Direct patterning of SnO2 composite films prepared with various contents of Pt nanoparticles by photochemical metal-organic deposition

The optical and electrical characteristics of SnO₂ composite films with various contents (0, 0.05, 0.1, 0.2, and 0.3 at.%) of Pt nanoparticles were evaluated. The Pt nanoparticles were synthesized by a methanol reduction method and their average size was controlled to 3 nm using poly(N-vinyl-2-pyrrolidone) as a protecting agent. The lowest resistivity of 2.031 × 10^− 2 Ω cm was obtained in the SnO₂ film containing 0.2 at.% Pt nanoparticles after annealing at 700 °C while its average transmittance in the visible region was 85.24%. The enhanced electrical properties were attributed to the increase of the carrier concentration and crystallinity of the films due to donation from Pt nanoparticles as well as the increased annealing temperature. Meanwhile, the slight degradation of the transmittance was due to scattering from the introduction of Pt nanoparticles and the increased crystallite size due to the increase of the annealing temperature to 700 °C. Well-defined 20-μm wide direct-patterned composite SnO₂ films containing Pt nanoparticles were formed by a simple photochemical metal-organic deposition process involving a photosensitive starting precursor, UV exposure, and removal of the unpatterned area by rinsing with solvent. Based on the results of this study, we suggest that direct-patternable SnO₂ films with Pt nanoparticles can be easily applied to transparent electrodes in electrical devices without requiring an expensive and toxic process such as dry etching.     

Preparation, dielectric and ferroelectric properties of Pb5Ge3O11 and Pb5Ge2.85Si0.15O11 thin films fabricated by sol-gel process

Lead germanate-silicate (Pb₅Ge_2.85Si_0.15O₁₁) ferroelectric thin films were successfully fabricated on Pt/Ti/SiO₂/(100)Si substrates by the sol-gel process. The thin films were fabricated by multi-coating at preheating temperatures of 350 and 450 °C. After annealing the thin films at 600 °C, the films exhibited c-axis preferred orientation. The degree of c-axis preferred orientation of the thin films preheated at 350 °C was higher than that of films preheated at 450 °C. Grain growth was influenced by the annealing time. The thin films exhibited a well-saturated ferroelectric P-E hysteresis loop when preheated at 350 °C and annealed at 600 °C for 1.5 h. The values of the remanent polarization (Pr) and the coercive field (Ec) were approximately 2.1 μC/cm² and 100 kV/cm, respectively.     

Crystallization and electrical resistivity of Cu2O and CuO obtained by thermal oxidation of Cu thin films on SiO2/Si substrates

In this work, we study the crystallization and electrical resistivity of the formed oxides in a Cu/SiO₂/Si thin film after thermal oxidation by ex-situ annealing at different temperatures up to 1000 °C. Upon increasing the annealing temperature, from the X ray diffractogram the phase evolution Cu → Cu + Cu₂O → Cu₂O → Cu₂O + CuO → CuO was detected. Pure Cu₂O films are obtained at 200 °C, whereas uniform CuO films without structural surface defects such as terraces, kinks, porosity or cracks are obtained in the temperature range 300-550 °C. In both oxides, crystallization improves with annealing temperature. A resistivity phase diagram, which is obtained from the current-voltage response, is presented here. The resistivity was expected to increase linearly as a function of the annealing temperature due to evolution of oxides. However, anomalous decreases are observed at different temperatures ranges, this may be related to the improvement of the crystallization and crystallite size when the temperature increases.     

Characterization and visible light germicidal efficacy of nitrogen doped TiO2 film crystallized by microwave irradiations

The visible light bactericidal ability of nitrogen doped TiO₂ (TiON) film on Si (100) has been enhanced greatly (by 22%) through a single-mode microwave irradiation annealing (f = 2.45 GHz, 20 s) in comparison with the conventional heat treatment at the same temperature (500 °C, 300 s). Analyses of X-ray photoelectron spectroscopy and transmission electron microscopy showed that the microwave annealed TiON film had a higher nitrogen concentration and much better crystallinity, both of which contribute to its prior bactericidal ability under visible light. The optimized annealing parameters of microwave irradiation are 500 °C within 20 s. Increase of annealing temperature and irradiation time resulted in the decrease of nitrogen concentration within the film. The crystallized TiON film has an anatase but not a rutile structure at the annealing temperature up to 800 °C.     

