Chemical beam deposition of titanium dioxide thin films

Titanium dioxide (TiO2) is a widely investigated material for its biological compatibility, high dielectric constant and refractive index, chemical and mechanical resistance, and catalytic activity. Several different techniques are available to produce TiO2 thin films, which are variously suited to provide the properties required for a specific application. Dense TiO2 coatings with high refractive index and low optical absorption are aimed at for optical applications. High thickness uniformity on large area coatings and a high, precisely controlled, growth rate are further advantages. A reactor for the production of optical coatings at 1% thickness uniformity on 150 mm diameter substrates has been designed according to a mathematical model, which has been extended to evaluate growth rates and precursor efficiency. The reactor design has been made suitable for light assisted TiO2 growth, so as to achieve selective or improved deposition or to locally modify the coating properties. Along this line, a light selective deposition of 3 µm resolution by mask projection is anticipated. The results obtained by operating the reactor in the Low Pressure Chemical Vapour Deposition (LPCVD) and Chemical Beam Deposition (CBD) indicate that the latter mode results in coatings with superior optical properties. Thickness uniformity better than 3% and a precursor impinging efficiency very close to the 5% calculated value have been achieved in the growth rate range from 50 to 1000 nm h-1. The causes of these small discrepancies are discussed and some reactor design improvements are proposed. The estimated resolution limit by mask projection has also been achieved by PET laser ablation, while for TiO2 a selective deposition of 30 µm structures has been obtained. Several characterization methods have been used to investigate the chemical composition (XPS, FTIR, Raman spectroscopy), the crystalline phase (XRD, GAXRD, Raman spectroscopy, TEM) and the morphology (XRR, TEM, SEM, AFM, RBS) of the thermally grown TiO2 films. Pure TiO2 with less than 1% carbon content with anatase crystalline phase is obtained in all the conditions explored (substrate temperature between 330 and 550°C). It is also shown that the anatase content increases with increasing substrate temperature and film thickness. The classical columnar growth related to the anatase crystalline phase is obtained with nanograins of smaller diameter than that of the columns (8-10 nm compared to 50-200 nm). Optical characterisation methods (photospectroscopy, spectral ellipsometry, and in situ Dynamic Optical reflectivity) have also been applied. Dense anatase has been obtained with refractive indexes n and k of 2.5 and 10-2 respectively for films up to 80-100 nm in thickness. For thicker films, an increasing porosity with increasing film thickness is observed resulting in enhanced Rayleigh scattering. A band gap blue shift is also observed when the Tauc model is applied due to increasing nanocrystallinity with thickness. To avoid this problem, SiO2 has been added so as to increase the temperature at which amorphous to anatase phase transition occurs, resulting in TiO2 amorphous phase deposition at 500°C substrate temperature with less than 10% SiO2 content. Alternating layers of TiO2 and TiO2-SiO2 as well as graded index films, both in the growth direction and perpendicular to the growth direction, have also been produced by thermal decomposition and their optical behaviour investigated. Laser assisted deposition has been used to improve optical properties of the film. A densification of the TiO2 anatase phase layer has been achieved resulting in higher refractive index n compared to pure thermal deposition even for films up to 400 nm thickness. A further densification with increasing laser fluence up to rutile phase transition is obtained. The band structure, extrapolated from spectral ellipsometry measurements, shows a progressive shift from the anatase to the rutile phase. Finally, the TiO2 selective deposition and the chemical composition variation in TiO2+SiO2 films as a function of laser repetition rate have been studied. In all cases the results obtained by means of the different characterization techniques are in mutual agreement and consistent with the global picture of the TiO2 growth resulting from the various studies reported in the literature.

