Abnormal Grain Growth in AlScN Thin Films Induced by Complexion Formation at Crystallite Interfaces

Sputter deposited Al(1-x)ScxN thin films with a Sc content from x = 0 to 43 at% are investigated by electron microscopy in order to study and explain the formation and growth of abnormally oriented grains (AOG). It is found that the latter did not nucleate at the interface with the substrate, but at high energy grain boundaries, at which systematically higher Sc concentrations are detected. The AOGs are thus formed during the growth of c-textured grains. They grow faster than those, and finally protrude from the c-textured film surface, having at their end a pyramidal shape with three facets of a hexagonal wurtzite crystal: one (0001) and two (112 over bar 0) facets. Process conditions favoring less compact grain boundaries, and lower surface diffusion across grain boundaries are thought to promote nucleation of AOGs. Finally, a 4-step growth mechanism explaining the nucleation from a Sc-rich complexion and proliferation of AOGs with increasing film thickness is proposed.

Free carriers in nanocrystalline titanium dioxide thin films

Simon Springer

This thesis analyzes the properties of heavily doped nanocrystalline titanium dioxide. Thin films were deposited by magnetron sputtering with either water vapor as reactive gas or a periodically interrupted oxygen supply. The samples were at the same time electrically conducting and transparent. They consisted of mixtures of rutile, anatase and amorphous phases. Titanium dioxide is chemically stable, hard, non-toxic, transparent, and inexpensive. Due to a high refractive index it is often found in optical applications as a thin film coating. For many purposes it is interesting to take advantage of a combination of good transparency and electrical conductivity. An even larger field of applications would open if the electric conductivity of TiO2 could be increased in a controlled manner. Conventional bulk doping is limited, however, by low solubility limits. Highly conducting nanocrystalline TiO2 thin films have been obtained recently by sputtering in presence of water vapor. The present project intends to elucidate the doping mechanisms at work in such films. In addition, an alternative process to achieve grain-boundary doping of TiO2 was explored. Spectrophotometry over a wide spectral range (0.05 to 5 eV) was the main tool in probing the mobile electrical charge carriers. The interpretation of these optical measurements required appropriate models. The models developed took many structural properties into account, such as thickness, surface roughness, density, anisotropy and crystalline phase composition. The phase and morphology of the films were analyzed by X-ray diffraction and reflection, scanning probe microscopy, and electron microscopy. The chemical analyses included electron-probe microanalyses, Rutherford backscattering and elastic recoil detection analysis. The DC electrical properties were measured between room temperature and 250 °C. Most water-deposited samples showed semiconducting behavior with an activation energy of the order of 100 meV. The optical measurements revealed a broad absorption band around 1 eV. The absorption coefficient scaled with conductivity. It was successfully modelled as a Lorentzian. Similar absorption bands have been reported for reduced rutile and anatase single crystals. Water-deposited samples containing anatase exhibited a metallic behavior. In these samples the thermal activation energy was reduced to about 30 meV and the charge carriers displayed a high mobility (3 cm2V-1s-1). The infrared absorption band was about 10 times less important than in the samples devoid of anatase. Thin films of TiO2 intercalated with the equivalent of nanometer-thick layers of Ti were prepared. By changing the period in the oxygen supply the grain size, and thereby the film properties, could be modified. The films obtained in this way had many properties in common with water-deposited films. They showed the same absorption band in the infrared, had comparable charge carrier densities and were electrically conductive (102 to 104 Sm-1 at room temperature). To our knowledge, this was the first time that such high electrical conductivities were achieved by sputtering in an oxygen plasma.

EPFL2004

Texture mechanisms and microstructure of biaxial thin films grown by oblique angle deposition