High-quality epitaxial Bi(111) films on Si(111) by isochronal annealing

Bi(111) films grown on Si(111) at room temperature show a significantly higher roughness compared to Bi films grown on Si(100) utilizing a kinetic pathway based on a low-temperature process. Isochronal annealing steps of 3 min duration each with temperatures up to 200 °C cause a relaxation of the Bi films' lattice parameter toward the Bi bulk value and yield an atomically flat Bi surface. Driving force for the relaxation and surface reordering is the magic mismatch of 11 Bi atoms to 13 Si atoms that emerges at annealing temperatures above 150 °C and reduces the remaining strain to less than 0.2%.     

Annealing effects on microstructure and mechanical properties of sputtered multilayer Cr(1 − x)AlxN films

Multilayer Cr_(1 − x)Al_xN films with a total thickness of 2 μm were deposited on high-speed steel by medium frequency magnetron sputtering from Cr and Al-Cr (70 at.% Al) targets. The samples were annealed in air at 400 °C, 600 °C, 800 °C and 1000 °C for 1 hour. Films were characterized by cross-sectional scanning electron microscopy and X-ray diffraction analysis. The grain size of the as-deposited multilayer films is about 10 nm, increasing with the annealing temperature up to 100 nm. Interfacial reactions have clearly changed at elevated annealing temperatures. As-deposited films' hardness measured by nanoindentation is 22.6 GPa, which increases to 26.7 GPa when the annealing temperature goes up to 400 and 600 °C, but hardness decreases to 21.2 GPa with further annealing temperature increase from 600 to 1000 °C. The multilayer film adhesion was measured by means of the scratch test combined with acoustic emission for detecting the fracture load. The critical normal load decreased from 49.7 N for the as-deposited films to 21.2 N for the films annealed at 1000 °C.     

Fabrication of a n-ZnO/p-Si heterojunction diode by ultra-high vacuum magnetron sputtering

Heterojunction diodes of n-type ZnO were fabricated on a p-type Si(100) substrate using an ultra-high vacuum radio frequency magnetron sputtering method at room temperature. A short-time post-annealing process was performed to prevent inter-diffusion of Zn, dopants, and Si atoms. The post-annealing process at 600 °C enhanced the crystallinity of ZnO films and produced a high forward to reverse current ratio of the heterojunction diode with a barrier height of approximately 0.336 eV. A thin SiO_x layer at the interface of the ZnO film and Si substrate appeared distinctly at the 600 °C annealing, however the post-annealing at 700 °C showed an a-(Zn_2xSi_1 − xO₂) structure caused by diffusion of silicon into the ZnO film. In the n-ZnO/p-Si sample annealed at 700 °C, a rapid change in the barrier height was considered due to the effect of the dopant segregation from the substrate and deformation of the a-SiO_x structure.     

Influence of aluminum nitride interlayers on crystal orientation and piezoelectric property of aluminum nitride thin films prepared on titanium electrodes

Highly c-axis-oriented aluminum nitride (AlN) thin films have been prepared on titanium (Ti) bottom electrodes by using AlN interlayers. The AlN interlayers were deposited between Ti electrodes and silicon (Si) substrates, such as AlN/Ti/AlN/Si. The crystallinity and crystal orientation of the AlN films and Ti electrodes strongly depended on the thickness of the AlN interlayers. Although the sputtering conditions were the same, the X-ray diffraction intensity of AlN (0002) and Ti (0002) planes drastically increased, and the full-width at half-maximum (FWHM) of the X-ray rocking curves decreased from 5.1° to 2.6° and from 3.3° to 2.0°, respectively. Furthermore, the piezoelectric constant d₃₃ of the AlN films was significantly improved from − 0.2 to − 4.5 pC/N.     

