Morphology of TiN thin films grown on SiO2 by reactive high power impulse magnetron sputtering

Thin TiN films were grown on SiO₂ by reactive high power impulse magnetron sputtering (HiPIMS) at a range of temperatures from 45 to 600 °C. The film properties were compared to films grown by conventional dc magnetron sputtering (dcMS) at similar conditions. Structural characterization was carried out using X-ray diffraction and reflection methods. The HiPIMS process produces denser films at lower growth temperature than does dcMS. Furthermore, the surface is much smoother for films grown by the HiPIMS process. The [200] grain size increases monotonically with increased growth temperature, whereas the size of the [111] oriented grains decreases to a minimum for a growth temperature of 400 °C after which it starts to increase with growth temperature. The [200] crystallites are smaller than the [111] crystallites for all growth temperatures. The grain sizes of both orientations are smaller in HiPIMS grown films than in dcMS grown films.     

High-rate deposition of high-quality Sn-doped In2O3 films by reactive magnetron sputtering using alloy targets

Sn-doped In₂O₃ (ITO) films were deposited on heated (200 °C) fused silica glass substrates by reactive DC sputtering with mid-frequency pulsing (50 kHz) and a plasma control unit combined with a feedback system of the optical emission intensity for the atomic O* line at 777 nm. A planar In-Sn alloy target was connected to the switching unit, which was operated in the unipolar pulse mode. The power density on the target was maintained at 4.4 W cm^− 2 during deposition. The feedback system precisely controlled the oxidation of the target surface in “the transition region.” The ITO film with lowest resistivity (3.1 × 10^− 4 Ω cm) was obtained with a deposition rate of 310 nm min^− 1 and transmittance in the visible region of approximately 80%. The deposition rate was about 6 times higher than that of ITO films deposited by conventional sputtering using an oxide target.     

Dielectric properties of DC reactive magnetron sputtered Al2O3 thin films

Alumina (Al₂O₃) thin films were sputter deposited over well-cleaned glass and Si < 100 > substrates by DC reactive magnetron sputtering under various oxygen gas pressures and sputtering powers. The composition of the films was analyzed by X-ray photoelectron spectroscopy and an optimal O/Al atomic ratio of 1.59 was obtained at a reactive gas pressure of 0.03 Pa and sputtering power of 70 W. X-ray diffraction results revealed that the films were amorphous until 550 °C. The surface morphology of the films was studied using scanning electron microscopy and the as-deposited films were found to be smooth. The topography of the as-deposited and annealed films was analyzed by atomic force microscopy and a progressive increase in the rms roughness of the films from 3.2 nm to 4.53 nm was also observed with increase in the annealing temperature. Al-Al₂O₃-Al thin film capacitors were then fabricated on glass substrates to study the effect of temperature and frequency on the dielectric property of the films. Temperature coefficient of capacitance, AC conductivity and activation energy were determined and the results are discussed.     

High-rate deposition of Ta-doped SnO2 films by reactive magnetron sputtering using a Sn-Ta metal-sintered target

Ta-doped SnO₂ films were deposited on glass substrate (either unheated or heated at 200 °C) by reactive magnetron sputtering with a Sn-Ta metal-sintered target using a plasma control unit (PCU) and mid-frequency (mf, 50 kHz) unipolar pulsing. The PCU feedback system precisely controlled the flow of the reactive and sputtering gases (O₂ and Ar, respectively) by monitoring either discharge impedance or the plasma emission of the atomic O* line at 777 nm. The planar target was connected to the switching unit, which was operated in unipolar pulse mode. Power density on the target was maintained at 4.4 W cm^− 2 during deposition. The lowest obtained resistivity for the films deposited on heated substrate was 6.4 × 10^− 3 Ωcm, where the deposition rate was 250 nm min^− 1.     

Nanocrystalline SnO2 and Au:SnO2 thin films prepared by direct current magnetron reactive sputtering

Nanocrystalline pure and gold doped SnO₂(Au:SnO₂) films were prepared on unheated glass substrates by dc magnetron reactive sputtering and, subsequently, the as deposited films were annealed in air. The films structure, surface morphology, photoluminescence, electrical and optical properties were investigated. After annealing the as deposited SnO₂ films, crystallinity increased and the surface roughness decreased. The intensity of PL peaks increases sharply with the annealing temperature. The optical transmittance of the films was around 89% after annealing the as deposited SnO₂ films at 450 °C. The as deposited Au:SnO₂ films show better crystallinity than the as deposited SnO₂ films, the average grain size was around 4.4 nm. The emission peaks of Au:SnO₂ films are slightly blue shifted as compare to undoped SnO₂ films. The Au:SnO₂ films show the lowest electrical resistivity of 0.001 Ωcm with optical transmittance of 76%, after annealing at 450 °C.     

