Sb doping behavior and its effect on crystal structure, conductivity and photoluminescence of ZnO film in depositing and annealing processes

The Sb-doped ZnO (ZnO:Sb) and undoped ZnO films with wurtzite structure and (0 0 2) preferred orientation were deposited on Si(1 0 0) substrate at 550 °C. It is deduced from XRD and XPS measurements that the Sb in the as-grown ZnO:Sb has high oxidation state and dopes in the form of oxygen-rich Sb-O clusters, which results in a large inner stress and a great increase of the c-axis lattice constant. After annealing at 750 °C under vacuum, the c-axis lattice constant of the ZnO:Sb decreases sharply to near the value of ZnO bulk, the electrical properties change from n-type to p-type and the PL intensity ratio of the visible to ultraviolet emission band goes down greatly, as the Sb content increases from 0 to 2.1 at.%. EDS and XRD measurements indicate that some of Sb dopants escape from the ZnO:Sb films and the oxygen-rich Sb-O clusters vanished after the annealing process. The effect of the change in Sb doping behavior on crystal structure, conductivity and PL is discussed in detail.     

Room temperature ferromagnetism of Si-doped ZnO thin films prepared by sol–gel method

Pure ZnO and Si-doped ZnO thin films were deposited on quartz substrate by using sol-gel spin coating process. X-ray diffraction analysis shows that all the thin films have hexagonal wurtzite structure and preferred c-axis orientation. Si-doped ZnO films show room temperature ferromagnetism (RTFM) and reach the maximum saturation magnetization value of 1.54 kAm-1 at 3% Siconcentration. RTFM of Si-doped ZnO decreases with the increasing annealing temperature because of the formation of SiO 2 . Photoluminescence measurements suggest that the RTFM in Si-doped ZnO can be attributed to the defect complex related to zinc vacancies V Zn and oxygen interstitials Oi .     

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.     

The effects of vacuum annealing on the structure of VO2 thin films

Noncrystalline VO_x thin films were deposited onto p-doped Si (100) substrates at 400 °C using magnetron sputtering. By vacuum annealing, we obtained polycrystalline VO₂ thin films with two different structures under a variety of annealing conditions. With the annealing temperature increasing and the annealing time developing, structures of the films underwent the following transformation: amorphous structure→metastable VO₂ (B)→VO₂ (B) + VO₂ (M). Vacuum annealing is useful of acquiring VO₂ thin films with high surface quality, but too high annealing temperature (500 °C) and too long time (15 h) are harmful, which make the surface degenerate.     

Doping and annealing effects on ZnO:Cd thin films by sol-gel method

In this article, ZnO:Cd films were successfully deposited on glass substrates by a sol-gel technique. The influence of doping concentration and annealing temperature effects was carefully investigated. All films exhibited c-axis preferential orientation and optical transparency with visible transmittance >80%. The minimum room temperature resistivity of 0.0341 Ω cm was obtained with 10 at.% Cd doping under 600 °C annealing temperature. The optical band gap of ZnO:Cd film was reduced as Cd doping concentration increased, while the band gap increased with the increase of annealing temperature.     

Electric and dielectric behavior of CaCu3Ti4O12-based thin films obtained by soft chemical method

CaCu₃Ti₄O₁₂ (stoichiometric) and Ca_1.1Cu_2.9Ti₄O₁₂ (non-stoichiometric) thin films have been prepared by the soft chemical method on Pt/Ti/SiO₂/Si substrates, and their electrical and dielectric properties have been compared as a function of the annealing temperature. The crystalline structure and the surface morphology of the films were markedly affected by the annealing temperature and excess calcium. The films show frequency-independent dielectric properties at room temperature which is similar to those properties obtained in single-crystal or epitaxial thin films. The room temperature dielectric constant of the 570-nm-thick CCTO thin films annealed at 600 °C at 10 kHz was found to be 124. The best non-ohmic behavior (α = 12.6) presented by the film with excess calcium annealed at 500 °C. Resistive hysteresis on the I-V curves was observed which indicates these films can be used in resistance random access memory (ReRAM).     

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.     