Preparation and characterization of transparent semiconductor RuO2-SiO2 films synthesized by sol-gel route

RuO₂-SiO₂ thin films with different Si/Ru molar ratios were prepared by the sol-gel method, using the hydrate ruthenium (III) chloride (RuCl₃·3.5H₂O) and tetraethylorthosilicate as precursors. The crystal structure, resistivity, chemical bonding configuration, transmittance, carrier concentration, and mobility of the RuO₂-SiO₂ films were investigated before and after annealing in N₂ ambient at 400-700 °C. The resistivity of the RuO₂-SiO₂ films with different Si/Ru molar ratios decreased abruptly after annealing at 400-700 °C. On the other hand, RuO₂ phase precipitated in the RuO₂-SiO₂ films with different Si/Ru molar ratios after annealing. Fourier transform infrared spectroscopy spectra indicated that the water absorption occurs for as-deposited RuO₂-SiO₂ films with different Si/Ru molar ratios. The transmittance of all RuO₂-SiO₂ films presented transmittance maximums after annealing at 700 °C. The carrier concentration and mobility of RuO₂-SiO₂ films are related to the Si/Ru molar ratios and the annealing temperature. This study discusses the connection among the material properties of the RuO₂-SiO₂ films and how they are influenced by the Si/Ru molar ratios and the annealing temperatures of RuO₂-SiO₂ films.     

Effect of post-annealing treatment in oxygen on dielectric properties of K0.5Na0.5NbO3 thin films prepared by chemical solution deposition

K_0.5Na_0.5NbO₃ thin films were prepared on Pt/Ti/SiO₂/Si substrates by chemical solution deposition method with different annealing temperatures of 550 °C, 600 °C, 700 °C. The post-annealing treatment was introduced at 550 °C for 3 min in oxygen ambient. It is found that the films were composed of pure provskite phase, and the post-annealing treatment promoted the crystallization and improved the quality of the films, which resulted in the enhancement of the dielectric property of the films. The effect of the post-annealing on the dielectric properties of the films was also discussed.     

Structure and optical properties of Zr1−xSixN thin films on sapphire

A series of zirconium silicon nitride (Zr_1−xSi_xN) thin films were grown on r-plane sapphire substrates using reactive RF magnetron co-sputtering of Zr and Si targets in a N₂/Ar plasma. X-ray diffraction pole figure analysis, X-ray reflectivity, X-ray photoelectron spectroscopy (XPS), optical microscopy, and optical absorption spectroscopy were used to characterize the film stoichiometries and structures after growth at 200 °C and post-deposition annealing up to 1000 °C in ultra-high vacuum. The atomically clean r-plane sapphire substrates induce high quality (100) heteroepitaxy of ZrN films rather than the (111) orientation observed on steel and silicon substrates, but the addition of Si yields amorphous films at the 200 °C growth temperature. After the annealing treatment, films with Si content x < 0.15 have compressive stress and crystallize into a polycrystalline structure with (100) fiber texture. For x > 0.15, the films are amorphous and remain so even after ultra-high vacuum annealing at 1000 °C. XPS spectra indicate that the bonding changes from covalent to more ionic in character as Si―N bonds form instead of Zr―N bonds. X-ray reflectivity, atomic force microscopy (AFM) and optical microscopy data reveal that after post-deposition annealing the 100 nm thick films have an average roughness < 2 nm, except for Si content near x = 0.15 corresponding to where the film becomes amorphous rather than being polycrystalline. At this stoichiometry, evidence was found for regions of film delamination and hillock formation, which is presumably driven by strain at the interface between the film and sapphire substrate. UV-visible absorption spectra also were found to depend on the film stoichiometry. For the amorphous Si-rich films (x > 0.15), the optical band gap increases with Si content, whereas for Zr-rich films (x < 0.15), there is no band gap and the films are highly conductive.     

Preparation of (ZnO)1−x(GaN)x:Mn powder and its photoluminescence properties

(ZnO)_1−x(GaN)_x:Mn²⁺ powder was prepared by a conventional solid-state reaction under an NH₃ gas flow. The sample preparation conditions including the mixing ratio of the raw materials, the annealing temperature, and the annealing time were varied. The crystallinity and the photoluminescence (PL) intensity of this fluorescent material were improved by increasing the amount of ZnO and by increasing the annealing time, and no changes was observed in the PL wavelength. The crystallinity of the samples was enhanced and the PL intensity increased markedly at annealing temperatures of 700 °C and 800 °C, respectively. Moreover, it was clarified that the sample could be synthesized at annealing temperatures of above about 650 °C.     