The synthesis of LiBH4 films under low hydrogen pressure at ambient temperature

Lithium borohydride (LiBH₄) films were first fabricated under low hydrogen pressure (5-70 Pa) at ambient temperature by pulsed laser deposition (PLD). The atomistic structures and chemical compositions of the films were investigated. It was found that during the formation process of LiBH₄, the intermediate compound Li₂B₁₂H₁₂ was formed. As the hydrogen pressure increased up to 70 Pa, the relative weight percent of LiBH₄ was over 70 wt.% even at ambient temperature. Moreover, the stress of the films was decreased as the hydrogen pressure increased.     

Electrolytic and electrophoretic deposition of CeO2 films

Cerium oxide films of thickness 0.1–300 μm were deposited on Ni substrates via cathodic electrolytic and electrophoretic deposition. The films were studied by X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. Experimental results obtained by both deposition methods are compared. The influence of deposition parameters and additives on deposition yields and film morphologies is studied and discussed.     

基片温度对磁控溅射沉积二氧化硅的影响

本文详细地研究了基片温度对磁控溅射沉积二氧化硅的影响,随着基片温度的增加,溅射沉积速率下降明显,薄膜的折射率也出现上升趋势,薄膜也由低温时的疏松粗糙发展为致密光滑.250℃时的溅射沉积速率仅为室温时的1/3,由此,针对间歇式在大面积玻璃上沉积二氧化硅薄膜,我们采取了沉积完ITO薄膜后,先快速降温,再沉积二氧化硅的工艺.     

Characterization of ZnO-In2O3 transparent conducting films by pulsed laser deposition

Transparent conducting oxide (TCO) films in the ZnO-In₂O₃ system were prepared by a pulsed laser deposition method. A target that consists of the mixture of ZnO and In₂O₃ powders was used. Influences of the target composition x (x = [Zn]/([Zn] + [In])) and heater temperature on structural, electrical and optical properties of the TCO films were examined. Introduction of oxygen gas into the chamber during the deposition was necessary for improvement in the transparency of the deposited films. The amorphous phase was observed for a wide range of x = 0.20-0.60 at 110 °C. Minimum resistivity was 2.65 × 10⁻⁴ Ω cm at x = 0.20. The films that showed the minimum resistivity had an amorphous structure and the composition shifted toward larger x, as the substrate temperature increased. The films were enriched in indium compared to the target composition and the cationic In/Zn ratio increased as the substrate temperature was increased.     

Synthesis and characterization of HfO2 and ZrO2 thin films deposited by plasma assisted reactive pulsed laser deposition at low temperature

A plasma assisted reactive pulsed laser deposition process was demonstrated for low-temperature deposition of thin hafnia (HfO₂) and zirconia (ZrO₂) films from metallic hafnium or zirconium with assistance of an oxygen plasma generated by electron cyclotron resonance microwave discharge. The structure and the interface of the deposited films on silicon were characterized by means of Fourier transform infrared spectroscopy, which reveals the monoclinic phases of HfO₂ and ZrO₂ in the films with no interfacial SiO_x layer between the oxide film and the Si substrate. The optical properties of the deposited films were investigated by measuring the refractive indexes and extinction coefficients with the aid of spectroscopic ellipsometry technique. The films deposited on fused silica plates show excellent transparency from the ultraviolet to near infrared with sharp ultraviolet absorption edges corresponding to direct band gap.     

VO2 thin films deposited on silicon substrates from V2O5 target: Limits in optical switching properties and modeling

Thermochromic VO₂ thin films presenting a phase change at T_c = 68 °C and having variable thickness were deposited on silicon substrates (Si-001) by radio-frequency sputtering. These thin films were obtained from optimized reduction of low cost V₂O₅ targets. Depending on deposition conditions, a non-thermochromic metastable VO₂ phase might also be obtained. The thermochromic thin films were characterized by X-ray diffraction, atomic force microscopy, ellipsometry techniques, Fourier transform infrared spectrometry and optical emissivity analyses. In the wavelength range 0.3 to 25 μm, the optical transmittance of the thermochromic films exhibited a large variation between 25 and 100 °C due to the phase transition at T_c: the contrast in transmittance (difference between the transmittance values to 25 °C and 100 °C) first increased with film thickness, then reached a maximum value. A model taking into account the optical properties of both types of VO₂ film fully justified such a maximum value. The n and k optical indexes were calculated from transmittance and reflectance spectra. A significant contrast in emissivity due to the phase transition was also observed between 25 and 100 °C.     

