Internal stresses and stability of the tetragonal phase in zirconia thin layers deposited by OMCVD

Zirconia thin films were deposited by OMCVD (organo-metallic chemical vapour deposition) at various temperatures and oxygen partial pressures on a AISI 301 stainless steel substrate with Zr(thd)₄ as precursor. The as deposited 250 nm thin zirconia films presented a structure consisting of two phases: the expected monoclinic one and also an unexpected tetragonal phase. According to the literature, the stabilization of the tetragonal phase (metastable in massive zirconia) can be related to the crystallite size and/or to the generated internal compressive stresses.To analyze the effect of internal and external stresses on the thin film behaviour, in-situ tensile experiments were performed at room temperature and at high temperature (500 °C).Depending on the process parameters, phase transformations and damage evolution of the films were observed. Our results, associated to XRD (X-ray diffraction) analyses, used to determine phase ratios and residual stresses within the films, before and after the mechanical experiments, are discussed with respect to their microstructural changes.     

Synthesis, structure, microstructure and mechanical characteristics of MOCVD deposited zirconia films

Zirconia (ZrO₂) thin films were deposited by metal organic chemical vapor deposition (MOCVD) on (1 0 0) Si over temperature and pressure ranges from 700 to 900 °C and 100 to 2000 Pa, respectively. The oxide films were characterized by field emission microscopy and X-ray diffraction so that microstructure and ratios of monoclinic and tetragonal phases could be estimated according to the process conditions. The mechanical behaviour of the substrate-film systems was investigated using Vickers micro-indentation and Berkovitch nano-indentation tests. The characteristics of silicon are not modified by the presence of a thin film of silicon oxide (10 nm), formed in the reactor during heating. Young's modulus and the hardness of tetragonal zirconia phase, 220 and 15 GPa, respectively, are greater than values obtained for monoclinic phase, 160 and 7 GPa, respectively. The zirconia films are well adherent and the toughness of tetragonal zirconia phase is greater than that of monoclinic phase.     

Phase compositions and ferroelectric properties of Pb(Zr0.52,Ti0.48)O3 thin films with different highly orientations prepared by a sol-gel route

It is shown that different highly oriented Pb(Zr_0.52,Ti_0.48)O₃ films can be obtained on Pt/Ti/SiO₂/Si substrate using a sol-gel technique. The effects of pyrolysis temperature on the orientation, phase composition and ferroelectric properties of the films are investigated. It is found the ferroelectric hysteresis loops of (1 1 1)-oriented film, (1 1 1) and (1 0 0) mix-oriented film can both be saturated when the external electric field is large enough, whereas the hysteresis loop of (1 0 0)-oriented film is difficult to saturate. The analysis of X-ray diffraction indicated the possibility of different phase composition in different oriented films under large film residual stress. Higher remnant polarization (53 μC/cm²) for (1 0 0)-oriented film can be attributed to its more tetragonal phase composition, which results in that the in-plane domain switching can continuously occur with external electric field increasing.     

Residual stress delaying phase transformation in Y-TZP bio-restorations

Engineering favorable residual stress for the complex geometry of bi-layer porcelain-zirconia crowns potentially prevents crack initiation and improves the mechanical performance and lifetime of the dental restoration. In addition to external load, the stress field depends on initial residual stress before loading. Residual stress is the result of factors such as the thermal expansion mismatch of layers and compliance anisotropy of zirconia grains in the process of sintering and cooling. Stress induced phase transformation in zirconia extensively relaxes the residual stress and changes the stress state. The objective of this study is to investigate the coupling between tetragonal to monoclinic phase transformations and residual stress. Residual stress, on the surface of the sectioned single load to failure crown, at 23 points starting from the pure tetragonal and ending at a fully monoclinic region were measured using the micro X-ray diffraction sin² ψ method. An important observation is the significant range in measured residual stress from a compressive stress of ?400?MPa up to tensile stress of 400?MPa and up to 100% tetragonal to monoclinic phase transformation.     

