Frans Munnik

Low temperature silicon dioxide by thermal atomic layer deposition: Investigation of material properties

SiO2 is the most widely used dielectric material but its growth or deposition involves high thermal budgets or suffers from shadowing effects. The low-temperature method presented here (150 °C) for the preparation of SiO2 by thermal atomic layer deposition (ALD) provides perfect uniformity and surface coverage even into nanoscale pores, which may well suit recent demands in nanoelectronics and nanotechnology. The ALD reaction based on 3-aminopropyltriethoxysilane, water, and ozone provides outstanding SiO2 quality and is free of catalysts or corrosive by-products. A variety of optical, structural, and electrical properties are investigated by means of infrared spectroscopy, UV-Vis spectroscopy, secondary ion mass spectrometry, capacitance-voltage and current-voltage measurements, electron spin resonance, Rutherford backscattering, elastic recoil detection analysis, atomic force microscopy, and variable angle spectroscopic ellipsometry. Many features, such as the optical constants (n, k) and optical transm...

A proposal for an unusually stiff and moderately ductile hard coating material: Mo2BC

The elastic properties of Mo2BC were studied using ab initio calculations. The calculated bulk modulus of 324 GPa is 45% larger than that of Ti0.25Al0.75N and 14% smaller than that of c-BN, indicating a highly stiff material. The bulk modulus (B) to shear modulus (G) ratio is 1.72 at the transition from brittle to ductile behaviour. This, in combination with a positive Cauchy pressure (c12 − c44), suggests moderate ductility. When compared with a typical hard protective coating such as Ti0.25Al0.75N (B = 178 GPa; B/G = 1.44; negative Cauchy pressure), Mo2BC displays considerable potential as protective coating for metal cutting applications. In order to test this proposal, Mo2BC thin films were synthesized using dc magnetron sputtering from three plasma sources on Al2O3(0 0 0 1) at a substrate temperature of ~900 °C. The calculated lattice parameters are in good agreement with values determined from x-ray diffraction. The measured Youngs modulus values of ~460 ± 21 GPa are in excellent agreement with the 470 GPa value obtained by calculations. Scanning probe microscopy imaging of the residual indent revealed no evidence for crack formation as well as significant pile-up, which is consistent with the moderate plasticity predicted. The apparent contradiction between moderate ductility on the one hand and indentation hardness values of 29 GPa can be understood by considering the electronic structure particularly the extreme anisotropy. The presence of stiff Mo–C and Mo–B layers with metallic interlayer bonding enables this intriguing and unexpected property combination.

Phase separation in carbon-nickel films during hyperthermal ion deposition

Microstructure evolution as a function of the substrate temperature and metal content of C:Ni nanocomposite films grown by hyperthermal ion deposition is investigated. The films were grown by pulsed filtered cathodic vacuum arc on thermally oxidized Si substrates held at temperatures in the range from room temperature (RT) to 500 °C and with the metal content ranging from 7 to 40 at. %. The elemental depth profiles and composition were determined by elastic recoil detection analysis. The film morphology and phase structure were studied by means of cross-sectional transmission electron microscopy and selected area electron diffraction. For RT deposition a transition from repeated nucleation dominated toward self-organized growth of alternating carbon and crystalline nickel carbide layers is observed at a Ni threshold content of ∼40 at. %. The surface diffusion increases concomitantly with the growth temperature resulting in the formation of elongated/columnar structures and a complete separation of the fil...

Establishing the mechanism of thermally induced degradation of ZnO:Al electrical properties using synchrotron radiation

X-ray absorption near edge structure and x-ray diffraction studies with synchrotron radiation have been used to relate the electrical properties of ZnO:Al films to their bonding structure and phase composition. It is found that Al-sites in an insulating metastable homologous (ZnO)3Al2O3 phase are favored above a certain substrate temperature (TS) leading to deterioration of both the crystallinity and the electrical properties of the films. The higher film resistivity is associated with lower carrier mobility due to increased free electron scattering. Lower metal to oxygen flux ratios during deposition expand the range of TS at which low-resistivity films are obtained.

Enhancement in the photocatalytic nature of nitrogen-doped PVD-grown titanium dioxide thin films

Nitrogen-doped titanium dioxide semiconductor photocatalytic thin films have been deposited by unbalanced reactive magnetron physical vapor deposition on glass substrates for self-cleaning applications. In order to increase the photocatalytic efficiency of the titania coatings, it is important to enhance the catalysts absorption of light from the solar spectra. Bearing this fact in mind, a reduction in the titania semiconductor band-gap has been attempted by using nitrogen doping from a coreactive gas mixture of N2:O2 during the titanium sputtering process. Rutherford backscattering spectroscopy was used in order to assess the composition of the titania thin films, whereas heavy-ion elastic recoil detection analysis granted the evaluation of the doping level of nitrogen. X-ray photoelectron spectroscopy provided valuable information about the cation-anion binding within the semiconductor lattice. The as-deposited thin films were mostly amorphous, however, after a thermal annealing in vacuum at 500 °C the ...

