The evolution behavior of structures and photoluminescence of K-doped ZnO thin films under different annealing temperatures

In this work, 1 at.% K-doped ZnO thin films were prepared by sol-gel method on Si substrates. The evolution behavior of the structures and photoluminescence of these films under different annealing temperatures was deeply studied. The crystal structures and surface morphology of the samples were analyzed by an X-ray diffractometer and an atomic force microscope, respectively. The photoluminescence spectra were used to study the luminescent behavior of the samples. The results showed that the films had a hexagonal wurtzite structure and were preferentially oriented along the c-axis perpendicular to the substrate surface. All the samples showed a strong ultraviolet emission and a weak blue emission. With the increase of annealing temperature, the ZnO grains gradually grew up; at the same time, the blue emission gradually decreased. The sample annealed at 500 °C showed the best crystalline quality and strongest ultraviolet emission. The authors think that the blue emission in these samples is mainly connected with K interstitial defects. When the 1 at.% K-doped ZnO thin film is annealed at high temperatures (≥600 °C), most of K interstitials move into ZnO lattice sites replacing Zn. As a result, the blue emission resulting from K interstitial defects also decreased.     

New process for synthesis of ZnO thin films: Microstructural, optical and electrical characterization

Nanocrystalline ZnO thin films were prepared on glass substrates by using spin coating technique. The effect of annealing temperature (400-700 °C) on structural, compositional, microstructural, morphological, electrical and optical properties of ZnO thin films were studied by X-ray diffraction (XRD), Energy dispersive Spectroscopy (EDS), Atomic Force Microscopy (AFM), High Resolution Transmission Microscopy (HRTEM), Scanning Electron Microscopy (SEM), Electrical conductivity and UV-visible Spectroscopy (UV-vis). XRD measurements show that all the films are nanocrystallized in the hexagonal wurtzite structure and present a random orientation. The crystallite size increases with increasing annealing temperature. These modifications influence the optical properties. The AFM analysis revealed that the surface morphology is smooth. The HRTEM analysis of ZnO thin film annealed at 700 °C confirms nanocrystalline nature of film. The SEM results shows that a uniform surface morphology and the nanoparticles are fine with an average grain size of about 40-60 nm. The dc room temperature electrical conductivity of ZnO thin films were increased from 10⁻⁶ to 10⁻⁵ (Ω cm)⁻¹ with increase in annealing temperature. The electron carrier concentration (n) and mobility (μ) of ZnO films annealed at 400-700 °C were estimated to be of the order of 4.75-7.10 × 10¹⁹ cm⁻³ and 2.98-5.20 × 10⁻⁵ cm² V⁻¹ S⁻¹.The optical band gap has been determined from the absorption coefficient. We found that the optical band gap energy decreases from 3.32 eV to 3.18 eV with increasing annealing temperature between 400 and 700 °C. This means that the optical quality of ZnO films is improved by annealing.It is observed that the ZnO thin film annealing at 700 °C has a smooth and flat texture suited for different optoelectronic applications.     

溅射气压对ZnO透明导电薄膜光电性能的影响

采用射频磁控溅射方法,在普通玻璃上制备了具有高度c轴取向的ZnO薄膜,研究了溅射气压(0.2～1.5 Pa)对ZnO薄膜的微观结构和光电性能的影响.AFM、XRD、UV-Vis分光光度计及四探针法研究表明:随着溅射气压的增大,ZnO薄膜沿c轴方向的结晶质量提高,晶粒细化,薄膜表面更加致密,晶粒大小更加均匀;ZnO薄膜在400～900nm范围内的平均透过率均高于85%,其中在0.5～1.5 Pa范围内其透过率高于90%;样品在高纯氮气气氛中经350 ℃,300 s退火后,电阻率最低达到10-2 Ω-cm量级.     

