ultra thin HfO₂ films were grown by the atomic layer deposition (ALD) technique using tetrakismethylethylaminohafnium (Hf[N(CH)₃(C₂H₅)]₄) and ozone (O₃) as the precursors and subsequently exposed to various plasma conditions, i.e., CCP (capacitively coupled plasma) and MMT (modified magnetron typed plasma) in N₂ or N₂/O₂ ambient. The conventional CCP treatment was not effective in removing the carbon impurities, which were incorporated during the ALD process, from the HfO₂ films. However, according to the X-ray photoelectron spectroscopy measurements, the MMT treated films exhibited a significant reduction in their carbon contents and the efficient incorporation of nitrogen atoms. Although the incorporated nitrogen was easily released during the post-thermal annealing of the MMT treated samples, it was more effective than the CCP treatment in removing the film impurities. Consequently, the MMT treated samples exhibited excellent electrical properties as compared to the as-deposited HfO₂ films, including negligible hysteresis (flatband voltage shift), a low leakage current, and the reduced equivalent oxide thickness of the gate stack. In conclusion, MMT post treatment is more effective than conventional CCP treatment in improving the electrical properties of high-k films by reducing the carbon contamination and densifying the as-deposited defective films.     

Single layer and multilayered films of plasma polymers analyzed by nanoindentation and spectroscopic ellipsometry

Well-defined single layer and multilayered a-SiC:H films, deposited from tetravinylsilane at different powers by plasma-enhanced chemical vapor deposition on silicon, were intensively studied by in situ spectroscopic ellipsometry, nanoindentation, and atomic force microscopy. A realistic model of the sample structure was used to analyze ellipsometric data and distinguish individual layers in the multilayered film, evaluate their thickness and optical constants. Dispersion dependences for the refractive index were well separated for each type of individual layer, if the thickness was decreased from 315 to 25 nm, and corresponded to those of the single layer. A beveled section of the multilayered film revealed the individual layers that were investigated by atomic force microscopy and nanoindentation to confirm that mechanical properties in multilayered and single layer films are similar.     

Deposition of nano-crystalline graphite films by cathodic plasma electrolysis

Atmospheric pressure plasma deposition of nano-crystalline graphite films on titanium substrates from a predominantly ethanolic liquid phase was carried out under varying applied voltage. A thorough study of the plasma electrolytic deposition mechanisms has been performed. The investigation of the composition, structural properties, and the morphology of these graphite coatings have been performed by visible and ultraviolet Raman spectroscopy, X-ray Photoelectron Spectroscopy, Scanning Electron Microscopy and X-ray elemental microanalysis. The experimental evidence of the reduction of the work function and the enhancement of the plasma intensity with the presence of the carbon film has been reported. These properties make such nano-crystalline graphite coatings very attractive for the production of inexpensive cold cathodes for electronics and plasma devices.     

Goniocolorimetric study of aluminum oxide films deposited by atomic layer deposition

The interference colors resulting from thin films of Al₂O₃ deposited by atomic layer deposition (ALD) on silicon have been rigorously analyzed using a recently developed robotic gonioreflectometer. A series of eleven increasingly thick films was deposited, up to 1613 Å, and their reflectance values obtained for the visible spectrum. A comparison of these values with the predictions of computer simulations employing Fresnel equations has revealed that while there was generally good agreement between predicted and measured spectra, there are some spectral regions that exhibit large deviations from predicted reflectances, typically at near-normal measurement angles and shorter wavelengths. The effect of these discrepancies on color appearance was investigated in the CIE L*a*b* color space for the daylight illuminant D65. Large iridescence is both predicted and measured for most film thicknesses. Chroma and hue differences as large as 20 CIELAB units between the predicted and the measured color centers were obtained. Simulation also predicts larger iridescence than what is actually measured. A likely cause for the observed discrepancies is that the dielectric constants of the ALD films deviate from the literature values for the bulk material.     

Atomic layer deposited aluminum oxide barrier coatings for packaging materials

Thin aluminum oxide coatings have been deposited at a low temperature of 80 °C on various uncoated papers, polymer-coated papers and boards and plain polymer films using the atomic layer deposition (ALD) technique. The work demonstrates that such ALD-grown Al₂O₃ coatings efficiently enhance the gas-diffusion barrier performance of the studied porous and non-porous materials towards oxygen, water vapor and aromas.     

