Studies on structural and electrical properties of copper-doped zinc oxide powders prepared by a solid state method at high temperatures

Abstract

The synthesis, crystal structure and electrical conductivity properties of Cu-doped ZnO powders (in the range of 0.25 – 15 mole %) is reported. I-phase samples, which were indexed as single phase with a hexagonal (wurtzite) structure in the Cu-doped ZnO binary system, were determined by X-ray diffraction. The limit solubility of Cu in the ZnO lattice at this temperature is 5 mole % at 1000°C. The impurity phase was determined as CuO when compared with standard XRD data using the PDF program. We focused on single I-phase ZnO samples which synthesised at 1000°C because the limit solubility range is widest at this temperature. It was observed that the lattice parameters a increased and c decreased with Cu doping concentration. The morphology of the I-phase samples was analysed with a scanning electron microscope. The electrical conductivity of the pure ZnO and single I-phase samples were studied using the four-probe dc method at temperatures between 100 and 950°C in an air atmosphere. The electrical conductivity values of pure ZnO and 5 mole % Cu-doped ZnO samples at 100°C were 2 × 10^?6 and 1.4 × 10^?4 ohm^?1 cm^?1, and at 950°C they were 1.8 and 3.4 ohm^?1 cm^?1, respectively. In other words, the electrical conductivity slightly increased with Cu doping concentration. Also, it was observed that the activation energy of the I-phase samples was decreased with Cu doping concentration.     

Influence of annealing temperature on structural,electrical and optical properties of undoped zinc oxide thin films

The undoped zinc oxide thin films were grown on quartz substrate at a substrate temperature of 750 °C by radio frequency magnetron sputtering and post annealed at different temperatures (600–800 °C) for a period of 30 min. The influence of annealing temperature on the structure, electrical and optical properties of undoped ZnO thin films was investigated by X-ray diffraction, Hall-effect, photoluminescence and optical transmission measurements. Results indicated that the electrical properties of the thin films were extremely sensitive to the annealing temperature and the conduction type could be changed dramatically from n-type to p-type, and finally changed to weak p-type when the temperature increased from 600 to 800 °C. Electrical and photoluminescence results indicate that native defects, such as oxygen and zinc vacancies, could play an important role in determining the conductivity of these nominally undoped ZnO thin films. The conversion of the conduction type was attributed to the competition between Zn vacancy acceptor and oxygen vacancy and interstitial Zn donors. At an intermediate annealing temperature of 750 °C, the film behaves the best p-type characteristic, which has the lowest resistivity of 12 Ωcm, hall mobility of 2.0 cm²/V s and carrier concentration of 1.5 × 10¹⁷ cm^?3. The photoluminescence results indicated that the Zn vacancy might be responsible for the intrinsic better p-type characteristic in ZnO thin films.     

Structural, electrical and optical properties of Si doped ZnO films grown by atomic layer deposition

Si doped ZnO (SZO) films with various Si concentrations were deposited by atomic layer deposition at 300 °C using triethyzinc, tris(dimethylamino)silane and H₂O₂ as the precursors. The influences of Si doping concentration on structural, electrical and optical properties of ZnO films have been investigated. All the films exhibited a highly preferential c-axis orientation. A minimum resistivity of 9.2 × 10^?4 Ω cm, with a carrier concentration of 4.3 × 10²⁰ cm^?3 and a Hall mobility of 15.8 cm²/Vs, was obtained for SZO film prepared with the Si concentration of 2.1 at%. The increase of conductivity with Si doping was attributed to the presence of Si in +3 valence state acting as donor in ZnO and the increases of oxygen vacancies with Si concentration as proven by XPS measurements. The optical bandgap of SZO films initially increased from 3.25 to 3.55 eV with increasing of Si concentration to 2.1 at%, then decreased with further increase of Si concentration. The blue shift of band gap of SZO films with increasing carrier concentration can be explained by the Burstein-Moss (B-M) effects.     