Elaboration and characterization of Al doped ZnO nanorod thin films annealed in hydrogen

ZnO thin films doped with Al concentrations of 1.0, 2.0, 3.0, 4.0, 5.0 at% were prepared by a sol-gel spin-coating method on glass substrates and respectively annealed at 550 °C for 2 h in hydrogen and air. The X-ray diffraction and selected-area electron diffraction results confirm that the Al doped ZnO thin films are of wurtzite hexagonal ZnO. The scanning electron microscope results indicate that the Al doped ZnO nanorod thin films can be got by annealing in hydrogen rather than in air. The optical properties reveal that the Al doped ZnO thin films have obviously enhanced transmittance in the visible region. The electrical properties show that the resistivity of 1.0 at% Al doped ZnO thin films has been remarkably reduced from 0.73 Ω m by annealing in air to 3.2 × 10⁻⁵ Ω m by annealing in hydrogen. It is originated that the Al doped ZnO nanorod thin films annealed in hydrogen increased in electron concentration and mobility due to the elimination of adsorbed oxygen species, and multicoordinated hydrogen.     

Effects of post-annealing on Schottky contacts of Pt/ZnO films toward UV photodetector

The Schottky contact of Pt/ZnO was formed by depositing ZnO films oriented along c-axis by pulsed-laser deposition on Pt/Ti buffer layer supported by SiO₂/Si substrate. Effects of the post-annealing on the crystallinity, uniformity and native defects of ZnO film as well as Schottky contacts of Pt/ZnO films were investigated. Results show that the annealing can improve the crystallinity of ZnO film, suppress the native defects, and enhance the performance of Pt/ZnO Schottky contacts dramatically. The best Schottky diode shows the largest barrier height of 0.8 eV with reverse leakage current of 1.5 × 10⁻⁵ A/cm². The zero-biased photodetector based on the best Schottky diode possesses responsivity of 0.265 A/W at 378 nm, fast photo-response component with rise time of 10 ns and fall time of 17 ns. This report demonstrates possibility of ZnO films/Pt hetero-junction with large area Schottky contact, and establishes the potential of this material for use in UV photodetector devices.     

Nanobeads of zinc oxide with rhodamine B dye as a sensitizer for dye sensitized solar cell application

Cost effective, ruthenium metal free rhodamine B dye has been chemically adsorbed on ZnO films consisting of nanobeads to serve as a photo anode in dye sensitized solar cells. These ZnO films were chemically synthesized at room temperature (27 °C) on to fluorine doped tin oxide (FTO) coated glass substrates followed by annealing at 200 °C. These films consisting of inter connected nanobeads (20-40 nm) which are due to the agglomeration of very small size particles (3-5 nm) leading to high surface area. The film shows wurtzite structure having high crystallinity with optical direct band gap of 3.3 eV. Optical absorbance measurements for rhodamine B dye covered ZnO film revealed the good coverage in the visible region (460-590 nm) of the solar spectrum. With poly-iodide liquid as an electrolyte, device exhibits photon to electric energy conversion efficiency (η) of 1.26% under AM 1.5G illumination at 100 mW/cm².     

Thermal behavior of an oxide layer on aluminum

Films 16 to 17 μm thick were obtained on the ^#AMg5 alloy by plasma electrolytic oxidation (PEO) in an orthophosphate-borate electrolyte. Air annealing at 250, 300, 400, and 500°C for 4 h did not affect the thickness, weight, and the elemental composition of the resulting films. The contact angle for water changed from 75° to zero. In a temperature range from 250 to 300°C, the content of the crystalline γ-Al₂O₃ phase jumped. Above 300°C, the film surface cracked and became less resistant to corrosion. Original Russian Text ? V.S. Rudnev, A. E. Lysenko, P. M. Nedozorov, T. P. Yarovay, A.N. Minaev, 2007, published in Zashchita Metallov, 2007, Vol. 43, No. 5, pp. 510–514.     

