Power and gas pressure effects on properties of amorphous In–Ga–ZnO films by magnetron sputtering

Amorphous In–Ga–ZnO thin films were deposited on quartz glass substrate at room temperature utilizing radio frequency magnetron sputtering technique. Sputtering power and oxygen flow rate effects on the physical properties of the In–Ga–ZnO films were systematically investigated. It is shown the film deposition rate and the conductivity of the In–Ga–ZnO films increased with the sputtering power. The as-grown In–Ga–ZnO films deposited at 500 W exhibited the Hall mobility of 17.7 cm²/Vs. Average optical transmittance of the In–Ga–ZnO films is greater than 80% in the visible wavelength. The extracted optical band gap of the In–Ga–ZnO films increased from 3.06 to 3.46 eV with increasing the sputtering power. The electrical properties of the In–Ga–ZnO films are greatly dependent on the O₂/Ar gas flow ratio and post-growth annealing process. Increasing oxygen flow rate converted the In–Ga–ZnO films from semiconducting to semi-insulating, but the resistivity of the films was significantly reduced after being annealed in vacuum. Both the as-grown and annealed In–Ga–ZnO films show n-type electrical conductivity.     

Synthesis and gas sensitivity of In-doped ZnO nanoparticles

Undoped and In-doped ZnO nanoparticles were produced by renovated hybrid induction and laser heating (HILH) in this study from Zn–In alloy, with different mole ratios, as the raw material in a flowing mixed gas atmosphere of Ar+O₂. The morphological characteristics, phase microstructure, and chemical state of In-doped ZnO nanoparticles were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The change in electrical resistance of thick film based on the In-doped ZnO nanoparticles and their gas sensitivities to volatile organic compounds (VOCs), benzene, acetone, ethyl alcohol, toluene, and xylene, as a function of temperature were measured in the temperature range of 200–500 °C, and compared with the undoped thick film. The results showed that the In-doped ZnO has lower resistance and higher sensitivity than that of the undoped ZnO. This was probably due to the fact that the In³⁺ ions, replacing the Zn²⁺ ions in the ZnO lattice, resulted in an increase of the concentration of free electrons followed by an increase of the adsorbed oxygen. Among the types of In-doped ZnO, 4.58 at % In-doped ZnO had the lowest resistance, and had the highest sensitivity. On increasing the concentration of In into ZnO, its resistance increased, while the sensitivity decreased. The sensitivity of the 4.58 at % In-doped ZnO to VOCs was in the order of acetone>alcohol>xylene>toluene> benzene at an operating temperature of 420 °C.     

Influence of In doping on electro-optical properties of ZnO films

Thin metallic films of Zn and In/Zn were deposited onto glass substrates by thermal evaporation under vacuum. The metallic films were submitted to a thermal oxidation in air, at 623 K, for different oxidation times (30–90 min), in order to be oxidized. Structural and morphological analyses (X-ray diffraction, transmission electron microscopy and scanning electron microscopy) revealed that the obtained undoped and In-doped ZnO thin films possess a polycrystalline structure. Transmission spectra were recorded in spectral domain from 280 to 1400 nm. The influence of In doping and oxidation parameters as well, on the optical parameters (transmittance, optical bandgap, Urbach energy) were analysed. It was clearly evidenced that by In doping, the optical properties of ZnO films were improved. The temperature dependence of electrical conductivity was studied using surface-type cells with Ag electrodes. The obtained results indicate that In-doped ZnO films exhibit an enhancement of electrical conductivity with few orders of magnitude when compared with non-doped ones.     

ZnO nanocrystalline thin films: a correlation of microstructural,optoelectronic properties

The compositional, structural, microstructural, dc electrical conductivity and optical properties of undoped zinc oxide films prepared by the sol–gel process using a spin-coating technique were investigated. The ZnO films were obtained by 5 cycle spin-coated and dried zinc oxide films followed by annealing in air at 600 °C. The films deposited on the platinum coated silicon substrate were crystallized in a hexagonal wurtzite form. The energy-dispersive X-ray (EDX) spectrometry shows Zn and O elements in the products with an approximate molar ratio. TEM image of ZnO thin film shows that a grain of about 60–80 nm in size is really an aggregate of many small crystallites of around 10–20 nm. Electron diffraction pattern shows that the ZnO films exhibited hexagonal structure. The SEM micrograph showed that the films consist in nanocrystalline grains randomly distributed with voids in different regions. The dc conductivity found in the range of 10⁻⁵–10⁻⁶ (Ω cm)⁻¹. The optical study showed that the spectra for all samples give the transparency in the visible range.     

