Scaling behavior and structure transition of ZrO2 films deposited by RF magnetron sputtering

ZrO₂ thin films were deposited onto Si wafers and glass slides by reactive rf magnetron sputtering with varying conditions of substrate temperature (T_s). Structural analysis was carried out using high-resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM). The scaling behavior of the AFM topographical profiles was analyzed using one-dimensional power spectral density method (1DPSD). Morphological and structural evolution of ZrO₂ films have been studied in relation to T_s. With substrate temperatures ranging from RT to 550 °C, the structural transition of the films is a-ZrO₂ (below 250 °C) → m-ZrO₂ with a little a-ZrO₂ (450 °C) → m-ZrO₂ with a little t-ZrO₂ (550 °C). The roughness exponent α is 1.53 ± 0.02, 1.04 ± 0.01, 1.06 ± 0.05, 1.20 ± 0.03 for ZrO₂ thin films deposited at RT, 250 °C, 450 °C, and 550 °C, respectively. Quantitative surface characterization by spatially resolved 1DPSD analyses identified three different growth mechanisms of surface morphology for ZrO₂ thin films deposited at RT, 250∼450 °C and 550 °C. The evolution and interactions of surface roughness and microstructure are discussed in terms of surface diffusion, grain growth, and flux shadowing mechanisms.     

Evaluation of ion conductivity of ZrO2 thin films prepared by reactive sputtering in O2, H2O, and H2O + H2O2 mixed gas

Hydrated ZrO₂ thin films were prepared by reactive sputtering in O₂, H₂O, and H₂O + H₂O₂ mixed gas, and the effect of the sputtering atmosphere on ion conductivity of the films was investigated. The results showed that the films deposited in O₂ gas exhibited poor ion conductivity; however, the ion conductivities of the films deposited in the other two kinds of atmosphere were similar and 300-500 times higher than that of the films deposited in O₂ gas. It was indicated that the higher ion conductivity of the films was caused by lower film density and higher water content.     

Photocatalytic TiO2 films deposited by reactive magnetron sputtering with unipolar pulsing and plasma emission control systems

TiO₂ films with thickness of about 500 nm were deposited on unheated non-alkali glass substrates by reactive magnetron sputtering using one Ti metal target with unipolar pulsed powering of 50 kHz and the plasma emission feedback system (PCU). In order to keep the very high deposition rate, the depositions were carried out in the “transition region” between the metallic and the reactive (oxide) sputter mode where the target surface was metallic and oxidized, respectively. Stable deposition was successfully carried out in the whole “transition region” with PCU at total gas pressure of 3.0 Pa. All the as-deposited films deposited in the “transition region” showed amorphous structure, which performed very low photocatalytic activity. After the post-annealing in air at higher than 300 °C, all the films crystallized to anatase polycrystalline structure. They performed both photoinduced decomposition of acetaldehyde and photoinduced hydrophilicity under UV light illumination. The highest deposition rate in this study to deposit the photocatalytic TiO₂ films in the “transition region” was 90 nm/min, which was over twenty times higher than that for conventional sputter deposition processes.     

Characterization of sol-gel derived TiO2/ZrO2 films and powders by Raman spectroscopy

The effect of zirconium dioxide addition on crystal structure of sol-gel TiO₂ mesoporous films and powders has been investigated by means of Raman spectroscopy, X-Ray diffraction, and Atomic force microscopy. Zirconium incorporation (up to 30 mol%) into TiO₂ lattice resulted in the formation of Ti_1 − xZr_xO₂ solid solution with anatase structure for the binary powders has been proved. Appearance of tetragonal ZrO₂ phase was observed for the samples with high zirconium content.     

Thermal treatment effect on the optical properties of ZrO2 thin films deposited by thermionic vacuum arc

This paper shows the ex situ thermal treatment effects of the ZrO₂ thin films obtained by TVA (thermionic vacuum arc) technique on the optical properties (e.g., transmittance, refractive index and band-gap energy) of ZrO₂ thin films. The crystal structure, surface and optical properties were investigated for ZrO₂ thin films deposited on glass substrates by thermionic vacuum arc (TVA) method. The thermal treatment effect on the optical properties of the thin films was determined. The XRD analysis showed that the deposited ZrO₂ thin films have baddeleyite (monoclinic) and zirconium (hexagonal) structures. The thicknesses and refractive index were determined by interferometric measurements. The thin films were thermal treated at different temperatures (350 °C, 450 °C and 550 °C), and the analysis showed that the optical properties of ZrO₂ deposited thin films were improved by thermal treatment at 450 °C.     