Effect of sintering temperature on electrical properties, dielectric characteristics, and aging behavior of ZnO–V2O5-based varistor ceramics modified with Bi2O3

The effect of sintering temperature on microstructure, electrical properties, dielectric characteristics, and aging behavior of ZnO–V₂O₅–MnO₂–Nb₂O₅–Bi₂O₃ varistor ceramics was systematically investigated at 875–950 °C. The sintered density decreased from 5.50 to 5.34 g/cm³ and the average grain size increased from 5.4 to 15.0 μm with an increase in the sintering temperature. The breakdown field (E_B) decreased from 5,785 to 1,181 V/cm with an increase in the sintering temperature. The varistor ceramics sintered at 900 °C exhibited a surprisingly high nonlinear coefficient (α = 61). The donor concentration (N_d) increased from 2.08 × 10¹⁷ to 4.64 × 10¹⁷ cm^?3 with an increase in the sintering temperature and the barrier height (Φ_b) exhibited 1.08 eV as the maximum value at 900 °C. Concerning stability, the varistors sintered at 950 °C exhibited the strongest accelerated aging characteristics, where %ΔE_B = ?1.4 % and %Δα = ?14.6 % for DC accelerated aging stress of 0.85 E_B/85 °C/24 h.     

Preparation and electrochemical properties of SrCe 0·4 Zr 0·4 Yb 0·2 O 2·9 electrolyte

The perovskite Yb-doped strontium cerate–zirconate material, SrCe_0·4Zr_0·4Yb_0·2O_2·9, was prepared by solid-state reaction and the structure was characterized by X-ray diffraction. The calcination process of the powder was investigated by thermogravimetric/differential thermal analysis (TG–DTA). The high temperature conductivities were measured by d.c. four-probe technique in the temperature range from 500 to 950°C in wet hydrogen and effect of temperature on conductivity was investigated. The conductivity increased with the elevation of temperature from 500 to 950°C. The highest conductivity of 4·4 × 10^???2 S· cm^???1 was observed for SrCe_0·4Zr_0·4Yb_0·2O_2·9 at 950°C. The current–voltage (I–V) and current–power (I–P) characteristics of the single cell (H₂, Pt/SrCe_0·4Zr_0·4Yb_0·2O_2·9/Pt, O₂) at temperature range from 600 to 850°C were tested. With the temperature increasing from 600 to 850°C, the open circuit voltage (OCV) decreased from 1·164 to 1·073 V and the ionic transfer number decreased from 0·996 to 0·946. At 850°C, the maximum power density of 25·2 mW· cm^???2 was observed.     

Effect of NiO doping on microstructural and electrical properties of ZnO-based linear resistance ceramics

The ZnO-based linear resistance ceramics were fabricated from ZnO–Al₂O₃–MgO–NiO at 1,340 °C. The effect of the different doping amounts of NiO on the microstructure and electrical properties were investigated in detail. Appropriate amount of NiO addition can reduces the nonlinear property and improves the resistance temperature coefficient of the ZnO-based linear resistance ceramics obviously. The samples with the NiO concentration of 15 mol% possess an energy density of 496 J/cm³ and a resistance temperature coefficient 1.15 × 10^?4/°C, which are improved by 10 and 79 %, respectively. Moreover, the nonlinear coefficient of voltage decrease to 1.14, decreased by 11 % and the resistivity reaches to 43.53 Ω cm, increased by 76 %.     

Microstructure and electrical properties of K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>NbO<Subscript>3</Subscript> lead-free piezoelectric ceramics sintered in low pO<Subscript>2</Subscript> atmosphere

Pure K_0.5Na_0.5NbO₃ lead-free piezoelectric ceramics without any dopants/additives were sintered at various temperatures (950–1125 °C) in low pO₂ atmosphere (pO₂?~?10^?6 atm). All ceramics exhibit high relative densities (>?94%) and low weight loss (<?0.6%). Compared to the ceramics sintered in air, the ceramics sintered in low pO₂ exhibit improved electrical properties. The piezoelectric constant d₃₃ and converse piezoelectric constant d₃₃* are 112 pC/N and 119 pm/V, respectively. The ceramics show typical ferroelectric behavior with the remnant polarization of 21.6 µC/cm² and coercive field of 15.5 kV/cm under measurement electric field of 70 kV/cm. The good electrical properties of the present samples are related to the suppression of volatility of the alkali cations during the sintering process in low pO₂ atmosphere.     