Solvent thermal synthesis and gas-sensing properties of Fe-doped ZnO

In this study, pure ZnO microbullets, ZnO–ZnFe₂O₄ composite, and ZnO–Fe₂O₃–ZnFe₂O₄ composite with micron structured balloons, rods, and particles were prepared by a simple solvent thermal process using methanol or ethanol as solvents. The influence of solvents on the composition and morphology of the products was studied, and their gas-sensing properties were also investigated. The morphology of ZnO microbullets synthesized in ethanol is similar to but more uniform than that of ZnO microbullets synthesized in methanol. The Fe-doped ZnO synthesized in ethanol contains many micron particles homogeneously dispersing on the surface of the microbullets, which is composed of hexagonal wurtzite ZnO and franklinite ZnFe₂O₄, while Fe-doped ZnO prepared in methanol consists of micron structured balloons, rods, and particles, which is composed of hexagonal wurtzite ZnO, hematite Fe₂O₃, and franklinite ZnFe₂O₄. Compared with pure ZnO and ZnO–ZnFe₂O₄ composite, the ZnO–Fe₂O₃–ZnFe₂O₄ composite presented high response, rapid response/recovery characteristics, good selectivity, and excellent stability to acetone at relatively low operating temperature of 190 °C. This sensor could detect acetone in wide range of 1–1000 ppm, which was expected to be a promising gas sensor for detecting acetone.     

Crystallization process and electro-optical properties of In2O3 and ITO thin films

Amorphous indium oxide (In₂O₃) and 10-wt% SnO₂ doped In₂O₃ (ITO) thin films were prepared by pulsed-laser deposition. These films were crystallized upon heating in vacuum at an effective heating rate of 0.00847 °C/s, while the evolution of the structure was observed by in situ X-ray diffraction measurements. Fast crystallization of the films is observed in the temperature ranges 165–210 °C and 185–230 °C for the In₂O₃ and ITO films, respectively. The crystallization kinetics is described by a reaction equation, with activation energies of 2.31 ± 0.06 eV and 2.41 eV and order of reactions of 0.75 ± 0.07 and 0.75 for the In₂O₃ and ITO films, respectively. The structures of the films observed here during heating are compared with those obtained upon film growth at different temperatures. The resistivity of the films depends on the evolution of the structure, the oxygen content and the activation of tin dopants in the films. A low resistivity of 5.5 × 10⁻⁴ Ω cm was obtained for the In₂O₃ and ITO films at room temperature, after annealing to 250 °C the resistivity of the ITO film reduces to 1.2 × 10⁻⁴ Ω cm.     

Effect of substrate temperature on the photoelectrochemical responses of Ga and N co-doped ZnO films

Ga–N co-doped ZnO thin films with reduced bandgaps were deposited on F-doped tin-oxide-coated glass by radio-frequency magnetron sputtering at different substrate temperatures in mixed N₂ and O₂ gas ambient. We found that Ga–N co-doped ZnO films exhibited enhanced crystallinity when compared to undoped ZnO films grown under the same conditions. Furthermore, Ga–N co-doping ensured enhanced N-incorporation ZnO thin films as the substrate temperature is increased. As a result, Ga–N co-doped ZnO thin films exhibited much improved photoelectrochemical (PEC) response, compared to ZnO thin films. Our results therefore suggest that the passive co-doping approach could be a means to improve PEC response for bandgap-reduced wide-bandgap oxides through impurity incorporation.     

Effect of Sn2O3 doping on structural,optical and dielectric properties of ZnO ceramics

The synthesis of the undoped ZnO and ZnO–Sn₂O₃ composites prepared by conventional solid-state reaction method has been reported. Besides, the effect of increasing Sn₂O₃ content from 5 to 15 wt% on structural, optical, dielectric and electrical properties of the ZnO–Sn₂O₃ composites has also been investigated. In fact, the X-ray diffraction analysis indicates that the as-prepared ZnO–Sn₂O₃ composites may contain some combined phases such as SnO and Zn₂SnO₄. The atomic force microscopy shows that the surfaces of the composites are rough. The band gap energy seems to depend on the amount of Sn₂O₃ addition, with the maximum obtained at 15 wt% Sn₂O₃. Concerning the optical band gap, it has been found to be in the range of 3.18–3.93 eV. The dielectric loss was found to decrease with the increase in frequency. The results obtained from the ac-conductivity revealed that the values of σ(ω) increases with the Sn₂O₃ adding content. The dc-conductivity of all the composites increases with the increase in temperature. The electrical conductivity was analyzed with the power law, and agrees with the correlation barrier hopping model.     