Effects of annealing temperature on the structural and photoluminescence properties of nanocrystalline ZrO2 thin films prepared by sol-gel route

Highly transparent nanocrystalline zirconia thin films were prepared by the sol-gel dip coating technique. XRD pattern of ZrO₂ thin film annealed at 400 °C shows the formation of tetragonal phase with a particle size of 13.6 nm. FT-IR spectra reveal the formation of Zr-O-Zr and the reduction of OH and other functional groups as the temperature increases. The transmittance spectra give an average transmittance greater than 80% in the film of thickness 262 nm. Photoluminescence (PL) spectra give intense band at 391 nm and a broad band centered at 300 nm. The increase of PL intensity with elevation of annealing temperature is related to reduction of OH groups, increase in the crystallinity and reduction in the non-radiative related defects. The luminescence dependence on defects in the film makes it suitable for luminescent oxygen-sensor development. The “Red shift” of excitation peak is related to an increase in the oxygen content of films with annealing temperature. The “Blue shift” of PL spectra originates from the change of stress of the film due to lattice distortion. The defect states in the nanocrystalline zirconia thin films play an important role in the energy transfer process.     

MOCVD of zirconium oxide thin films: Synthesis and characterization

The synthesis of thin films of zirconia often produces tetragonal or cubic phases, which are stable at high temperatures, but that can be transformed into the monoclinic form by cooling. In the present study, we report the deposition of thin zirconium dioxide films by metalorganic chemical vapor deposition using zirconium (IV)-acetylacetonate as precursor. Colorless, porous, homogeneous and well adherent ZrO₂ thin films in the cubic phase were obtained within the temperature range going from 873 to 973 K. The deposits presented a preferential orientation towards the (1 1 1) and (2 2 0) planes as the substrate temperature was increased, and a crystal size ranging between 20 and 25 nm. The kinetics is believed to result from film growth involving the deposition and aggregation of nanosized primary particles produced during the CVD process. A mismatch between the experimental results obtained here and the thermodynamic prediction was found, which can be associated with the intrinsic nature of the nanostructured materials, which present a high density of interfaces.     

Influence of oxygen partial pressure on the properties of pulsed laser deposited nanocrystalline zirconia thin films

ZrO₂ thin films were deposited at various oxygen partial pressures (2.0 × 10⁻⁵-3.5 × 10⁻¹ mbar) at 973 K on (1 0 0) silicon and quartz substrates by pulsed laser deposition. The influence of oxygen partial pressure on structure, surface morphology and optical properties of the films were investigated. X-ray diffraction results indicated that the films are polycrystalline containing both monoclinic and tetragonal phases. The films prepared in the oxygen partial pressures range 2.0 × 10⁻⁵-3.5 × 10⁻¹ mbar contain nanocrystals of sizes in the range 54-31 nm for tetragonal phase. The peak intensity of the tetragonal phase decreases with the increase of oxygen partial pressures. Surface morphology of the films examined by AFM shows the formation of nanostructures. The RMS surface roughness of the film prepared at 2.0 × 10⁻⁵ mbar is 1.3 nm while it is 3.2 nm at 3.5 × 10⁻¹ mbar. The optical properties of the films were investigated using UV-visible spectroscopy technique in the wavelength range of 200-800 nm. The refractive index is found to decrease from 2.26 to 1.87 as the oxygen partial pressure increases from 2.0 × 10⁻⁵ to 3.5 × 10⁻¹ mbar. The optical studies show two different absorption edges corresponding to monoclinic and tetragonal phases.     

Hydrogen-induced buckling of Pd films studied by positron annihilation

Hydrogen loading of thin films introduces very high compressive stresses which grow in magnitude with increasing hydrogen concentration. When the hydrogen-induced stresses exceed a certain critical in-plane stress value, the loaded film starts to detach from the substrate. This results in the formation of buckles of various morphologies in the film layer. Defect studies of a hydrogen loaded Pd film which undergoes a buckling process are presented, using slow positron implantation spectroscopy, in situ acoustic emission, and direct observations of the film structure by transmission electron and optical microscopies. It is found that buckling of the film occurs at hydrogen concentrations x_H ≥ 0.1 and causes a significant increase of the dislocation density in the film.     