SbVO4 doped ZnO–V2O5-based varistor ceramics: microstructure, electrical properties and conductive mechanism

The effects of SbVO₄ addition on the microstructure, electrical properties and characteristics of grain and grain boundary of ZnO–V₂O₅ based varistor ceramics were studied using SEM, E–J measurements and impedance spectroscopy. XRD analysis revealed that all the samples consist of main phase of ZnO and the second phase of BiVO₄ and Zn₇Sb₂O₁₂. The microstructural homogeneity of the ceramic was improved through adding SbVO₄. With an increase of SbVO₄, the average grain sizes decrease from 16.1 to 6.1 μm. The resistivity of grain boundary is approximately constant (~10³ Ω). The ZnO–V₂O₅-based varistor ceramics added with 0.3 mol % SbVO₄ sintered at 940 °C for 4 h exhibited good nonlinear properties of α = 51, J = 13.4 μA/mm² and E _1mA = 416 V/mm.     

Low-temperature preparation of transparent conductive Al-doped ZnO thin films by a novel sol–gel method

We developed a novel sol–gel method to prepare transparent conductive Al-doped ZnO (AZO) thin film at low temperature. The AZO nanocrystals were prepared by a solvothermal method and then they were dispersed in the monoethanolamine and methanol to form AZO colloids. A (002)-oriented ZnO thin film was used as a nucleation layer to induce the (002)-oriented growth of AZO thin films. The AZO thin films were prepared on Si(100) and fused quartz glass substrates with the (002)-oriented ZnO nucleation layer and annealed at 400 °C for 60 min. All AZO thin films showed (002) orientation. For electrical and optical measurements, the films deposited on glass substrates were post-annealed at 400 °C for 30 min in forming gas (100 % H₂) to improve their conductivity. These samples had high transparency in the visible wavelength range, and also showed good conductivity. A 0.2 mol L^?1 AZO solution with 3 at.% Al content was heated in a Teflon autoclave at 160 °C for 30 min to form AZO nanocrystals, and then the AZO nanocrystals were suspended in the MEA and methanol to obtain the stable AZO colloid. The Al content in the AZO nanocrystals was 2.7 at.%, and the high Al doping coefficient was mainly attributed to the formation of AZO nanocrystals in the autoclave. The AZO thin film using this colloid had the lowest resistivity of 3.89 × 10^?3 Ω cm due to its high carrier concentration of 3.29 × 10²⁰ cm^?3.     

Effect of rapid thermal annealing on Zn/ZnO layers

Zn/ZnO layers were deposited on SiO₂/Si substrate by magnetron sputtering at room temperature, and then these layers were annealed at various temperatures from 200 to 400 °C in nitrogen atmosphere for 1 min. The structural and electrical properties of the Zn/ZnO layers before and after annealing are systematically investigated by X-ray diffraction, scanning electron microscopy, current–voltage measurement system, and Auger electron spectroscopy. Current–voltage measurements show that the Zn/ZnO layers exhibit an Ohmic contact behavior. It is shown that, initially, the specific contact resistivity decreases with the increase of the annealing temperature and reaches a minimum value of 9.76 × 10^?5 Ω cm² at an annealing temperature of 300 °C. However, with a further increase of the annealing temperature, the Ohmic contact behavior degrades. This phenomenon can be explained by considering the diffusion of zinc interstitials and oxygen vacancies. It is also shown that Zn-rich ZnO thin films can be obtained by annealing Zn on the surface of ZnO film and that good Ohmic contact between Zn and ZnO layers can be observed when the annealing temperature was 300 °C.     