Interfacial layer growth of ZrO2 films on silicon

In this work, the interfacial layer growth for both as-deposited and annealed ZrO₂ thin films on silicon is analyzed in detail by the high-resolution cross-sectional transmission electron microscope and spectroscopic ellipsometry. For as-deposited ZrO₂/SiO₂/Si, the thickness of a SiO₂-like layer at the silicon interface was found to depend on the oxygen partial pressure during deposition. At oxygen partial pressure ratio of above 50% the interfacial silicon oxide thickness increased through oxygen diffusion through the ZrO₂ film and silicon consumption at the interface. At oxygen partial pressure ratio in the range 7-50%, the visible growth of interfacial silicon oxide layer was not present. The interfacial layer for ZrO₂/Si with optimal partial pressure (15%) during annealing at 600 °C was found to be the two-layer structure composed of the ZrSi_xO_y overlayer and the SiO_x downlayer. The formation of the interfacial layer is well accounted for diffusion mechanisms involving Si indiffusion and grain-boundary diffusion.     

Structure and property changes of ZrO2/Al2O3/ZrO2 laminate induced by low-temperature NH3 annealing applicable to metal-insulator-metal capacitor

Phase transformation and morphology evolution of ZrO₂/Al₂O₃/ZrO₂ laminate induced by the post-deposition NH₃ annealing at 480 °C were studied and the effect on the electrical property of the TiN/ZrO₂/Al₂O₃/ZrO₂/TiN capacitor module was evaluated in dynamic random access memory cell. Experimental results indicated N could indeed be incorporated into the dielectric laminate by the low-temperature NH₃ annealing, resulting in tetragonal-to-cubic phase transformation and small crystallites in the ZrO₂ layers. The C residue and Cl impurity in the ZrO₂/Al₂O₃/ZrO₂ laminate, which derived from the dielectric film formation and capping TiN layer deposition, respectively, could also be reduced by the nitridation process. As a result of the better surface morphology and less impurity content, lower dielectric leakage current and longer reliability lifetime were observed for the nitrided ZrO₂/Al₂O₃/ZrO₂ capacitor. This study demonstrates the low-temperature NH₃ annealing on ZrO₂/Al₂O₃/ZrO₂ dielectric can be applicable to the metal-insulator-metal capacitor structure with nitride-based electrode, which brings advantages over mass production-wise property improvements and extends the practical applicability of the ZrO₂/Al₂O₃/ZrO₂ dielectric.     

Low temperature stabilized rutile phase TiO2 films grown by sputtering

The deposition of rutile phase TiO₂ films on unheated substrates by radio frequency magnetron sputtering is elaborated. The effect of total pressure and O₂/Ar flow ratio on the growth of rutile film on different substrates has been studied thoroughly. The development of crystalline phase along with film deposition rate, surface morphology, optical transmission and band gap were also investigated for various growth conditions. It was found that the rutile phase crystallinity increased with decrease in total pressure and increase in O₂ flow. In addition, the grown rutile films have interesting optical characteristics such as high transmittance (~ 85%) and high refractive index (~ 2.7) with a band gap about 3.2 eV.     

Comparative properties of ternary oxides of ZrO2-TiO2-Y2O3 obtained by laser ablation, magnetron sputtering and sol-gel techniques

Thin films of ternary oxides of zirconium (Zr), yttrium (Y) and titanium (Ti) were obtained by the sol-gel, magnetron sputtering and laser ablation techniques. Zirconium propoxide, titanium isopropoxide and yttrium nitrate hexahydrate reagents were used as precursors in the sol-gel process. The Zr/Ti and Zr/Y molar ratios have been controlled by varying the precursors and surfactant concentration. The obtained gels were supported by dip coating on α-alumina supports, dried at 373 K and calcinated at 873 K. The powders obtained after the removal of carbon residuals were subsequently pressed and calcinated for using as targets for the magnetron sputtering and pulsed laser deposition techniques. The chemical composition was determined by Auger Electron Spectroscopy. The surface topography was investigated by Atomic Force Microscopy, while the crystallinity was evaluated from X-ray diffraction. The electrical response of the deposits to nitrogen oxides (NO_x) toxic gas is discussed according to the experimental conditions.     