Epitaxial growth and exchange coupling of spinel ferrimagnet Ni0.3Zn0.7Fe2O4 on multiferroic BiFeO3

Thin films of the zinc nickel ferrite, Zn_0.7Ni_0.3Fe₂O₄ (ZNFO), were deposited by the RF magnetron sputtering on a number of substrates, including (001) oriented single crystals of LaAlO₃ (LAO) and SrTiO₃ (STO), polycrystalline Pt/Si, and epitaxial films of BiFeO₃ (BFO) and LaNiO₃ (LNO). Except for the films on Pt/Si, the ZNFO films grown on other substrates were epitaxial and their magnetic properties were affected by the heteroepitaxy induced strains. Typically, the coercivity (H_c) was increased with the strain, i.e. H_c varied from 31 Oe for the 150 nm thick polycrystalline films grown on Pt/Si, to 55 Oe and 155 Oe for the 20 nm thick epitaxial films grown on BFO and LAO, respectively. The saturation magnetization of the epitaxial films was reduced accordingly to about 470 emu/cm³ from 986 emu/cm³ in the polycrystalline films. The all-oxide architecture allowed field-annealing to perform at the temperature above the Neel temperature of BFO (~ 370 °C), after which clear exchange bias was observed.     

Piezoelectric properties of Bi4Ti3O12 thin films annealed in different atmospheres

Bismuth titanate (Bi₄Ti₃O₁₂—BIT) films were evaluated for use as lead-free piezoelectric thin-films in micro-electromechanical systems. The films were grown by the polymeric precursor method on Pt/Ti/SiO₂/Si (1 0 0) (Pt) bottom electrodes at 700 °C for 2 h in static air and oxygen atmospheres. The domain structure was investigated by piezoresponse force microscopy (PFM). Annealing in static air leads to better ferroelectric properties, higher remanent polarization, lower drive voltages and higher piezoelectric coefficient. On the other hand, oxygen atmosphere favors the imprint phenomenon and reduces the piezoelectric coefficient dramatically. Impedance data, represented by means of Nyquist diagrams, show a dramatic increase in the resistivity for the films annealed in static air atmopshere.     

Physical properties of electrically conductive Sb-doped SnO2 transparent electrodes by thermal annealing dependent structural changes for photovoltaic applications

We have investigated the optical and electrical characteristics of antimony (Sb)-doped tin oxide (SnO₂) films with modified structures by thermal annealing as a transparent conductive electrode. The structural properties were analyzed from the relative void % by spectroscopic ellipsometry as well as the scanning electron microscopy images and X-ray diffraction patterns. As the annealing temperature was raised, Sb-doped SnO₂ films exhibited a slightly enhanced crystallinity with the increase of the grain size from 17.1 nm at 500 °C to 34.3 nm at 700 °C. Furthermore, the refractive index and extinction coefficient gradually decreased due to the increase in the relative void % within the film during the annealing. The resistivity decreased to 8.2 × 10⁻³ Ω cm at 500 °C, but it increased rapidly at 700 °C. After thermal annealing, the optical transmittance was significantly increased. For photovoltaic applications, the photonic flux density and the figure of merit over the entire solar spectrum were obtained, indicating the highest values of 5.4 × 10¹⁴ cm⁻² s⁻¹ nm⁻¹ at 1.85 eV after annealing at 700 °C and 340.1 μA cm⁻² Ω⁻¹ at 500 °C, respectively.     

Fabrication of TiO2-based transparent conducting oxide on glass and polyimide substrates

We report on preparation and properties of anatase Nb-doped TiO₂ transparent conducting oxide films on glass and polyimide substrates. Amorphous Ti_0.96Nb_0.04O₂ films were deposited at room temperature by using sputtering, and were then crystallized through annealing under reducing atmosphere. Use of a seed layer substantially improved the crystallinity and resistivity (ρ) of the films. We attained ρ = 9.2 × 10^− 4 Ω cm and transmittance of ~ 70% in the visible region on glass by annealing at 300 °C in vacuum. The minimum ρ of 7.0 × 10^− 4 Ω cm was obtained by 400 °C annealing in pure H₂.     