Nanostructures bilayer ZnO/MgO dielectrics for metal–insulator–metal capacitor applications

Bilayer ZnO/MgO dielectrics for metal–insulator–metal (MIM) capacitor application were successfully deposited using simple chemical technique which is sol–gel spin coating method with different annealing temperatures. Important criteria in determining good dielectric layer have been investigated which include structural, electrical and dielectric properties. Cubic-like grain was observed for films annealed at 400 and 425 °C which enhance the carrier density and polarization that resulted in high k value produced. Bilayer film annealed at 475 °C improved in small surface roughness (17.629 nm), minimum leakage current density (~10^?8 A cm^?2) and high resistivity (3.14 × 10⁵ Ω cm). Dielectric constant, k was varied with frequency and k value was found to be 5.09 at 10 kHz. The results obtained in this study indicated that film annealed at temperature of 475 °C is suitable to be used as dielectrics for MIM capacitor application.     

Synthesis and characterization of nanocrystalline TiO<Subscript>2</Subscript> thin films

Nanocrystalline thin films of TiO₂ have been synthesized by sol gel spin coating technique Thin films of TiO₂ annealed at 700 °C were characterized by X-ray diffraction(XRD), Atomic Force Microscopy, High resolution TEM and Scanning Electron Microscopy (SEM), The XRD shows formation of tetragonal anatase and rutile phases with lattice parameters a = 3.7837 Å and c = 9.5087 Å. The surface morphology of the TiO₂ films showed that the nanoparticles are fine with an average grain size of about 60 nm. Optical studies revealed a high absorption coefficient (10⁴ cm^?1) with a direct band gap of 3.24 eV. The films are of the n type conduction with room temperature electrical conductivity of 10^?6 (Ω cm)^?1.     

Effect of La–Zn Substitution on the Structure and Magnetic Properties of Low Temperature Co-Fired M-Type Barium Ferrite

Ba(LaZn) _x Fe_12?2x O₁₉ (0≤x≤0.5) powders with Bi₂O₃ as an additive was synthesized by a sintered route at 900 °C or 950 °C. The structure and magnetic properties of La–Zn substituted M-type barium ferrites were also investigated. When 0≤x≤0.5, only one crystal phase existed in the sample, and the morphology of the grains were shown to be gradually irregular. The little amount of La³⁺ ions and Zn²⁺ ions changed the equilibrium of Fe²⁺ and Fe³⁺ at the 2a site, which increased the Fe³⁺–O–Fe²⁺ superexchange interaction strength, and the saturation magnetization (Ms) of the samples was also improved. Meanwhile, the substitution of La³⁺ and Zn²⁺ ions and the grains’ size bought great effects on the magnetocrystalline anisotropy field. As a result, with sintering at 950 °C for 6 h, the max Ms value of the samples with x=0.1 was 67.26 emu/g, and the minimum coercivity (H _c ) value was 1718.89 Oe with x=0.3, respectively.     

A novel route for synthesis, characterization of molybdenum diselenide thin films and their photovoltaic applications

Molybdenum diselenide thin films were deposited by chemical method. The precursor solution contains ammonium molybdate, sodium selenosulphite with hydrazine hydrate as a reducing agent. Various preparative conditions were optimized for the formation of thin films. The X-ray diffraction pattern shows that thin films have a layer-hexagonal phase. EDAX analysis shows that the films are nearly stoichiometric of Mo: Se: 1:2. Optical properties show a direct band gap nature with band gap energy 1.43 eV and having specific electrical conductivity in the order of 10^?5 (Ωcm)^?1. The configuration of fabricated cell is n-MoSe₂ | NaI (2 M) + I₂ (1 M) | C (graphite). The photoelectrochemical characterization of the films is carried out by studying current–voltage characterization, capacitance–voltage and power output characteristics. The fill factor and efficiency of the cell were found to be 34.22 and 1.01 % respectively.     