Alireza Karimi, Akshath Raghu Shetty

In order to understand the texture formation mechanism in thin films grown under oblique angle deposition (OAD), TiAlN films were deposited at room temperature (RT) under various incident angles. We show that both in-plane and out-of-plane crystallographic orientations respond strongly to the deposition angle. For a?=?0 degrees, the pole figures show a (111) and (200) mixed out-of-plane orientation with random in-plane alignment. In contrast, under OAD, inclined textures are observed with the (111) direction moving toward the incident flux direction and the (200) moving away, showing substantial in-plane alignment. This observation suggests that TiAlN crystals prefer to grow with the (200) direction perpendicular to the substrate while maintaining the minimization of the surface free energy by maximizing the (111) surface area toward the incident flux. The in-plane texture, which is randomly oriented at normal incidence, gives rise to two preferred orientations under oblique angles one along the direction of flux and other away from the deposition source. The biaxial texture results from a competition among texture mechanism related to surface mobilities of adatoms, geometrical and directional effects. The surface and cross-section of the films were observed by scanning electron microscopy (SEM). OAD films develop a kind of smooth tiles of a roof structure, with no faceted crystallites. The columns of these films were tilted toward the direction of incident flux. The dependence of (111) texture tilt angle and column angle beta on the incidence flux angle a is evaluated using four well-known models. Transmission electron microscopy (TEM) study reveals a voided, intercolumnar structure with oblique growth toward the flux direction. The selected area diffraction pattern (SAED) pattern supports the pole figure observations. Measurements of the nanoindentation test were performed in order to discuss the change of mechanical properties as a function of incident flux angle.

Wiley-V C H Verlag Gmbh2012

Selective light induced chemical vapour deposition of titanium dioxide thin films

Estelle Wagner

Light Induced Chemical Vapour Deposition (LICVD) of titanium dioxide thin films is studied in this work. It is shown that this technique enables to deposit locally and selectively a chosen crystalline phase with a precise controlled thickness at low substrate temperature, allowing even the use of polymer substrates. A home made LICVD reactor was set up, consisting of a main chamber in which the substrate was placed on a temperature controlled plate and could be irradiated perpendicularly through a window by a 250 ns long pulse XeCl excimer laser (308 nm) with a controlled fluence (energy per surface area per pulse). A liquid precursor (titanium tetra-isopropoxide) was brought by an oxygen carrier gas flow in the chamber and a nitrogen flow was added to prevent deposition on the window. The total pressure in the chamber was maintained at 10 mbar. Projection of a mask image on the substrate was realized. Titanium dioxide films could be deposited locally by this technique with a thickness ranging from few nanometers to several micrometers. Deposits were realized at substrate temperatures as low as room temperature and with fluences between 1 and 400 mJ/cm2. The deposited films were characterized by profilometry, Atomic Force Microscopy, optical microscopy, Scanning Electron Microscopy, Transmission Electron Microscopy, X-ray diffraction, Raman spectroscopy, X-ray Photoelectron Spectroscopy, UV-vis spectroscopy and ellipsometry. A detailed and systematic study of the influence of some selected process parameters (substrate temperature and irradiation dose principally) on the deposition rate and material properties was realized on glass and silicon substrates. An empirical equation of the growth rate as a function of the different experimental parameters was derived and was tested successfully to obtain a precise control of the deposited thickness (a precision better than 10 nm was demonstrated for films below 300 nm), with growth rates up to 300 nm/min. From this equation, a deposition mechanism involving both a photolytic reaction and a thermal contribution of the substrate temperature was proposed. The deposited material was shown to consist of TiO2 with a possible very low additional carbon contamination. Depending on the deposition conditions, amorphous, anatase or rutile material was deposited. One parameter explaining the variation of the crystalline state of the material was the variation of the laser induced temperature rise which was simulated theoretically in parallel. Surface temperature rises in the order of several hundreds of degrees were calculated during the laser pulse, varying with the substrate, the fluence and the film thickness. The optical properties of the deposited material vary in a correlated way with the crystalline state of the material, and high indexes of refraction (up to 2.6 at 633 nm) were measured. Selective deposition in the irradiated area was studied. Provided substrate temperature was kept below 150°C, no thermal deposition was observed, and deposits were strictly located in the irradiated area. The edge resolution (around 10 micrometers) was demonstrated to be due to the optical aberrations of the mask projection set up. No effect of substrate temperature and irradiation conditions on the resolution could be evidenced, but resolution decreased with increasing deposited thickness due to optical effects. Thanks to the low substrate temperature required for the deposition process, deposition on thermo- fragile substrates (such as polymers, in particular PMMA) was demonstrated. However, in the case of polymer substrates, the fluence had to be kept below 15 mJ/cm2 not to damage or ablate the polymers, resulting in very low growth rates (in the order of 10-3 nm/pulse). In these conditions, only amorphous films with about 10% of carbon contamination could be obtained. Additionally, films were shown to crack above a certain deposited thickness, which is attributed to thermal effects. As a matter of fact, calculations showed a high temperature rise up to 70°C of the polymer/oxide interface. Deposition on polymers coated with transparent conductive oxide was also demonstrated.

EPFL2003