Electronic properties of nano-crystalline titanium dioxide thin films

Titanium dioxide is a cheap, chemically stable and non-toxic material. However its electrical properties are unstable and it is a modest semiconductor and a mediocre insulator. For several applications it would be interesting to make it either more insulating or more conducting. The goal of this work was to modify the electrical properties of nano-crystalline TiO2 thin films deposited by reactive sputtering and to understand the mechanism leading to these modifications. The principal factors that influence the electrical conductivity are on the one hand the concentration and nature of the chemical impurities incorporated in TiO2, and on the other hand the morphology of the thin films. The study was split into two parts. The fist part describes the modifications of the sputtered material obtained by chemical doping of the TiO2 thin films. Niobium, cerium, iron, and fluorine were incorporated successfully in TiO2. The second part describes the modifications obtained by modifying the reactive gas used during the sputtering process: thus oxygen was substituted with water vapor. Several analysis techniques have been used to characterize the TiO2 thin films. They are essentially divided in four categories. The chemical analyses included electron probe microanalyses, x-ray photoemission spectroscopy, and secondary ion mass spectrometry. The structure and morphology analyses of thin films were carried out with x-ray diffraction and atomic force microscopy. The electrical properties in dc or ac mode were measured between room temperature and 350°C. Finally optical transmission provided information on the electronic states and morphology of the thin films. With an appropriate choice of impurities, titanium dioxide can be made more insulating (TiO2:Ce), more conducting with an n-type electrical conductivity (TiO2:Nb) or p-type electrical conductivity (TiO2:Fe). Chemical doping is also the cause of important structure and morphology changes, for example it can force the transformation from the anatase to the rutile structure. It is shown in particular that dopant atoms generate defects such as oxygen vacancies. These defects impede the variation of the electrical conductivity produced by the impurities, thus, in spite of dopant concentration in the percent range, the variation of the electrical conductivity is an increase or a decrease of three order of magnitude at most when compared with undoped TiO2. Thin films deposited with water vapor as the reactive gas present an increase in the electrical conductivity by height order of magnitude compared to samples prepared with oxygen in similar conditions. No atom other than titanium or oxygen could be detected in the thin films in significant concentration. The dramatic conductivity increase is due to the injection inside TiO2 grains of electrons donated by unsaturated titanium atoms lying on the grain surface. A nanometric grain size is a requirement to make such high doping levels possible. Depending on the impurities or reactive gas selected, titanium dioxide can be made either into a good insulator with a high breakdown field and a high permittivity or into a reasonably conducting, transparent film. The electrical conductivity of the samples prepared for this study cover the range from 10-10 to 103 S m-1.

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

A multi-technique approach to study the microstructural properties of tin-based transparent conductive oxides

Federica Landucci

Transparent conductive oxides (TCOs) are semiconductor-like materials that exhibit high electrical conductivity and high optical transparency combined. They are adopted in various applications ranging from gas sensors, to electrochromic windows, to photovoltaic cells. Indium-based TCOs represent the industry standard. Nevertheless, indium is among the less abundant elements in the earth crust and forecasts based on its current consumption envisage an urgent need to replace it. Tin-based TCOs are a promising alternative, since their opto- electronic characteristics mimic the ones of indium-based materials. This thesis aims to investigate the link between optoelectronic and microstructural properties of tin dioxide and zinc tin oxide (ZTO) with a composition Zn0.05Sn0.30O0.65 and their stability when submitted to thermal treatments. Indeed, lots of practi- cal applications require the TCO to operate in high temperature conditions. To conduct this study, a combination of analytical techniques, such as transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X- ray diffraction (XRD), electron paramagnetic resonance (EPR) and differential scanning calorimetry (DSC) was employed. Amorphous SnO2 and ZTO were deposited by RF sputtering and annealed up to 1050°C in different atmospheres. The influence of annealing temperature and atmosphere were decoupled and led us to an in-depth comprehension of the mechanisms governing the optoelectronic properties of both materials. When annealed in air, between room temperature and 300°C, ZTO exhibits increased mobility and carrier concentration with respect to the as-deposited state. This increase, investigated with DSC, was ascribed to a structural relaxation that allows point defects to release electrons in conduction band. Between 300°C and 500°C atmospheric oxygen passivates oxygen vacancies, drastically decreasing the carrier concentration and therefore causing a large drop of the conductivity. EPR experiments allowed to ascribe the drop in conductivity to the decrease of carrier concentration, which occurs slightly before the phase change. At 570°C (and 930°C for the case of vacuum annealing) the phase change occurs and the ZTO crystallizes in the rutile form of SnO2. The material becomes completely insulating. When the temperature is increased to 1050°C, evaporation of zinc is observed. In order to improve the electrical conductivity of ZTO at high temperature, a doping strategy was implemented starting from DFT calculations conducted by a partner group, who screened among the entire periodic table, which elements are the best candidates to act as n-dopants for ZTO. Bromine and iodine were retained, since they were found to be the most energetically favorable to become substitutional defects for a tin site. An exploratory doping route is therefore presented and the treated samples analyzed with TEM, EDX and UV-VIS-IR spectroscopy. Finally, the structural properties of an indium-based TCO (zirconium-doped indium oxide) were investigated and used as a benchmark to propose a crystallization model for the tin-based, as well as the indium-based materials. The influence of pa- rameters such as the material thickness, annealing atmosphere and temperature and deposition pressure are discussed for both materials.

EPFL2019

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