Wet chemical route to transparent BiFeO3 films on SiO2 substrates

BiFeO₃ nanoparticles were prepared by a wet chemical synthesis method. Transparent films were deposited on glass and quartz substrates by dip and spin coating processes from the synthesized sol. We obtained thicker films (~ 2 µm) by dip coating process and thinner films (~ 200 nm) by spin coating process. Transmission electron microscopy images confirmed that the particles are nanocrystalline in size. From the optical transmittance spectra the band gap of the BiFeO₃ nanoparticles was determined in the range of ~ 3.03-2.88 eV (~ 410-430 nm). Electrical resistivity, polarization, zero-field-cooled and field-cooled magnetizations versus temperature characteristics were also studied for these films.     

Fabrication and characterization of Fe3O4 thin films deposited by reactive magnetron sputtering

Fe-O thin films with different atomic ratio of iron to oxygen were deposited on glass and thermally oxidized silicon substrates at temperatures of 300, 473 and 593 K, by reactive magnetron sputtering in Ar+O₂ atmosphere. The composition and structure of the thin films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrical resistivity. It was found from XRD that with increasing the oxygen partial pressure in the working gas, the crystalline structure of the Fe-O films deposited at the substrate temperature of 473 K gradually changed from α-Fe, amorphous Fe-O, Fe₃O₄, γ-Fe₂O₃ to Fe_21.34O₃₂. The structure and chemical valence of the Fe₃O₄ films were analyzed by electron microscopy and XPS, respectively.     

Enhanced photocatalytic activity of silver nanoparticles modified TiO2 thin films prepared by RF magnetron sputtering

Ag-TiO₂ nanostructured thin films with silver volume fraction of 0–40% were prepared by RF magnetron sputtering. The microstructure, surface topography, and optical properties of the films were characterized by X-ray diffractometer, transmission electron microscope, and ultraviolet–visible spectrophotometer. Photocatalytic activity of the films was evaluated by light-induced degradation of methyl orange (C₁₄H₁₄N₃NaO₃S) solution using a high pressure mercury lamp as lamp-house. The relation of photocatalytic activity and silver content was studied in detail. It is found that silver content influences microstructure of TiO₂ thin films, and silver in the films is metallic Ag (Ag⁰). Photocatalytic activity of the films increases with increasing silver content up to 5 vol.% Ag and then decreases to values significantly still bigger than that of pure TiO₂ thin films. Silver nanoparticles significantly enhance the photocatalytic activity of TiO₂ films. The better separation between electrons and holes on silver modified TiO₂ thin films surface allowed more efficiency for the oxidation and reduction reactions. The enhanced photocatalytic activity was mainly attributed to the decrease of energy gap of the films and the increase of oxygen anion radicals O₂⁻ and reactive center of surface Ti³⁺ on silver modified TiO₂ thin films surface.     

Photoluminescence optimization of Er-doped SiO2 films synthesized by radiofrequency magnetron sputtering with energetic treatments during and after deposition

By radiofrequency magnetron sputtering co-deposition we synthesized Er:SiO₂ film 0.5 μm thick on silica substrates, with Er content < 0.3 atomic %. By changing the preparation condition (during deposition we have used an additional negative bias voltage applied to the substrates for inducing a low-energy ion bombardment, with or without a contemporary heating) and by varying the thermal treatment after the synthesis (the best conditions were 1 h in the range 700-800 °C, in air) we have obtained an Er:SiO₂ system with an intense photoluminescence emission at λ = 1.54 μm. The best-performing Er:SiO₂ samples obtained by sputtering have shown a photoluminescence response comparable to that of the typical Er:SiO₂ thin film systems obtained by conventional techniques used in applicative framework.     

Characterization of Al2O3/ZrO2 nano multilayer thin films prepared by pulsed laser deposition

Microstructural characterization of pulsed laser deposited Al₂O₃/ZrO₂ multilayers on Si (1 0 0) substrates at an optimized oxygen partial pressure of 3 × 10⁻² mbar and at room temperature (298 K) has been carried out. A nanolaminate structure consisting of alternate layers of ZrO₂ and Al₂O₃ with 40 bi-layers was fabricated at different zirconia layer thicknesses (20, 15 and 10 nm). The objective of the work is to study the effect of ZrO₂ layer thickness on the stabilization of tetragonal ZrO₂ phase for a constant Al₂O₃ layer thickness of 5 nm. The Al₂O₃/ZrO₂ multilayer films were characterized using high temperature X-ray diffraction (HTXRD) in the temperature range 298–1473 K. The studies showed that the thickness of the zirconia layer has a profound influence on the crystallization temperature for the formation of tetragonal zirconia phase. The tetragonal phase content increased with the decrease of ZrO₂ layer thickness. The cross-sectional transmission electron microscope (XTEM) investigations were carried out on a multilayer thin films deposited at room temperature. The XTEM studies showed the formation of uniform thickness layers with higher fraction of monoclinic and small fraction of tetragonal phases of zirconia and amorphous alumina.     