Study of amorphous lithium silicate thin films grown by atomic layer deposition

Lithium silicate thin films, which are interesting materials for example in lithium ion batteries, were grown by the atomic layer deposition technique from lithium hexamethyldisilazide [LiHMDS, Li(N(SiMe3)2)] and ozone precursors. Films were obtained at a wide deposition temperature range between 150 and 400 °C. All the films were amorphous except at 400 °C, where partial decomposition of LiHMDS was also observed. The growth behavior was examined in detail at 250 °C, and saturation of growth rates and refractive indices with precursor doses was confirmed, thereby verifying self-limiting surface reactions. Likewise, the linear thickness dependence of the films with the number of deposition cycles was verified. Strong dependence of growth rate and film composition on deposition temperature was also seen. Overall, the amorphous films grown at 250 °C had a stoichiometry close to lithium metasilicate (Li2.0SiO2.9) with 0.7 at. % carbon and 4.6 at. % hydrogen impurities. The corresponding growth rate and refrac...

Bulk diffusion induced structural modifications of carbon-transition metal nanocomposite films

The influence of transition metal (TM = V,Co,Cu) type on the bulk diffusion induced structural changes in carbon:TM nanocomposite films is investigated. The TMs have been incorporated into the carbon matrix via ion beam co-sputtering, and subsequently the films have been vacuum annealed in the temperature range of 300 – 700 °C. The structure of both the dispersed metal rich and the carbon matrix phases has been determined by a combination of elastic recoil detection analysis, x-ray diffraction, transmission electron microscopy, and Raman spectroscopy. The as-grown films consist of carbidic (V and Co) and metallic (Cu) nanoparticles dispersed in the carbon matrix. Thermal annealing induces surface segregation of Co and Cu starting at ≥ 500 °C, preceded by the carbide-metal transformation of Co-carbide nanoparticles at ∼ 300 °C. No considerable morphological changes occur in C:V films. In contrast to the surface diffusion dominated regime where all the metals enhance the six-fold ring clustering of C, in th...

Stopping powers of 200–3200 keV 4He and 550–1550 keV 1H ions in polyimide

Accurate stopping powers of polyimide have been determined for mean energies (E) in the range of 200 keV≤E≤3200 keV for 4He ions and 550 keV≤E≤1550 keV for 1H ions, using the transmission method for foils with areal densities of 30–225 μg/cm2. The overall uncertainties of ∼2% are mainly due to the foil thickness determination. The present data have been parametrized and compared to results obtained by previous authors in the upper energy range and to various parametrizations found in the literature. The best description of the data is given by Bragg’s rule calculations using parametrized elemental stopping powers that were derived from large data sets (deviations <2%). No support is found for the cores‐and‐bonds model showing deviations of 3%–5%, that may be due to the neglect of phase state effects.

Single crystal strontium titanate surface and bulk modifications due to vacuum annealing

Vacuum annealing is a widely used method to increase the electric conductivity of SrTiO3 single crystals. The induced oxygen vacancies act as intrinsic donors and lead to n-type conductivity. Apart from the changed electronic structure, however, also crystal structure modifications arise from this treatment. Hence, electronic properties are determined by the interplay between point defects and line defects. The present paper provides a survey of the real structure of commercially available SrTiO3 single crystals and the changes induced by reducing vacuum heat-treatment. Therefore, all investigations were performed ex situ, i.e., after the annealing process. Used characterization methods include atomic force microscopy, transmission electron microscopy, spectroscopic ellipsometry, infrared spectroscopy, and photoluminescence spectroscopy. Besides the expected variation of bulk properties, especially surface modifications have been detected. The intrinsic number of near-surface dislocations in the samples w...

Study on Atomic Layer Deposition of Amorphous Rhodium Oxide Thin Films

Atomic layer deposition (ALD) of rhodium oxide thin films was studied using Rh(acac) 3 [acetylacetonato (acac)] and ozone as precursors. Amorphous Rh 2 0 3 thin films were deposited between 160 and 180°C. The sublimation temperature of Rh(acac) 3 set the low temperature limit for the oxide film deposition, while the high temperature limit was governed by the partial reduction of the film to metallic rhodium. The rhodium oxide films were successfully deposited on Al 2 O 3 nucleation layers, soda lime glasses, and native oxide-covered silicon substrates. The films demonstrated excellent conformality as a characteristic to ALD. The films were not uniform across the substrate, which was most likely due to the catalyzing effect of Rh 2 O 3 for ozone decomposition. However, the nonuniformity was repeatable and could simply be compensated in the cross-flow reactor. By splitting the deposition in two stages with 180° substrate rotation in between, good uniformity across the substrate was accomplished. The resistivities of about 80 nm thick Rh 2 O 3 films were from 5 to 8 mΩ cm.