Effects of thermal treatment on the characteristics of boron and tantalum-doped ZnO thin films deposited by the electrospraying method at atmospheric pressure

Metal-doped (B and Ta) ZnO thin films were deposited by the electrospraying method onto a heated glass substrate. The structural, electrical and optical properties of the films were investigated as a function of dopant concentration in the solution and also as a function of annealing temperature. The results show that all the prepared metal-doped ZnO films were polycrystalline in nature with a (0 0 2) preferred orientation. As the amounts of dopant were increased in the starting solution, the crystallinity and transmittance decreased. On the other hand, heat treatment of the films enhanced the transmittance, Hall mobility, carrier concentration and crystallinity. It was also observed that 2 at.% is the optimal doping amount in order to achieve the minimum resistivity and maximum optical transmittance. As-deposited films have high resistivity and low optical transmittance. The annealing of the as-deposited thin films in air resulted in the reduction of resistivity. Depending on the characteristics of dopant, mainly ionic radius, the effects of dopant were studied on the properties of ZnO thin films. Boron and tantalum have been considered as dopants, tantalum being the superior of the two, since it showed the lower resistivity and higher carrier concentration as well as higher mobility. The minimum value of resistivity was 1.95 × 10^− 4 Ω cm (15 Ω/□) with an optical transmittance more than 93% in the visible region and minimum resistivity of 2.16 × 10^− 4 Ω cm (18 Ω/□) with an optical transmittance greater than 96% for 2 at. % tantalum- and boron-doped ZnO films respectively. The present values of resistivities were closer to the indium tin oxide (ITO) resistivity and also closest to the lowest resistivity values among the ZnO films that were previously reported. The prepared films exhibit the good crystalline structure, homogenous surface, high optical transmittance and low resistivity that are preferable for optical devices.     

Switching characteristics of copper-doped GexTe1−x solid electrolyte films incorporated by nitrogen for programmable metallization cell memory applications

The switching characteristics of PMC devices (device diameter =0.5 μm) with copper-doped Ge_xTe_1−xN electrolyte films were investigated as a function of the Te composition of the electrolyte films. Nitrogen doped in order to increase the crystallization temperature of GeTe chalcogenide films was incorporated into the Ge lattice alone, and copper in Ge_xTe_1−xN films was incorporated into the Te lattice. The copper concentration in copper-doped Ge_xTe_1−xN layers is directly related to the Te concentration in GeTeN films. PMC devices with copper-doped Ge₇₅Te₂₅N electrolytes were swept at a threshold voltage of 1.0 V and showed stable switching characteristics with a switching time of 1 μs with a set voltage of 2.5 V and a reset voltage of −4.0 V.     

Preparation and optical characteristics of ZnO films by chelating sol-gel method

The effect of different annealing temperatures on the structure, morphology, and optical properties of ZnO thinf ilms prepared by the chelating sol-gel method was investigated. Zinc-oxide thin films were coated on quartz glass substrates by dip coating. Zinc nitrate, absolute ethanol, and citric acid were used as precursor, solvem, and chelating agent, respectively. The results show that ZnO films derived flom zinc-citrate have lower crystallization temperature (below 400℃),and that the crystal structure is wurtzite. The films, treated over 500℃, consist of nano-pardcles and show to be porous at 600℃. The particle size of the film increases with the increase of the annealing temperature. The largest particle size is 60 nm at 600℃. The optical transmittances related to the annealing temperatures become 90% higher in the visible range. The film shows a stalting absorption at 380 ran, and the optical band-gap of the thin film (fired at 500℃) is 3.25 eV and close to the intrinsic band-gap of ZnO (3.2 eV).     