Effect of calcination temperature on structure and thermoelectric properties of CuAlO<Subscript>2</Subscript> powders

Copper aluminum oxide (CuAlO₂) with delafossite phase was synthesized by the Pechini method using different calcination temperatures to evaluate its influence on the structure and thermoelectric material properties. X-ray diffraction and Raman spectroscopy confirm that delafossite phase was formed at 1100 °C with the presence of 2H-CuAlO₂ and Al₂O₃ impurities, while at lower calcination temperatures (900 and 1000 °C), a mixture of CuO + CuAl₂O₄ (spinel phase) was observed. Energy-dispersive X-ray elemental maps display an even distribution of copper, aluminum and oxygen in the sample calcined at 1100 °C. Direct optical band gap, E _g = 3.6 eV, was calculated from reflectance diffuse spectra by Kubelka–Munk and Tauc methods. An absorption band at 1.7 eV accounts for defect levels, masking the characteristic indirect transition. The thermoelectric properties, such as Seebeck coefficient, and thermal and electrical conductivities of the sample calcined at 1100 °C were measured at different temperatures. Hall voltage and positive values of the Seebeck coefficient (425.8–434.4 µV K^?1) confirm the material’s p-type character. The independence of the Seebeck coefficient on the operation temperature indicates a small polaron electrical conduction mechanism. Thermal conductivity decreases exponentially with the temperature from 43.45 to 23.9 W m^?1 K^?1, where the principal contribution is due to phonons. Figure of merit ZT of sample calcined at 1100 °C between 100 and 800 °C increases from 1.42 × 10^?8 to 4.94 × 10^?4 in the order of the literature reports. From the Arrhenius plot ln(σT) versus 1000/T, an activation energy E _a = 0.32 eV for the electrical conductivity was calculated.     

Bi4Ti3O12 modified low voltage ZnO-based varistors: microstructure, electrical properties and aging characteristics

The effects of Bi₄Ti₃O₁₂ addition on the microstructure, electrical properties and aging characteristics of ZnO-based varistors were investigated. The addition of Bi₄Ti₃O₁₂ can reduce the formation of Zn₂TiO₄ spinel phase and promote the growth of ZnO grain. Bi₄Ti₃O₁₂ doped ZnO-based varistors sintered at 1,130 °C possessed excellent performance of I _L = 2.9 μA, E _1mA = 29.7 V/mm, α = 30.2, and good surge absorption capability with %△E _1mA = ?3.5 % for 500 A 8/20 μs impulse current. In addition, the varistors exhibited the most stable accelerated aging characteristics with %△E _1mA = ?0.3 % for DC accelerated aging stress of 125 °C/7 h. These results revealed that Bi₄Ti₃O₁₂ addition is highly beneficial to attain enhanced varistor properties of ZnO ceramics.     

Influence of oxygen vacancies on the structural,dielectric, and magnetic properties of (Mn,Co) co-doped ZnO nanostructures

We analysed the variation and effect of oxygen vacancies on the structural, dielectric and magnetic properties in case of Mn (4%) and Co (1, 2 and 4%) co-doped ZnO nanoparticles (NPs), synthesized by chemical precipitation route and annealed at 750 °C for 2 h. From the XRD, the calculated average crystallite size increased from15.30?±?0.73 nm to 16.71?±?012 nm, when Co content is increased from 1 to 4%. Enhancement of dopants (Mn, Co) introduced more and more oxygen vacancies to ZnO lattice confirmed from EDX and XPS. The high-temperature annealing leads to reduction of the dielectric properties due to enhancement in grain growth (large grain volume and lesser number of grain boundaries) with the incorporation of Co and Mn ions into the ZnO lattice. The electrical conductivity of the Mn doped and (Mn, Co) co-doped ZnO samples were enhanced due to increase in the volume of conducting grains and charge density (liberation of trapped charge carriers in oxygen vacancies and free charge carriers at higher frequencies). The Mn-doped and (Mn, Co) co-doped ZnO NPs show ferromagnetic (FM) behaviour. The saturation and remnant magnetizations (M_s and M_r) elevates from (0.235 to 1.489)?×?10^?2 and (0.12 to 0.27)?×?10^?2 emu/g while Coercivity (H_c) reduced from 97 to 36 Oe with enhancement in the concentration of dopants in ZnO matrix. Oxygen vacancies were found to be the main reason for room-temperature ferromagnetism (RTFM) in the doped and co-doped ZnO NPs. The results show that the enhanced dielectric and magnetic properties of Mn doped and (Mn, Co) co-doped ZnO is strongly correlated with the concentration of oxygen vacancies. The observed enhanced RTFM, dielectric properties and electrical conductivity makes TM doped ZnO nanoparticles suitable for spintronics, microelectronics and optoelectronics based applications.     