Effect of annealing on the characteristics of Au/Cr bilayer films grown on glass

Au layers with thickness of about 110 nm were sputter-deposited on unheated glass substrates coated with a Cr layer about 20 nm thick. The chamber was evacuated to a pressure of 2 Pa and then sputtering was carried out at Ar pressure of 4 Pa. The Au/Cr bilayer films were annealed in a vacuum of 5×10⁻⁴ Pa at 170°C, 180°C, 200°C and 250°C for from 5 to 120 min, respectively. Atomic force microscopy was used to observe the structural characteristic of the bilayer films. Auger electron spectroscopy was used to analyze the composition inside the Au layers. The sheet resistance of the films was measured using the four-point probe technique. The grain size of the bilayer film gradually increases with an increase in annealing temperature while its average surface roughness ranging from 4.5 to 6.8 nm does not show any systematic change with annealing temperature and time. No impurities such as carbon, nitrogen and oxygen are detected inside all of the Au layers. When the annealing temperature reaches 200°C and the annealing time exceeds 30 min, chromium atoms markedly diffuse into the Au layer. Furthermore, for the bilayer films annealed at 250°C, chromium atoms have markedly diffused into the Au layer even for annealing time of 5 min. Regardless of the increase in grain size of the Au layer, the diffusion of chromium atoms into the Au layer causes an increase in the resistivity of the bilayer film.     

Structural, dielectric and ferroelectric properties of multilayer lithium tantalate thin films prepared by sol-gel technique

Multilayer lithium tantalate thin films were deposited on Pt-Si [Si(111)/SiO₂/TiO₂/Pt(111)] substrates by sol-gel process. The films were annealed at different annealing temperatures (300, 450 and 650 °C) for 15 min. The films are polycrystalline at 650 °C and at other annealing conditions below 650 °C the films are in amorphous state. The films were characterized using X-ray diffraction, atomic force microscopy (AFM) and Raman spectroscopy. The AFM of images show the formation of nanograins of uniform size (50 nm) at 650 °C. These polycrystalline films exhibit spontaneous polarization of 1.5 μC/cm² at an application of 100 kV/cm. The dielectric constant of multilayer film is very small (6.4 at 10 kHz) as compared to that of single crystal.     

Inkjet-printing of indium tin oxide (ITO) films for transparent conducting electrodes

Indium-tin-oxide (ITO) films have been prepared by inkjet-printing using ITO nanoparticle inks. The electrical and optical properties of the ITO films were investigated in order to understand the effects of annealing temperatures under microwave. The decrease in the sheet resistance and resistivity of the inkjet-printed ITO films was observed as the annealing temperature increases. The film annealed at 400 °C showed the sheet resistance of 517 Ω/sq with the film thickness of ∼580 nm. The optical transmittance of the films remained constant regardless of their annealing temperatures. In order to further reduce the sheet resistance of the films, Ag-grid was printed in between two layers of inkjet-printed ITO. With 3 mm Ag-grid line-to-line pitch, the Ag-grid inserted ITO film has the sheet resistance of 3.4 Ω/sq and the transmittance of 84% after annealing at 200 °C under microwave.     

Effect of annealing on the characteristics of Au layers grown on the high-temperature deposited Ni50Fe50 layers

80 nm-thick Ni₅₀Fe₅₀ layers were sputter-deposited on glass substrates at 400 °C and then Au layers were sputter-deposited on the Ni₅₀Fe₅₀ layers. The Au/Ni₅₀Fe₅₀ bilayer films were annealed in a vacuum of 5×10⁻⁴ Pa from 250 to 450 °C for 30 min or 90 min. The characteristics of the Au layers were studied by Auger electron spectroscopy, field emission scanning electron microscopy, X-ray diffraction and a four-point probe technique. When the annealing temperature reaches 450 °C, Fe and Ni atoms diffuse markedly into the Au layer and the Fe content is more than the Ni content. When the annealing temperature is lower than 450 °C, the grain size of the Au layers does not change markedly with annealing temperature. However, as the annealing temperature reaches 450 °C, the annealing promotes the grain growth of the Au layer. As the annealing temperature exceeds 300 °C, the resistivity of the bilayer films increases with increasing annealing temperature. The diffusion of Fe and Ni atoms into the Au layer results in an increase in the resistivity of the annealed bilayer film. Large numbers of Fe and Ni atoms diffusing into the Au layer of the annealed Au/Ni₅₀Fe₅₀ bilayer film lead to a significant decrease in the lattice constant of the Au layer.