Microstructure and tribological behavior of WS2-Ag composite films deposited by RF magnetron sputtering

WS₂-Ag composite films were deposited on medium carbon steel substrate by RF magnetron sputtering method. The morphology and microstructure of the composite films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The tribological behavior was investigated using a ball-on-disk tribometer in vacuum and in humid air. In the range of Ag content of the film from 4.2 at.% to 40.4 at.%, Ag phase dispersed in amorphous WS₂ matrix, and it changed from amorphous to crystalline structure with the increase of Ag content. The friction coefficients of composite films in humid air were lower and more stable than those of pure WS₂ film, and the environmental sensitivity of tribological behavior decreased obviously with the addition of Ag in the films. At the content of 16.2 at.% Ag, the composite film was dense and adherent, and exhibited excellent tribological performance both in vacuum and in humid air.     

Energetic negative ions in titanium oxide deposition by reactive sputtering in Ar/O2

The flux of energetic negative ions was measured during the preparation of TiO₂ in Ar/O₂ as a function of oxygen partial pressure. The Ti surface was so active that the small amount of O₂ contained in Ar was sufficient to oxidize the target surface. Ti target is also oxidized as similarly to the other metals such as Zr and Zn. Oxide islands form, which coalesce and cover the target surface with an oxide layer. The thickness of the Ti oxide layer on the target surface increased with increasing target current and Ar/O₂ gas pressure, which increased the oxygen flux incident on the target. This is due to the high reactivity of the Ti surface with oxygen. The data revealed that the flux of energetic negative ions in reactive sputtering of Ti in Ar/O₂ is fairly small compared with the sputtering of Zr and Zn. This indicates that the generation rate of negative ions on the Ti target during the reactive sputtering is very small.     

Photocatalytic activity of TiO2 thin films deposited by RF magnetron sputtering

Nano-TiO₂ thin films were deposited on silicon and glass substrates by radio-frequency (RF) magnetron sputtering using TiO₂ ceramic target and characterized by X-ray diffractometer, X-ray photoelectron spectrometer, atomic force microscope, and ultraviolet-visible spectrophotometer. Photocatalytic activity was evaluated by light induced degradation of 5 ppm methyl orange solution using a high pressure mercury lamp as lamp-house. It was found that the film as deposited is polymorph, with energy gap of 3.02 eV, and can absorb visible light. The film was repeatedly used for six times in degradation of 5 ppm methyl orange, and the degradation rates of methyl orange solution are 36.566%, 33.112%, 32.824%, 32.248%, 30.521% and 28.794%, respectively. After ultrasonic treatment in de-ionized water for ten minutes, the degradation rate of methyl orange solution resumes to 33.975%.     

rf-Magnetron sputter deposited ZrO2 dielectrics for metal-insulator-semiconductor capacitors

ZrO₂ gate dielectric thin films were deposited by radio frequency (rf)-magnetron sputtering, and its structure, surface morphology and electrical properties were studied. As the oxygen flow rate increases, the surface becomes smoother. The experimental results indicate that a high temperature annealing is desirable since it improves the electrical properties of the ZrO₂ gate dielectric thin films by decreasing the number of interfacial traps at the ZrO₂/Si interface. The carrier transport mechanism is dominated by the thermionic emission.     

Photocatalytic Zn-doped TiO2 films prepared by DC reactive magnetron sputtering

Zn-doped TiO₂ films were prepared by means of pulsed DC reactive magnetron sputtering method using Ti and Zn mixed target. The deposition condition was optimized to produce uniform and transparent TiO₂ films. Titanium was in the Ti⁴⁺ oxidation state in all Zn-doped TiO₂ films. The zinc oxide deposited on the substrate was in the fully oxidized state of ZnO. Increase of zinc concentration inhibited the crystal growth in the TiO₂ films. The surface morphology gradually changed from crystalline to amorphous along with the increase of doped zinc concentration. The optical transmittances of these films decreased only slightly with increasing zinc concentration due to very similar band edges of ZnO and anatase TiO₂. The doped ZnO had weak influence on light absorption of the TiO₂ films. When zinc concentration was very low (<1 at%), the photocatalytic activities of the doped films had nearly no difference from that of pure TiO₂ film. Photocatalytic activities decreased obviously in the films containing high amount of zinc oxide.     

Structures and mechanical properties of TiN/SiNx multilayer films deposited by magnetron sputtering at different N2/Ar gas flow ratios

Polycrystalline TiN/SiN_x multilayer films are deposited using reactive magnetron sputtering Ti and Si, respectively, discharging a mixture of N₂ and Ar gas with different N₂/Ar gas flow ratios, and their structures and mechanical properties are characterized by X-ray reflectivity (XRR), X-ray diffraction (XRD) and nanoindentation. It is found that when the N₂/Ar gas flow ratio is low, the interface between TiN and SiN_x layer for the obtained TiN/SiN_x film is sharp and the preferred orientation for TiN layer is TiN (200). In contrast, when the N₂/Ar gas flow ratio is high, the interface becomes rough and the preferred orientation for TiN layer changes to TiN (111). Nanoindentation experiments exhibit that the TiN/SiN_x film with a TiN (111) preferred orientation is harder than that with a TiN (200) preferred orientation, and all films have nano-scale fracture characteristics.     