Investigation of physico-chemical properties of conductive Ga-doped ZnO thin films deposited on glass and silicon wafers by RF magnetron sputtering

We report on the physico-chemical properties of Undoped and Ga-doped ZnO films fabricated on glass and p-Silicon wafers at room temperature by RF magnetron sputtering using a ZnO and Ga₂O₃ mixture raw powder target without sintering procedure. X-ray diffraction (XRD) and energy dispersion spectroscopy (EDS), scanning electronic microscopy, Raman scattering, ultraviolet–visible spectroscopy, photoluminescence (PL), Hall effect and impedance spectroscopy technique have been applied for the comparative study of ZnO and ZnO:Ga thin films. XRD and Raman studies have shown that the deposited films have a preferred orientation growth with Ga atoms both in substitutional and interstitial positions. EDS analyses have allowed to show that the metallic Ga atoms have been incorporated in the ZnO films. Doping by gallium resulted in a slight increase in the optical band gap energy of the films while the optical transmittance remains about 80 %. The PL analysis at room temperature revealed violet, blue, green and red emissions. Room temperature Hall measurements show that the lowest resistivity was 3.40 × 10^?4 Ω cm with an electron mobility of 18.56 cm²/V.s for an optimum Ga concentration of 4 wt%. Impedance spectroscopy study showed that σ_ac obeys the relation \(\sigma_{ac} = A\omega^{s}\). The exponent ‘‘s’’ was found to decrease with increasing the temperature. It is found that, the AC conductivity of all samples follow the correlated barrier hopping model. The Nyquist plots showed a single semicircle, indicating an equivalent circuit with a single parallel resistor R and capacitance C network. The values of the activation energy E _a deduced from both DC conductivity and relaxation frequency for all the studied samples ranged from 0.51 to 0.73 eV and the results are explained on the basis of the induced defects due to the addition of Ga into the ZnO films.     

Novel process for synthesis of α-Fe2O3: microstructural and optoelectronic investigations

Novel chemical synthesis method has been successfully employed for the preparation of n type α-Fe₂O₃ nanoparticles. Thin films of annealed Fe₂O₃ powders processed on glass substrates using spin coating technique. The effects of process temperature on the structural, morphological, electrical transport and optical properties were studied. X-ray diffraction study revealed formation of single phase nanocrystalline hexagonal α-Fe₂O₃. Microstructural analysis confirms nanostructured morphology. Dc electrical conductivity measurement reveled the semiconducting nature with room temperature electrical conductivity increased from 10^?4 to 10^?3 (Ω cm)^?1 as process temperature of Fe₂O₃ increased from 400 to 700 °C respectively. The n-type electrical conductivity is confirmed from thermo-emf measurement with no appreciable change in thermoelectric power after increasing processing temperature. The decrease in the band gap energy from 3.88 to 2.62 eV was observed after increasing process temperature.     

Activation of p-type conduction in ZnO:N films by annealing in atomic oxygen

ZnO:N epitaxial films have been grown by reactive magnetron sputtering. The effect of annealing in atomic oxygen on the structural and electrical properties of the ZnO:N films has been studied by X-ray diffraction, atomic force microscopy, Hall effect measurements, and X-ray photoelectron spectroscopy. By annealing at temperatures from 500 to 700°C, we have obtained p-type ZnO:N films with a resistivity of ～57 Ω cm, hole mobility of ～2.7 cm²/(V s), and hole concentration of ～6.8 × 10¹⁷ cm^?3. X-ray photoelectron spectroscopy results suggest that the p-type conductivity of the films is due to a decrease in the concentration of (N₂)_O and V _O donors.