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

High vacuum chemical vapor deposition (HV-CVD) of alumina thin films

Xavier Multone

We analyzed along this work the feasibility to produce high quality alumina thin films by High Vacuum Chemical Vapor Deposition (HV-CVD). We study the influence of various parameters on the growth process and on the film quality, such as substrate temperature, gas flow or pressure. We aim to highlight the advantages and the limitations of the HV-CVD technique. A high vacuum CVD reactor has been designed, built and optimized. A novel effusing source has been designed to guarantee a molecules distribution uniformity of 95% on the substrate surface. The main technical challenges faced were to reach the maximum substrate temperature in vacuum, to control the precursor flux and to control the temperature of the gas lines to avoid condensation. For the first time, films of Al2O3 are obtained by HV-CVD from aluminum isopropoxide as precursor in a novel HV-CVD reactor. The HV-CVD approach stands out of all the other CVD methods as it allows excellent prediction of growth rates and film thickness homogeneities if the decomposition probability of the precursor is once determined. In this work, the latter was determined to increase with increasing substrate temperature to 0.2, further increase of temperature reduces the decomposition probability due to increased desorption rate. Pure alumina films are obtained in a reliable and reproducible way. The presence of oxidizing agents, as decomposition partners, reduces the activation energy of deposition process from 33.1 ± 8.2 kJ/mol to 11.4 ± 5.3 kJ/mol in presence of sufficient oxidizing agent. The Al2O3 films are growing at deposition rate from 1 to 50 nm/min. It has been found that, the lower the deposition temperature, the higher the density of the deposited films therefore the higher refractive index. The index of refraction varies from 1.65 ± 0.01 to 1.35 ± 0.01 at 632 nm wavelength from lowest to highest deposition temperature. At low deposition temperature, Al2O3 can contain residual OH-groups and Al=O entities. This content is independent of the total flow rates of the precursor in the range of 5·1015 molecules/cm2·s to 3·1016 molecules/cm2·s impinging on the substrate. Substrate effects have not been observed in the limited range of tests on natural oxidized silicon, 3 µm SiO2 on silicon, quartz, stainless steel, fused silica and 100 nm silicon nitride on top of silicon. The chemical composition of the deposited alumina films measured by EDX and XPS is nearly stoichiometric with 35 ± 5 at% Al and 65 ± 5 at% O, without carbon contamination. Remaining hydrogen in the films has not been studied in detail, but the difference of OH- absorption peaks by FTIR indicates that, a low temperature deposition, hydrogen incorporation is possible. Concerning the optical properties of the HV-CVD deposited films, absorption is very low from 250 nm to 1800 nm wavelength, but due to the porosity and granular structure of the films, light scattering can take place. But propagation loss smaller than 2 dB/cm were measured in channel waveguides fabricated from the HV-CVD alumina films. Planar and channel waveguides demonstrate good guiding properties at 670 nm and 1.55 µm, as well. This work also opens new possibilities to deposit in situ local structures of or in transparent alumina on large surface. Light induced high vacuum chemical vapor deposition of alumina microstructures by 248 nm excimer laser is presented and shows an activation energy of 5.2 ± 0.4 kJ/mol, much smaller than for thermal deposition. The influence of the fluence and the repetition rate is discussed. Electron beam assisted HV-CVD of alumina is demonstrated and proves the feasibility of in situ structuration under HV-CVD conditions.

EPFL2009

Combinatorial High-Vacuum Chemical Vapor Deposition of Lithium Niobate Thin Films

Ali Dabirian

Lithium niobate is a key material for photonics with applications in optical modulators and light frequency converters. Present lithium niobate optical devices are realized in bulk lithium niobate single crystals while interests in higher integration and also better performance derives efforts towards high quality epitaxial lithium niobate thin films. In the past, epitaxial lithium niobate thin films obtained using chemical vapor deposition (CVD), pulsed-laser deposition and crystal-ion slicing. Among these methods CVD is the one that can provide large area growth. Optimizing films properties stays an issue in CVD because in CVD of multi-element oxides using multiple precursors the stoichiometry of the film does not reflect the precursor ratios and additionally it varies with precursors total flux values. In this thesis optimization and discovery of multi-element oxide thin films were performed in a high-vacuum CVD reactor that is capable of performing combinatorial experiments. Using this reactor epitaxial lithium niobate thin films were obtained on sapphire {001g} and lithium tantalate {001} substrates with rocking curve full-width at half-maximum (FWHM) values of 0.03° and 0.024° respectively. The epitaxial growth of lithium niobate films was confirmed from X-ray diffraction (XRD) measurements and transmission-electron microscope (TEM) observations. Niobium tetra-ethoxy-di-methy-amino-ethoxide (Nb(OEt)4(dmae)) and lithium tert-butoxide (Li(OBut)) were used as precursors. Optically induced inhomogeneities, also known as optical damage, in lithium niobate limit its usage for high laser intensity applications. Lithium niobate single crystals doped with hafnium showed improved optical damage thresholds. Therefore combinatorial HVCVD experiments were conducted and textured {001} hafnium-doped lithium niobate films, with about 6 [mol%] hafnium, were obtained on sapphire f001g. Although the crystalline quality of the film is not high (rocking curve FWHM 0.8°) its Raman spectrum is still quite close to lithium niobate single crystal and epitaxial lithium niobate films on sapphire. Hafnium tert-butoxide (Hf(OBut)4) was used as precursor for hafnium. In the HVCVD reactor, a precursor transport system was applied such that spatial control of the precursor impinging rate on the substrate can be tailored. The precursor flux distribution that was mostly used in this thesis was a linear gradient with ratio of three across a 150 mm diameter circular area. In fact combinatorial experiments were performed by producing a linear gradient for individual precursors over the substrate with a certain angle between the gradient directions. The linear gradient feature was used to perform efficiently the systematic study of single precursors providing the benefit that one deposition at certain substrate temperature gives information about deposition kinetics for a vast range of precursor flux values. A systematic study of the Nb(OEt)4(dmae) precursor was performed using this feature and chemical-reaction-limited, mass-transport-limited, and desorption-limited regimes of CVD process were identified. The possibility of screening a large range of precursor flux values led us to discovering a CVD regime in which deposition rate is decreased by raising the precursor flux. A model was proposed for interaction of gas with surfaces that can explain all the different CVD regimes observed. The precursor molecules in HVCVD reactor reach the substrate with nearly no gasphase collision. Based on this fact a lift-off process was proposed for large-area in-situ patterning of multi-element oxide thin films.

EPFL2010