Structure and magnetic properties of sputtered Nd-Fe-B alloys

Studies were conducted on the relationship between the composition of Nd-Fe-B alloys, the temperature of the substrate, additional heat treatment and magnetic properties, crystalline phases, and microstructure and texture of films 30 to 300 μm thick produced by ion-plasma sputtering of cast targets. The sputtering rate was maintained at ~30 μm/h. The axial crystalline texture (001) along the normal to the sputtering plane is formed at a sputtering temperature within the limits ranging from 300 to 450 °C and higher than 600 °C. In the intermediate domain of sputtering temperatures, there is a deterioration of the texture (001), or such a change of the indices of the texture when the normal to one of the planes of the zone [010] becomes its axis. Within the framework of the classical theory of crystallization, a model of growth texture formation during the course of sputtering is suggested. The model explains the nonmonotonic change of texture with the change of sputtering temperature. The data obtained about the structure and properties of films have made it possible to optimize the sputtering process with a view to obtaining sputtered magnets with very good permanent magnet properties. Examples of magnetic systems and devices with sputtered magnets are given.     

Microstructure and nanomechanical properties of Mn-rich Ni–Mn–Ga thin films

We report the effect of post-annealing on the crystalline phase, grain growth, magnetic and mechanical properties of Ni–Mn–Ga thin films deposited at room temperature followed by post-annealing at different temperatures. The phase and microstructural analysis reveal that amorphous to crystalline transformation occurs in as-deposited films after post-annealing above 873 K. The transformation of disordered phase into nanocrystalline phase by the influence of annealing has been confirmed by transmission electron microscopy. The crystalline films exhibit soft magnetic behavior with the Curie temperature of 314 K, while the amorphous films exhibit the Pauli-paramagnetic behavior even down to 4 K. The mechanical properties like hardness and elastic modulus of the films also show a strong dependence on the annealing temperature with crystalline film exhibiting maximum values of 6 GPa and 103 GPa, respectively. The Ni–Mn–Ga film annealed at 873 K exhibits enhanced nanomechanical properties and room temperature ferromagnetism which make this a potential candidate for use in MEMS devices.     

Structural and optical properties of electrodeposited ZnO thin films on conductive RuO2 oxides

ZnO thin films were grown on the 150 nm-thick RuO₂-coated SiO₂/Si substrates by electrochemical deposition in zinc nitrate aqueous solution with various electrolyte concentrations and deposition currents. Crystal orientation and surface structure of the electrodeposited ZnO thin films were characterized by X-ray diffraction (XRD) and scanning electron microscopy, respectively. The XRD results show the as-electrodeposited ZnO thin films on the RuO₂/SiO₂/Si substrates have mixed crystallographic orientations. The higher electrolyte concentration results in the ZnO thin films with a higher degree of c-axis orientation. Moreover, the use of an ultra-thin 5 nm-thick ZnO buffer layer on the RuO₂/SiO₂/Si substrate markedly improves the degree of preferential c-axis orientation of the electrodeposited ZnO crystalline. The subsequent annealing in vacuum at a low temperature of 300 °C reduces the possible hydrate species in the electrodeposited films. The electrodeposited ZnO thin films on the 5 nm-thick ZnO buffered RuO₂/SiO₂/Si substrates grown in 0.02 M electrolyte at −1.5 mA with a subsequent annealing in vacuum at 300 °C had the best structural and optical properties. The UV to visible emission intensity ratio of the film can reach 7.62.     

Coating of Ni powders through micronozzle in a nano particle deposition system

Nano particle deposition system (NPDS) is a novel method to deposit ceramic and metal powders at room temperature. Nickel powders with a size of 3 μm in diameter were sprayed through the fabricated micro nozzle, varying stand-off distance (SoD), which is a gap between the end of the nozzle and the substrate. Injection time for Ni powders was set to 1 min and the flow rate of air-powder was kept to 10 l/min. When SoD was 300 μm, the average deposition thickness was measured to be 2.49 μm, whereas the average deposition thickness was 300 nm for SoD being 500 μm. Therefore, Ni powder deposition at a SoD of 300 μm was successful compared to a SoD of 500 μm with minimal deposition. Moreover, electrical resistance of the deposited film was measured to study its characteristics. Resistivity of the film deposited at a SOD of 300 μm was substantially lower than that of the film deposited at a SoD of 500 μm, confirming the successful deposition at a SoD of 300 μm. Finally, heated treatment of the deposited Ni powders to 150 °C improved the electrical conductivity significantly by lowering its resistivity to 4.4 × 10⁻⁷ Ωm.     