Monocrystalline zinc oxide films grown by atomic layer deposition

In the present work we report on the monocrystalline growth of (00.1) ZnO films on GaN template by the Atomic Layer Deposition technique. The ZnO films were obtained at temperature of 300 °C using dietylzinc (DEZn) as a zinc precursor and deionized water as an oxygen precursor. High resolution X-ray diffraction analysis proves that ZnO layers are monocrystalline with rocking curve FWHM of the 00.2 peak equals to 0.07°. Low temperature photoluminescence shows a sharp and bright excitonic line with FWHM of 13 meV.     

Artifacts in SPM measurements of thin films and coatings

Ideally, scanning probe microscopy (SPM) should generate a three-dimensional map of a sample surface such that the result is an exact replication of the actual sample. Any measurement data that result in an image differing from the actual sample surface are artifacts. The chief sources of SPM artifacts are mechanical systems, piezoelectric crystals, electronic scanners, tip-sample interaction, and image processing. For example, choosing the proper SPM probe for a specific sample is only the first step in minimizing probe-related artifacts. In fact, geometrical effects cause the largest number of artifacts. Good quality atomic SPM images can be clearly seen in raw data and should respond appropriately when the scan range or rotation is changed. Because SPM images are often periodic, it is possible for heavily filtered “data” to sometimes be misinterpreted as “atomic resolution images”. This paper presents SPM image studies using a range of materials from hard rough diamond films to soft nanometer smooth polyimide films. The investigation brings out the hidden sources of SPM artifacts for samples with different geometries and physical properties. Ten suggestions are presented which, if implemented/followed, should minimize the number of SPM image artifacts thereby assuring high quality images.     

Effects of argon and oxygen flow rate on water vapor barrier properties of silicon oxide coatings deposited on polyethylene terephthalate by plasma enhanced chemical vapor deposition

Plasma polymer coatings were deposited from hexamethyldisiloxane on polyethylene terephthalate (PET) substrates while varying the operating conditions, such as the Ar and O₂ flow rates, at a fixed radio frequency power of 300 W. The water vapor transmission rate (WVTR) of the untreated PET was 54.56 g/m²/day and was decreased after depositing the silicon oxide (SiO_x) coatings. The minimum WVTR, 0.47 g/m²/day, was observed at Ar and O₂ flow rates of 4 and 20 sccm, respectively, with a coating thickness of 415.44 nm. The intensity of the peaks for the Si-O-Si bending at 800-820 cm^− 1 and Si-O-Si stretching at 1000-1150 cm^− 1 varied depending on the Ar and O₂ flow rates. The contact angle of the SiO_x coated PET increased as the Ar flow rate was increased from 2 to 8 sccm at a fixed O₂ flow rate of 20 sccm. It decreased gradually as the oxygen flow rate increased from 12 to 28 sccm at a fixed Ar carrier gas flow rate. The examination by atomic force microscopy revealed a correlation of the SiO_x morphology and the water vapor barrier performance with the Ar and O₂ flow rates. The roughness of the deposited coatings increased when either the O₂ or Ar flow rate was increased.     

The uniformity of Al distribution in aluminum-doped zinc oxide films grown by atomic layer deposition

We investigated the aluminum distribution in aluminum-doped zinc oxide films grown by atomic layer deposition. Surface morphology, structure, composition and electrical properties of obtained films were studied. For the aluminum content less than 2 at.%, a periodicity of Al distribution along the layer depth was observed. This periodicity diminished significantly after annealing the samples in nitrogen atmosphere at 300 °C. For the Al content higher than 2 at.%, its distribution in ZnO:Al films was uniform within the depth measurement accuracy of ∼5-10 nm.     

The role of trimethylgallium flow during nucleation layer deposition in the optimization of epitaxial GaN films

The effects of the trimethylgallium flow (14–55 μmol/min) during the deposition of the GaN nucleation layer on the structure and electronic properties of GaN epilayers were examined. X-ray and mobility studies indicate that GaN epilayers, grown using non-optimal trimethylgallium (TMG) flow, result in wide FWHM peak and low electron mobility. On the contrary, an optimal TMG flow during the nucleation layer growth leads to films with superior structural and electronic properties. Atomic force microscopy (AFM) was used to systematically investigate the morphological evolution of as-grown nucleation layers, and the nucleation layers were heated to 1000°C under different TMG flows.     