Growth of oxide thin films for optical gas sensor applications

Tungsten trioxide and titanium dioxide thin films were synthesised by pulsed laser deposition. We used for irradiations of oxide targets an UV KrF* (λ = 248 nm, τ_FWHM ≅ 20 ns, ν = 2 Hz) excimer laser source, at 2 J/cm² incident fluence value. The experiments were performed in low oxygen pressure. The (0 0 1) SiO₂ substrates were heated during the thin film deposition process at temperature values within the 300-500 °C range. The structure and crystalline status of the obtained oxide thin films were investigated by high resolution transmission electron microscopy. Our analyses show that the films are composed by nanoparticles with average diameters from a few to a few tens of nm. Moreover, the films deposited at substrate temperatures higher than 300 °C are crystalline. The tungsten trioxide films consist of a mixture of triclinic and monoclinic phases, while the titanium dioxide films structure corresponds to the tetragonal anatase phase. The oxide films average transmittance in the visible-infrared spectral range is higher than 80%, which makes them suitable for sensor applications.     

Spatially resolved Raman spectroscopy evaluation of residual stresses in 3C-SiC layer deposited on Si substrates with different crystallographic orientations

Raman scattering studies were performed on hot-wall chemical vapor deposited (heteroepitaxial) silicon carbide (SiC) films grown on Si substrates with orientations of (1 0 0), (1 1 1), (1 1 0) and (2 1 1), respectively. Raman spectra suggested that good quality cubic SiC single crystals could be obtained on the Si substrate, independent of its crystallographic orientation. Average residual stresses in the epitaxially grown 3C-SiC films were measured with the laser waist focused on the epilayer surface. Tensile and compressive residual stresses were found to be stored within the SiC film and in the Si substrate, respectively. The residual stress exhibited a marked dependence on the orientation of the substrate. The measured stresses were comparable to the thermal stress deduced from elastic deformation theory, which demonstrates that the large lattice mismatch between cubic SiC and Si is effectively relieved by initial carbonization. The confocal configuration of the optical probe enabled a stress evaluation along the cross-section of the sample, which showed maximum tensile stress magnitude at the SiC/Si interface from the SiC side, decreasing away from the interface in varied rate for different crystallographic orientations. Defocusing experiments were used to precisely characterize the geometry of the laser probe in 3C-SiC single crystal. Based on this knowledge, a theoretical convolution of the in-depth stress distribution could be obtained, which showed a satisfactory agreement with stress values obtained by experiments performed on the 3C-SiC surface.     

Studies and correlation among the structural, electrical and gas response properties of aerosol spray deposited self assembled nanocrystalline CuO

Nanostructured CuO films have been grown on to the glass substrate by varying the deposition time from 10 to 30 min and substrate temperature from 300 to 400 °C by a simple ultrasonic spray pyrolysis technique, using aqueous a cupric nitrate solution as precursor. The effect of the substrate temperature on the textural, structural, electrical, and gas sensing properties of CuO films was studied and correlated. Thermal analysis of the dried precursor shows the elimination of physisorbed and chemisorbed water. It suggests the formation of CuO phase on substrate at temperature of 300 °C. X-ray diffractograms of the films indicate the formation of polycrystalline monoclinic CuO having monoclinic with crystallite size around 18 nm. The texture coefficient finds the (0 0 2) plane as the preferred orientation in films. The microstrain and dislocation densities have been calculated and found to decreases with increase in substrate temperature. The scanning electron micrographs indicate the formation of trapezium like facet structures on the film surface. AFM analysis shows uniform deposition of the CuO film over the entire substrate surface. Observations reveal that the film deposited at 300 °C show comparatively higher activation energy and appreciable response to ammonia at room temperature. The use of aqueous cupric nitrate as precursor results in the deposition of single phase copper oxide films.     

Stress analysis, structure and magnetic properties of sputter deposited Ni-Mn-Ga ferromagnetic shape memory thin films

The residual stress instituted in Ni-Mn-Ga thin films during deposition is a key parameter influencing their shape memory applications by affecting its structural and magnetic properties. A series of Ni-Mn-Ga thin films were prepared by dc magnetron sputtering on Si(1 0 0) and glass substrates at four different sputtering powers of 25, 45, 75 and 100 W for systematic investigation of the residual stress and its effect on structure and magnetic properties. The residual stresses in thin films were characterized by a laser scanning technique. The as-deposited films were annealed at 600 °C for 1 h in vacuum for structural and magnetic ordering. The compressive stresses observed in as-deposited films transformed into tensile stresses upon annealing. The annealed films were found to be crystalline and possess mixed phases of both austenite and martensite, exhibiting good soft magnetic properties. It was found that the increase of sputtering power induced coarsening in thin films. Typical saturation magnetization and coercivity values were found to be 330 emu/cm³ and 215 Oe, respectively. The films deposited at 75 and 100 W display both structural and magnetic transitions above room temperature.     