Structural, optical and electrical properties of N-doped ZnO thin films prepared by thermal oxidation of pulsed filtered cathodic vacuum arc deposited ZnxNy films

In this study, N-doped ZnO thin films were fabricated by oxidation of Zn_xN_y films. The Zn_xN_y thin films were deposited on glass substrates by pulsed filtered cathodic vacuum arc deposition (PFCVAD) using metallic zinc wire (99.999%) as a cathode target in pure nitrogen plasma. The influence of oxidation temperature, on the electrical, structural and optical properties of N-doped ZnO films was investigated. P-type conduction was achieved for the N-doped ZnO obtained at 450 °C by oxidation of Zn_xN_y, with a resistivity of 16.1 Ω cm, hole concentration of 2.03 × 10¹⁶ cm⁻³ and Hall mobility of 19 cm²/V s. X-ray photoelectron spectroscopy (XPS) analysis confirmed the incorporation of N into the ZnO films. X-ray diffraction (XRD) pattern showed that the films as-deposited and oxidized at 350 °C were amorphous. However, the oxidized films in air atmosphere at 450-550 °C were polycrystalline without preferential orientation. In room temperature photoluminescence (PL) spectra, an ultraviolet (UV) peak was seen for all the samples. In addition, a broad deep level emission was observed.     

Conductive and transparent Bi-doped ZnO thin films prepared by rf magnetron sputtering

Bi-doped ZnO thin films were grown on glass substrates by ratio frequency (rf) magnetron sputtering technique and followed by annealing at 400 °C for 4 h in vacuum (~ 10^− 1 Pa). The effect of argon pressure on the structural, optical, and electrical properties of the Bi-doped films were investigated. The XRD patterns show that the thin films were highly textured along the c-axis and perpendicular to the surface of the substrate. Some excellent properties, such as high transmittance (about 85%) in visible region, low resistivity value of 1.89 × 10^− 3 W cm and high carrier density of 3.45 × 10²⁰ cm^− 3 were obtained for the film deposited at the argon pressure of 2.0 Pa. The optical band gap of the films was found to increase from 3.08 to 3.29 eV as deposition pressure increased from 1 to 3 Pa. The effects of post-annealing treatments had been considered. In spite of its low conductivity comparing with other TCOs, Bi-doping didn't appreciably affect the optical transparency in the visible range of ZnO thin films.     

Investigation of amorphous Ni-Al-N film as diffusion barrier between Cu and SiO2

Barrier performance of 10 nm-thick Ni-Al-N layer, prepared by magnetron sputtering, in the Cu/Ni-Al-N/SiO₂/Si heterostructure, is investigated. It is found that the Ni-Al-N film keeps amorphous and no obvious reactions/interdiffusions are observed after high temperature annealing at temperatures up to 650 °C, indicating that the amorphous Ni-Al-N layer has good barrier performance. Unlike the conventional failure mechanism of a barrier layer resulting from that Cu diffuses into SiO₂/Si and reacts with Si to form copper silicides, agglomeration of Cu film in the Cu/Ni-Al-N/SiO₂/Si heterostructure happens when the annealing temperature is higher than 700 °C, which is attributed to the dewetting of Cu film with Ni-Al-N during high temperature annealing. Moreover, the activation energy is estimated to be 1.1 eV based on the Kissinger equation.     

Effects of lanthanum doping on the preferred orientation, phase structure and electrical properties of sol-gel derived Pb1-3x/2Lax (Zr0.6Ti0.4)O3 thin films

Pb_1-3x/2La_x (Zr_0.6Ti_0.4)O₃ thin films (0 ≤ x ≤ 0.08) were prepared on the Pt (1 1 1)/Ti/SiO₂/Si (1 0 0) substrates by a sol-gel method. The morphology, preferred orientation, phase structure, dielectric and ferroelectric properties of the films have been investigated. Our results show that lanthanum doping is favorable to enhance crystalline and obtain (1 0 0)-preferred orientation of the films. Meanwhile, it is suggested that the films undergo a structure change from “rhombohedral” phase to monoclinic phase as the lanthanum-doped content is increased to x ≈ 0.05. Results of dielectric properties and ferroelectric properties indicate that lanthanum doping contributes to improve film dielectric constant and dielectric loss while it brings about a striking decrease in remnant polarization value. Possible explanations for the variations of electrical properties have been discussed in terms of preferred orientation, phase structure and large lattice distortion.     

Chemically synthesized hydrous RuO2 thin films for supercapacitor application

The hydrous RuO₂ thin films have been successfully synthesized at low temperature on glass and stainless steel substrates using lucrative chemical bath deposition (CBD) method. Their structural, morphological, optical, electrical and wettability properties were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), UV-vis-NIR spectrophotometer, two point probe method and water contact angle measurement techniques. The results showed that, the CBD method allows to formation of amorphous, porous, superhydrophilic, semiconducting, hydrous RuO₂ thin films with optical band gap of 2.7 eV. The supercapacitive behavior of hydrous RuO₂ in 0.5 M H₂SO₄ electrolyte examined by cyclic voltammetric (CV) measurements showed maximum specific capacitance of 73 F g⁻¹.     

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.     

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.     