Use of ultra-thin aluminum oxide layer to reduce photoluminescence decay in poly(p-phenylene vinylene) films

The degradation of conjugated polymer poly(p-phenylene vinylene) (PPV) in the atmosphere upon exposure to ultraviolet light limits its applications as the emitting layer in organic light emitting diodes. In this paper we show that a thin layer of aluminum oxide around 10 nm in thickness prevents photoluminescence degradation of PPV during exposure to blue light in the atmosphere but not at lower excitation wavelengths. This oxide film is free of cracks and pinholes from transmission electron microscopy analysis.     

Investigation of the growth of In2O3 on Y-stabilized ZrO2(100) by oxygen plasma assisted molecular beam epitaxy

Thin films of In₂O₃ have been grown on Y-stabilised ZrO₂(100) substrates by oxygen plasma assisted molecular beam epitaxy over a range of substrate temperatures between 650 °C and 900 °C. Growth at 650 °C leads to continuous but granular films and complete extinction of substrate core level structure in X-ray photoelectron spectroscopy. However with increasing substrate temperature the films break up into a series of discrete micrometer sized islands. Both the continuous and the island films have excellent epitaxial relationship with the substrate as gauged by X-ray diffraction and selected area electron diffraction and lattice imaging in high resolution transmission electron microscopy.     

Surface morphology and structure of ultra-thin magnesium oxide grown on (100) silicon by atomic layer deposition oxidation

Ultra-thin magnesium oxide layers were elaborated by atomic layer deposition and oxidation process on silicon (100) starting from (2 × 1) thermally-reconstructed or hydrogen-terminated Si surfaces. Low-energy electron diffraction experiments show (2 × 3) and (3 × 3) reconstructions while depositing a magnesium monolayer on Si clean surfaces, and a 3-dimentional growth of the oxide as confirmed by ex-situ atomic force microscopy. For hydrogen-terminated or clean surfaces previously physisorbed by oxygen, uniform cobalt/magnesium-oxide/silicon stacks of layers are observed by transmission electron microscopy. Annealing above 150 °C leads to MgO dissolution and formation of an interfacial complex compound by inter-diffusion of Si and Co.     

Self-assembled tungsten oxide nanowires by electron beam assisted rapid thermal annealing

We report on the fabrication of WO₃ nanowires on Si (100) substrate using nickel catalyzed electron beam assisted rapid thermal annealing process. A 7 nm thick W layer deposited on the nickel coated substrate was annealed under high vacuum using electron beam (3 keV) for 30, 60 and 90 s. The nickel activates the growth of tungsten nanowires with a high aspect ratio and subsequently is oxidized due to the high refractory nature of tungsten under exposure to oxygen gas. The resulting changes in surface morphology, oxidization state and elemental composition of WO₃ nanowires were investigated systematically. The oxidization of metallic tungsten nanowire was found to depend on the annealing time.     

Native oxide consumption during the atomic layer deposition of TiO2 films on GaAs (100) surfaces

The consumption of the surface native oxides is studied during the atomic layer deposition of TiO₂ films on GaAs (100) surfaces. Films are deposited at 200 °C from tetrakis dimethyl amido titanium and H₂O. Transmission electron microscopy data show that the starting surface consists of ~2.6 nm of native oxide and X-ray photoelectron spectroscopy indicates a gradual reduction in the thickness of the oxide layer as the thickness of the TiO₂ film increases. Approximately 0.1-0.2 nm of arsenic and gallium suboxide is detected at the interface after 250 process cycles. For depositions on etched GaAs surfaces no interfacial oxidation is observed.     

Vapor-solid-solid growth of crystalline silicon nanowires using anodic aluminum oxide template

Silicon nanowires (SiNWs) were grown at low temperatures close to metal silicon eutectic point on a silicon substrate using gold catalyst coupled with assistance of the aluminum anodic oxide template. Either a vapor-solid-solid (VSS) growth process below metal silicon eutectic temperature or a vapor-liquid-solid (VLS) process at slightly higher temperatures was observed. The transmission electron microscopy coupled with both the X-ray energy dispersive spectroscopy and the selected area electron diffraction was adopted to characterize the SiNWs. Although the mechanism triggering the VSS process is still not clear, both the geometric and morphological characteristics of the SiNWs grown by the VSS process are discussed and compared with the SiNWs grown by the VLS process. The VSS SiNWs have a much slower growth rate (less than 100 nm/h), a smaller and more uniform diameter (in the range of 15.22 nm) due to a much slower rate of silicon diffusion and much smaller amount of silicon (6.8 wt.%) dissolved in the solid nanocatalyst.