Filtered vacuum arc deposition of undoped and doped ZnO thin films: Electrical, optical, and structural properties

Filtered vacuum (cathodic) arc deposition (FVAD, FCVD) of metallic and ceramic thin films at low substrate temperature (50-400 °C) is realized by magnetically directing vacuum arc produced, highly ionized, and energetic plasma beam onto substrates, obtaining high quality coatings at high deposition rates. The plasma beam is magnetically filtered to remove macroparticles that are also produced by the arc. The deposited films are usually characterized by their good optical quality and high adhesion to the substrate. Transparent and electrically conducting (TCO) thin films of ZnO, SnO₂, In₂O₃:Sn (ITO), ZnO:Al (AZO), ZnO:Ga, ZnO:Sb, ZnO:Mg and several types of zinc-stannate oxides (ZnSnO₃, Zn₂SnO₄), which could be used in solar cells, optoelectronic devices, and as gas sensors, have been successfully deposited by FVAD using pure or alloyed zinc cathodes. The oxides are obtained by operating the system with oxygen background at low pressure. Post-deposition treatment has also been applied to improve the properties of TCO films.The deposition rate of FVAD ZnO and ZnO:M thin films, where M is a doping or alloying metal, is in the range of 0.2-15 nm/s. The films are generally nonstoichiometric, polycrystalline n-type semiconductors. In most cases, ZnO films have a wurtzite structure. FVAD of p-type ZnO has also been achieved by Sb doping. The electrical conductivity of as-deposited n-type thin ZnO film is in the range 0.2-6 × 10^− 5 Ω m, carrier electron density is 10²³-2 × 10²⁶ m^− 3, and electron mobility is in the range 10-40 cm²/V s, depending on the deposition parameters: arc current, oxygen pressure, substrate bias, and substrate temperature. As the energy band gap of FVAD ZnO films is ∼ 3.3 eV and its extinction coefficient (k) in the visible and near-IR range is smaller than 0.02, the optical transmission of 500 nm thick ZnO film is ∼ 0.90.     

Effects of Annealing Temperature on the Structural,Optical,and Electrical Properties of ZnO Thin Films Grown on n-Si<100>Substrates by the Sol–Gel Spin Coating Method

The effects of annealing temperature on the sol–gel-derived ZnO thin films deposited on n-Sh100 i substrates by sol–gel spin coating method have been studied in this paper.The structural,optical,and electrical properties of ZnO thin films annealed at 450,550,and 650 °C in the Ar gas atmosphere have been investigated in a systematic way.The XRD analysis shows a polycrystalline nature of the films at all three annealing temperatures.Further,the crystallite size is observed to be increased with the annealing temperature,whereas the positions of various peaks in the XRD spectra are found to be red-shifted with the temperature.The surface morphology studied through the scanning electron microscopy measurements shows a uniform distribution of ZnO nanoparticles over the entire Si substrates of enhanced grain sizes with the annealing temperature.Optical properties investigated by photoluminescence spectroscopy shows an optical band gap varying in the range of 3.28–3.15 eV as annealing temperature is increased from 450 to 650 °C,respectively.The fourpoint probe measurement shows a decrease in resistivity from 2:1 10 2to 8:1 10 4X cm with the increased temperature from 450 to 650 °C.The study could be useful for studying the sol–gel-derived ZnO thin film-based devices for various electronic,optoelectronic,and gas sensing applications.     

