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

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.

Combinatorial High-Vacuum Chemical Vapor Deposition of Textured Hafnium-Doped Lithium Niobate Thin Films on Sapphire

Giacomo Benvenuti, Ali Dabirian, Scott Harada, Patrik Hoffmann, Yury Kuzminykh, Paul Muralt, Silviu Cosmin Sandu, Estelle Wagner

Combinatorial high-vacuum chemical vapor deposition (HV-CVD) was used to identify the conditions required to obtain hafnium-doped lithium niobate thin films on sapphire {001} substrates. Niobium tetraethoxydimethylaminoethoxide (Nb(OEt)(4)(dmae)), lithium tert-butoxide (Li(OBut)), and hafnium tert-butoxide (Hf(OBut)(4)) were used as precursors. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated that a single phase of textured {001} Hf-doped lithium niobate film was obtained under certain precursor flux conditions. The lithium content ([Li]/([Li] + [Nb])) of the textured film was estimated using Raman spectroscopy to be about 49 mol %. The presence of hafnium inside the films was confirmed by X-ray photoelectron spectroscopy (XPS) measurements, and the hafnium content of the textured film ([Hf]/([Hf] + [Nb])) was estimated to be about 3 mol %. XPS data confirmed that Hf and Nb, respectively, are in the +4 and +5 oxidation states inside the film. The film consists of nearly parallel {001} hafnium-doped lithium niobate columns with different in-plane orientations.

2011

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

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.