Cu2O thin films deposited by reactive direct current magnetron sputtering

The Cu₂O thin films were prepared on quartz substrate by reactive direct current magnetron sputtering. The influences of oxygen partial pressure and gas flow rate on the structures and properties of deposited films were investigated. Varying oxygen partial pressure leads to the synthesis of Cu₂O, Cu₄O₃ and CuO with different microstructures. At a constant oxygen partial pressure of 6.6 × 10^− 2 Pa, the single Cu₂O films can be obtained when the gas flow rate is below 80 sccm. The as-deposited Cu₂O thin films have a very high absorption in the visible region resulting in the visible-light induced photocatalytic activity.     

Characterization of the aqueous peroxomethod for the synthesis of transparent TiO2 thin films

This article summarizes our progress made on an aqueous chemical solution deposition method used for the deposition of photocatalytically active TiO₂ thin films. Starting from Titanium(IV)butoxide we achieved a stable titanium precursor solution containing titanium-peroxo compounds by reaction between Titanium(IV)butoxide and hydrogen peroxide. We were able to deposit anatase TiO₂ films with good optical transparency and abrasion resistance. Dip-coating was used to deposit thin films on glass substrates from the solution. The occurring reaction mechanism was examined via thermal analysis, mass spectrometry and Raman spectroscopy. Decomposition of organic polluents was confirmed by the breakdown of ethanol. The obtained results show promising possibilities of this low-carbon containing synthesis method towards transparent, photocatalytic coatings. Presence of carbon was minimized by avoiding organic complexing agents. These materials are of great importance in the synthesis of self-cleaning materials.     

Structural,electrical and photoluminescence properties of ZnO:Al network films grown on nanochannel Al2O3 substrates by direct current magnetron sputtering with an oblique target

ZnO:Al network films were grown on nanochannel Al₂O₃ substrates at 300 K by direct current magnetron sputtering with an oblique target. The film thicknesses are 60 nm, 160 nm and 190 nm. The holes of the network films diminish with increasing film thickness. For the 60-nm thick film, the network is formed by connecting grains. For the 160-nm and 190-nm thick films, however, the network is formed by connecting granules. The granules consist of many small grains. All the network films have a wurtzite structure. The 60-nm and 160-nm thick network films mainly have a [1 0 1] orientation in the film growth direction while the 190-nm thick network film grows with a random crystallographic orientation. A temperature dependence of the resistance within 160–300 K reveals that the network films exhibit a semiconducting behavior and their carrier transport mechanism is thermally activated band conduction. Room temperature photoluminescence spectra for wavelengths between 300 nm and 700 nm reveal a violet emission centered at 405 nm for the 60-nm thick network film and a blue emission centered at 470 nm for both the 160-nm and the 190-nm thick network films. Annealing decreases the resistivity of the network film.     

Analysis of precursors for crystal growth of YBaCuO thin films in magnetron sputtering deposition

We correlated the crystallinity of YBaCuO films prepared by magnetron sputtering deposition using Ar/O₂ mixture gas with the atomic and molecular composition in the gas phase. YBaCuO films were deposited on MgO substrates at 670 °C. Two-dimensional distributions of Y, Ba, Cu, YO, BaO, and CuO densities and one-dimensional distribution of O density were measured by laser-induced fluorescence spectroscopy. The Y and Ba densities decreased significantly with the increase of the O₂ partial pressure, and they were below the detection limit at an O₂ flow ratio of 10% and a total gas pressure of 53 Pa. The decrease in the Y and Ba densities was compensated by an increase in the YO and BaO densities. The decrease in the Cu density with the increase of the O₂ partial pressure was less significant, while the CuO density was below the detection limit at all the discharge conditions. The O density was evaluated to be 10¹²-10¹³ cm^− 3, which was much higher than the Cu density. On the other hand, YBaCuO films with high crystallinity were obtained at total gas pressures of 53-80 Pa and O₂ flow ratios of 50-70%. Therefore, it is concluded that the precursors for the deposition of YBaCuO films with high crystallinity are Cu, YO, BaO, and O.