Synthesis,Fabrication and Characterization of ZnO-Based Thin Films Prepared by Sol–Gel Process and H<Subscript>2</Subscript> Gas Sensing Performance

In this paper, an attempt is made to deposit ZnO thin films using sol–gel process followed by dip-coating method on p-silicon (100) substrates for intended application as a hydrogen gas sensor owing to the low toxic nature and thermal stability of ZnO. The thin films are annealed under annealing temperatures of 350, 450 and 550 °C for 25 min. The crystalline quality of the fabricated thin films is then analyzed by field-emission scanning electron microscopy and transmission electron microscope. The gas sensing performance analysis of ZnO thin films is demonstrated at different annealing temperatures and hydrogen gas concentrations ranging from 100 to 3000 ppm. Results obtained show that the sensitivity is significantly improved as annealing temperature increases with maximum sensitivity being achieved at 550 °C annealing temperature and operating temperature of 150 °C. Hence, the modified ZnO thin films can be applicable as H₂ gas sensing device showing to the improved performance in comparison with unmodified thin-film sensor.     

Structure and properties of the crystalline-silicon-dioxide-based macroporous ceramics

Samples of macroporous ceramics based on crystalline silicon dioxide-(the pore diameter > 50 μm) with superficial membrane layers (the pore diameter 10–20 μm) are obtained. They meet the demands to porous materials for filtering. The samples based on the polydisperse powder of crystalline silicon dioxide with granulometric composition 100–315 μm, containing 11 wt % of silica-alumina binder, were formed under a pressure of 30 MPa; they demonstrated an optimal combination of porosity and mechanical strength. After thermal treatment the samples’ porosity came to ≈30%; the ultimate stress (compression) limit, to ≈35 MPa. It is shown that multilayer elements for filtering, with membrane layers formed of the silicon dioxide powder suspension, provide the water purification from iron impurity (from 1–2 mg/l and down to 0.3 mg/l, a sanitary standard). The elements for filtering with doubly deposited crystalline silica-based membrane layer (the particle size 10–50 μm) showed optimal combination of operation characteristics and the purity of water from iron. Original Russian Text ? A.I. Ratíko, A.I. Ivanets, T.A. Azarova, S.M. Azarov, 2008, published in Zashchita Metallov, 2008, Vol. 44, No. 2, pp. 217–222.     

Effect of annealing temperature on the structure and optical properties of sputtered TiO2 films

TiO₂ thin films were deposited by DC reactive magnetron sputtering. Some TiO₂ thin films samples were annealed for 5 min at different temperatures from 300 to 900 °C. The structure and optical properties of the films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and ultraviolet-visible (UV-vis) spectrophotometry, respectively. The influence of the annealing temperature on the structure and optical properties of the films was investigated. The results show that the as-deposited TiO₂ thin films are mixtures of anatase and rutile phases, and possess the column-like crystallite texture. With the annealing temperature increasing, the refractive index and extinction coefficient increase. When the annealing temperature is lower than 900 °C, the anatase phase is the dominant crystalline phase; the weight fraction of the rutile phase does not increase significantly during annealing process. As the annealing temperature rises to 900 °C, the rutile phase with the large extinction coefficient becomes the dominant crystalline phase, and the columnar structure disappears. The films annealed at 300 °C have the best optical properties for the antireflection coatings, whose refractive index and extinction coefficient are 2.42 and 8 × 10⁻⁴ (at 550 nm), respectively.     

The effect of multilayer structure on magnetic properties of FePt thin films

The Fe/Pt multilayer films with different structures were deposited by RF magnetron sputtering on glass substrates, and the L1₀-FePt films were obtained after theas-deposited samples were subjected to vacuum annealing at various temperatures. Results show that the Fe/Pt multilayer structure can effectively reduce the ordering temperature of FePt film, and the in-plane coercivity of [Fe (5.2 nm)/Pt (5.2 nm)]₇ multilayers can reach 161.2 kA/m after annealed at 350 ℃ for 30 min. When Fe and Pt layer thickness is equal, the coercivity of the film is the largest. On the other hand, the different Fe-Pt crystalline phases such as Fe₃Pt and FePt₃ phases are formed after annealing when the thickness ratio of Fe/Pt deviates from 1 after annealing. When Fe and Pt have the same thickness, the thinner single layer gets the lower ordering temperature and the larger coercivity.