应力作用下EuTiO3铁电薄膜电热效应的唯象理论研究

基于Laudau-Devonshire的热动力学模型, 计算了EuTiO₃铁电薄膜材料的电热效应. 结果显示在外加应力的调控下, 电极化、电热系数以及绝热温差都会随之变化. 外加垂直于表面的张应力加大, 薄膜的相变温度升高, 绝热温差增加, 最大绝热温差所对应的工作温度向高温区移动. 对于二维平面失配应变u_m =-0.005的薄膜, 当外加张应力σ₃ = 5 GPa时, 其最大电热系数为1.75×10^-3 C/m²·K, 电场变化200 MV/m 时室温下绝热温差ΔT 的最大值可达到14 K 以上, 绝热温差ΔT ≥13 K 的工作温区超过120 K, 表明可以通过调控外部应力来获取室温时较大的绝热温差. 此结果预示着铁电EuTiO₃ 薄膜在室温固态制冷方面可能具有较好的应用前景.     

Characterization and structure study of the anodic oxide film on Zircaloy-4 synthesized using NaOH electrolytes at room temperature

Thick crystalline zirconium oxide films were synthesized on Zircaloy-4 substrates by anodic oxidation at room temperature in NaOH solution with a stable applied voltage (300 V). The film is approximately 4.7 μm in thickness. The XPS and SEM analysis shows that the film is a three-layer structure in water, hydroxide and oxide parts. The thickness of that order is ∼0.01 μm, ∼1 μm, ∼3.7 μm, respectively. The oxide layer is composed of tetragonal and monoclinic phases with the volume ratio about 0.2. Furthermore, the thick anodic film acts as a barrier to oxygen and zirconium migrations. It effectively protects zirconium alloys against the worse corrosion. An extremely low passive current density of ∼0.018 μA/cm² and a low oxidation weight gain of ∼0.411 mg/cm² were also observed in the films.     

Formation of CuO nanowires by thermal annealing copper film deposited on Ti/Si substrate

Nanowires of various inorganic materials have been fabricated due to the realization of their applications in different fields. Large-area and uniform cupric oxide (CuO) nanowires were successfully synthesized by a very simple thermal oxidation of copper thin films. The copper films were deposited by electron beam evaporation onto Ti/Si substrates, in which Ti film was first deposited on silicon substrate to serve as adhesion layer. The structure characterization revealed that these nanowires are monoclinic structured single crystallites. The effects of different growth parameters, namely, annealing time, annealing temperature, and film thickness on the fabrication of the CuO nanowires were investigated by scanning electron microscopy. A typical procedure simply involved the thermal oxidation of these substrates in air and within the temperature range from 300 to 700 °C. It is found that nanowires can only be formed at thermal temperature of 400 °C. It is observed that the growth time has an important effect on the length and density of the CuO nanowires, whereas the average diameter is almost the same, i.e.50 nm. Different from the vapor-liquid-solid (VLS) and vapor-solid (VS) mechanism, the growth of nanowires is found to be based on the accumulation and relaxation of the stress.     

The role of target-to-substrate distance on the DC magnetron sputtered zirconia thin films’ bioactivity

Zirconium dioxide thin films were deposited on 316L-stainless steel type substrates using DC unbalanced magnetron sputtering. The process parameter of this work was the target-to-substrate distance (d_t-s), which was varied from 60 to 120 mm. The crystal structure and surface topography of zirconium dioxide thin films were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). The results demonstrate that all of the ZrO₂ thin films are composed monoclinic phase. The film sputtered at short d_t-s (60 mm) shows a rather heterogeneous, uneven surface. The grain size, roughness, and thickness of thin films were decreased by increasing d_t-s. The bioactivity was assessed by investigating the formation of hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) on the thin film surface soaked in simulated body fluids (SBF) for 7 days. XRD and scanning electron microscopy (SEM) were used to verify the formation of apatite layers on the samples. Bone-like apatites were formed on the surface of the ZrO₂ thin film in SBF immersion experiments. A nanocrystalline hydroxyapatite (HA) with a particle size of 2-4 μm was deposited. Higher crystallinity of HA on the surface was observed when the distance d_t-s increased to more than 80 mm. Therefore, it seems that a d_t-s greater than 80 mm is an important sputtering condition for inducing HA on the zirconia film.     