Lanthanum silicate thin films for SOFC electrolytes synthesized by magnetron sputtering and subsequent annealing

Thin films of La and Si with Si/(La + Si) atomic ratios ranging from 0.36 to 0.44 were produced by magnetron sputtering in pure Ar. For all compositions, the apatite-like La_9.33Si₆O₂₆ phase was formed during annealing in air at 900 °C. A preferential orientation was developed during annealing of the films with higher silicon content while formation of oxide impurities was detected for the films with less silicon. Silicon segregation to the thin film/substrate interface was observed after annealing for thin films with higher Si/(La + Si) atomic ratios. The higher ionic conductivity values were obtained with the films with lower silicon content (2.81 × 10^− 3 Scm^− 1 at 800 °C for the film with Si/(La + Si) atomic ratio of 0.36). This film presented the lower activation energy E_a (0.94 eV).     

Structural, morphological and optical properties of Bi2−xSbxSe3 thin films grown by electrodeposition

Ternary single-phase Bi_2−xSb_xSe₃ alloy thin films were synthesized onto Au(1 1 1) substrates from an aqueous solution containing Bi(NO₃)₃, SbCl₃, and SeO₂ at room temperature for the first time via the electrodeposition technique. The electrodeposition of the thin films was studied using cyclic voltammetry, compositional, structural, optical measurements and surface morphology. It was found that the thin films with different stoichiometry can be obtained by controlling the electrolyte composition. The as-deposited films were crystallized in the preferential orientation along the (0 1 5) plane. The SEM investigations show that the film growth proceeds via nucleation, growth of film layer and formation of spherical particles on the film layer. The particle size and shape of Bi_2−xSb_xSe₃ films could be changed by tuning the electrolyte composition. The optical absorption spectra suggest that the band gap of this alloy varied from 0.24 to 0.38 eV with increasing Sb content from x = 0 to x = 0.2.     

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.     

Nano-grain Al2O3 crystals grown by sputtering of aluminium on CoCrPt thin films for potential application in ultra-high-density recording media

Designing supraceramic assemblies based on Al₂O₃ has remained a challenge due to the problems associated with the suitable dispersion in neat compounds and ability to control the preferred orientation in a unique fashion. Herein, granular HCP-(CoCrPt)_100−X(Al₂O₃)_X (X represents the percent weight) thin films with Si(1 0 0) substrates have been fabricated using sputtering technique followed by annealing treatment. Structural and magnetic properties of thin film have been investigated for potential application in magnetic recording media. It was shown that coercivity increased from 0.5 to 2.5 kOe by increasing the nano-grain Al₂O₃ content in the CoCrPt magnetic layers. In CoCrPt-Al₂O₃ thin films coercivity of 2.5 kOe has been obtained with increasing the Al₂O₃ content from 3 to 13 wt.% in the annealed thin films. The structural properties of the samples were studied using X-ray diffraction (XRD) and transmission electron microscope (TEM) equipped with selected area electron diffraction (SAED). The magnetic properties of the samples were measured with a vibrating sample magnetometer (VSM). The VSM results showed that the HCP-CoCrPt-Al₂O₃ granular films are a promising candidate for ultra-high-density recording media because of its low Al₂O₃ content and simple manufacturing process.     

Effect of working pressure and temperature on ZnO film deposited on free-standing diamond substrates

The structure characteristic and electric performance of ZnO film deposited on nucleation side of free-standing diamond substrates under different heating temperatures (T_h) of substrate and working pressures (p) were studied. The structure of the ZnO films tested by X-ray diffraction shows that ZnO film of high c-axis orientation is deposited on the nucleation side of free-standing diamond substrate which is extremely smooth when T_h=250 °C and p=0.4 Pa. After annealing at 480 °C in N₂ atmosphere, the SEM and the AFM analyses demonstrate that the c-axis orientation of ZnO film is obviously enhanced. The resistivity of ZnO films also increases up to 8×10⁵ Ωcm which is observed by I–V test.     

Fabrication of GdBa2Cu3O7−x films by TFA-MOD process

GdBa₂Cu₃O_7−x (GdBCO) films have been deposited on LaAlO₃ (LAO) (0 0 l) single crystal substrates by trifluoroacetate metal organic deposition (TFA-MOD) method. The effects of oxygen partial pressure and firing temperature on microstructure and critical properties of GdBCO films were discussed. The phase formation, texture and microstructure of films were characterized by X-ray diffraction and scanning electron microscopy. The oxygen partial pressure was considered to play a great role for formation of impurity phase and a-axis oriented grains. The degree of c-axis orientation was also influenced by the firing temperature. The highly c-axis oriented GdBCO film obtained at 815 °C under an oxygen partial pressure of 100 ppm has a high performance critical current density J_c (77 K, self field) = 1.8 MA/cm².