Effect of sputtering pressure and post-annealing on hydrophilicity of TiO2 thin films deposited by reactive magnetron sputtering

A series of TiO₂ thin films was deposited onto glass substrates without intentional heating or biasing by magnetron sputtering of a titanium target using Ar/O₂ reactive mixtures over a broad range of total sputtering pressures from 0.12 Pa to 2.24 Pa. Each of the film types was deposited by the threshold poisoned mode at a specific given oxygen flow rate monitored in-situ by optical emission spectroscopy. Both the sputtering pressure and thermal annealing are the key factors for the TiO₂ films to yield fast-response superhydrophilicity with a water contact angle of 5°. The mechanism of superhydrophilicity for the TiO₂ films deposited by high-pressure sputtering will be discussed based on empirical studies of X-ray diffractometry, high-resolution scanning microscopy and atomic force spectroscopy.     

Photocatalytic TiO2 films deposited on cenosphere particles by pulse magnetron sputtering method

In the present study, TiO₂ films were deposited on the surface of cenosphere particles using the modified magnetron sputtering equipment under different working conditions. The resulting films were characterized by field emission scanning electron microscopy (FE-SEM), Atomic Force Microscopy (AFM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The FE-SEM and AFM results show that the grain sizes and root-mean-square (RMS) roughness values of the TiO₂ films increase with the increase in deposition time and film thickness. The XRD results indicate that the film was TiO₂ film and sputtering time is an importance condition to influence the films crystal. With the increasing of sputtering time, the crystallization of the TiO₂ film was increased. The XPS results show that only TiO₂ films existed on the surface of cenosphere particles. In addition, the photocatalytic activities of these films were investigated by degrading methyl orange under UV irradiation. The results suggest that the photocatalytic activity of cenosphere particles with anatase TiO₂ films is remarkable and this catalyst can be applicable for the photocatalytic degradation of other organic compounds under UV lights.     

Influence of N2 partial pressure on mechanical properties of (Ti,Al)N films deposited by reactive magnetron sputtering

The influence of the nitrogen partial pressure on the mechanical properties of (Ti,Al)N films deposited by DC reactive magnetron sputtering using a Ti-Al mosaic target at a substrate bias of −100 V is investigated. Nanoindentation tests reveal that with increasing N₂ partial pressure, the film hardness and elastic modulus increase initially and then decrease afterwards. The maximum hardness and elastic modulus are 43.4 GPa and 430.8 GPa, respectively. The trend is believed to stem from the variations in the grain size and preferential orientation of the crystals in the (Ti,Al)N films fabricated at varying N₂ partial pressure. The phenomenon is confirmed by results acquired using glancing angle X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS).     

UV-enhanced atomic layer deposition of ZrO2 thin films at room temperature

A UV-enhanced atomic layer deposition (UV-ALD) process was developed to deposit ZrO₂ thin films on poly(ethylene terephthalate) (PET) polymer substrates using zirconium tetra-tert-butoxide (ZTB) and H₂O as precursors with UV light. In the UV-ALD process, the surface reactions were found to be self-limiting and complementary enough to yield uniform, conformal, and pure ZrO₂ thin films on polymer substrates at room temperature. The UV light was very effective to obtain the high-quality ZrO₂ thin films with good adhesive strength on polymer substrates. The ZrO₂ thin films exhibit large-scale uniformity, sharp interfaces, and unique electrical properties.     

Thermal treatment effects on interfacial layer formation between ZrO2 thin films and Si substrates

This paper describes the growth condition of stoichiometric ZrO₂ thin films on Si substrates and the interfacial structure of ZrO₂ and Si substrates. The ZrO₂ thin films were prepared by rf-magnetron sputtering from Zr target with mixed gas of O₂ and Ar at room temperature followed by post-annealing in O₂ ambient. The stoichiometric ZrO₂ thin films with smooth surface were grown at high oxygen partial pressure. The thick Zr-free SiO₂ layer was formed with both Zr silicide and Zr silicate at the interface between ZrO₂ and Si substrate during the post-annealing process due to rapid diffusion of oxygen atoms through the ZrO₂ thin films. After post annealing at 650-750 °C, the multi-interfacial layer shows small leakage current of less than 10⁻⁸ A/cm² that is corresponding to the high-temperature processed thermal oxidized SiO₂.