The properties of the Y2O3 films exposed at elevated temperature

Yttrium trioxide (Y₂O₃) thin films have been deposited on silicon (1 1 1) substrates by RF magnetron sputtering. The influences of thermal exposure at high temperature in air on the structure, the surface morphology, roughness, and the refractive index of the Y₂O₃ thin film were investigated by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM), and spectroscopic ellipsometry (SE). The results indicate that chemical composition of the as-deposited Y₂O₃ film is apparently close to the stoichiometric ratio, and it has a cubic polycrystalline structure but the crystallinity is poor. The monoclinic and cubic phases can coexist in the Y₂O₃ film after thermal exposure to 900 °C, and the monoclinic phase disappears completely after 300 s exposure to 950 °C. The changes of the surface morphology, roughness, and the refractive index of the Y₂O₃ film are closely related to the crystal structure, the internal stress, and various defects influenced by thermal exposure temperature and time.     

Structural phase transitions in nanosized ferroelectric barium strontium titanate films

The lattice parameters of epitaxial barium strontium titanate films with various thicknesses (from 6 to 960 nm) were measured as a function of temperature in the normal and tangential directions with respect to the film plane using x-ray diffraction. The films were grown through the layer-by-layer mechanism by rf cathode sputtering under elevated oxygen pressure. A critical film thickness (～ 50 nm) was found to exist, below and above which the films are subjected to compressive and tensile stresses, respectively. As the temperature varies from 780 to 100 K, the films undergo two diffuse structural phase transitions of the second order over the entire thickness range. The transitions in the films under tensile stresses are likely to be transformations from the paraelectric tetragonal to aa phase and then to r phase, whereas the transitions under compressive stresses are transformations from the tetragonal paraelectric to ferroelectric c phase and then, with further decreasing temperature, to r phase.     

Transmission electron microscopy studies of HfO2 thin films grown by chloride-based atomic layer deposition

Detailed transmission electron microscopy characterization of HfO₂ films deposited on Si(1 0 0) using atomic layer deposition has been carried out. The influence of deposition temperature has been investigated. At 226 °C, a predominantly quasi-amorphous film containing large grains of cubic HfO₂ (a₀ = 5.08 Å) was formed. Grain morphology enabled the nucleation sites to be determined. Hot stage microscopy showed that both the cubic phase and the quasi-amorphous phase were very resistant to thermal modification up to 500 °C. These observations suggest that nucleation sites for the growth of the crystalline cubic phase form at the growing surface of the film, rather homogeneously within the film. The films grown at higher temperatures (300-750 °C) are crystalline and monoclinic. The principal effects of deposition temperature were on: grain size, which coarsens at the highest temperature; roughness with increases at the higher temperatures due to the prismatic faceting, and texture, with texturing being strongest at intermediate temperatures. Detailed interfacial characterization shows that interfacial layers of SiO₂ form at low and high temperatures. However, at intermediate temperatures, interfaces devoid of SiO₂ were formed.     

The effect of applied negative bias voltage on the structure of Ti-doped a-C:H films deposited by FCVA

Ti-doped hydrogenated diamond-like carbon (DLC) films were deposited on Si(1 0 0) substrates by a filtered cathodic vacuum arc (FCVA) method using Ar and CH₄ as the feedstock. The composition and microstructure of the films were investigated by Raman spectroscopy, X-ray photoelectron spectroscopy and IR spectroscopy. The internal stress was determined by the radius of curvature technique. The influence of the bias voltage on the microstructure of the as-deposited films was investigated. It was found that the graphite-like bonds was dominated in the Ti-doped DLC film deposited at 0 V bias voltage. When bias voltage was increased to −150 V, more diamond-like bond were produced and the sp³ content in film reached the maximum value, after which it decreased and more graphite-like bonds feature produced with further increase of the negative bias voltage. The compressive internal in the Ti-doped DLC films also exhibited a maximum value at −150 V bias voltage. IR results indicated that CH bonded intensity reduced, and H atoms bonded with C atoms were substituted for the Ti atoms as the negative bias voltage increasing. All the composition and microstructure change can be explained by considering the plasma conditions and the effect of negative bias voltage applied to the substrate.