The study of optical properties of In2O3 and of mixed oxides In2O3−MoO3 system deposited by coevaporation

A discussion of the optical properties of two systems of dielectric films i.e. In₂O₃ and of mixed oxides In₂O₃−MoO₃ system is presented. Film thickness, substrate temperature, annealing and composition (in molar%) have a profound effect on the structure and optical properties of these films. The decrease in optical band gap with the increase in film thickness of In₂O₃ is interpreted in terms of incorporation of oxygen vacancies in the In₂O₃ lattice. The decrease in optical band gap with the increase in substrate temperature and annealing of In₂O₃ thin films is ascribed to the release of trapped electrons by thermal energy or by the outward diffusion of the oxygen-ion vacancies, which are quite mobile even at low temperature. For the mixed oxides In₂O₃−MoO₃ system the results are found to be compatible with the reduction in the value of optical band gap of these materials as the molar fraction of MoO₃ increases in the In₂O₃ thin films and is attributed to the incorporation of Mo(VI) ions in an In₂O₃lattice that causes the indium orbital to become a little less tightly bound. The decrease in optical band gap of mixed oxides In₂O₃−MoO₃ system, with increasing film thickness is interpreted in terms of incorporation of oxygen vacancies in both In₂O₃ and MoO₃ lattice which are also believed to be the source of conduction electrons in In₂O₃–MoO₃ complex. The decrease in optical band gap with increasing substrate temperature and annealing of mixed oxides In₂O₃−MoO₃ system is due to the increasing concentration of oxygen vacancies, formation of indium and molybdenum species of lower oxidation state and indium interstitials. The blue colouration of mixed oxides In₂O₃–MoO₃ samples is due to the inter-electron transfer from oxygen 2p to molybdenum 4d level due to which Mo species of lower oxidation states are formed.     

Fabrication and comparative study of top-gate and bottom-gate ZnO–TFTs with various insulator layers

Transparent ZnO thin film transistors (ZnO–TFTs) with different structures and dielectric layers were fabricated by rf magnetron sputtering. The PbTiO₃, AlO _x , SiN _x and SiO _x films were attempted to serve as the gate dielectric layers in the devices, respectively, and XRD was employed to investigate the crystal structure of ZnO films deposited on these dielectric layers. The optical properties of transparent TFTs were measured and revealed the average transmittance ranged from 60 to 80% in the visible part of the spectrum. Electrical measurement shows the properties of the ZnO–TFTs have great relations with the device structure. The bottom-gate TFTs have better behaviors than top-gate ones with the mobility, threshold voltage and the current on/off ratio of 18.4 cm² V⁻¹ s⁻¹, −0.7 V and 10⁴, respectively. The electrical difference of the devices may be due to different character of the interface between the channel and dielectric layers.     

In掺杂β-Zn_4Sb_3热电材料的制备与电热输运

设计了一系列名义组成为Zn4Sb3-xInx(0~0.08,Δx=0.02)的In掺杂β-Zn4Sb3基块体材料,并用真空熔融-随炉冷却-放电等离子体烧结工艺成功制备出无裂纹的In掺杂单相β-Zn4Sb3基块体材料.300~700K内材料的电热输运特性表明,In杂质对Zn4Sb3化合物的Sb位掺杂可导致载流子浓度和电导率大幅度增大、高温下本征激发几乎消失和晶格热导率显著降低,x=0.04和0.08的Zn4Sb3-xInx的In掺杂β-Zn4Sb3化合物700K时晶格热导率均仅为0.21W/(m·K).与纯β-Zn4Sb3块体材料相比,所有In掺杂β-Zn4Sb3基块体材料的ZT值均显著增大,x=0.06的Zn4Sb3-xInx的In掺杂β-Zn4Sb3基块体材料700K时ZT值达到1.13,提高了69%.     

Polycrystalline ZnO-In2O3 thin films as gas sensors

Polycrystalline ZnO-In₂O₃ thin films were prepared by thermal oxidation in air of metallic Zn-In films deposited onto glass substrates by thermal evaporation under vacuum. Different oxidation conditions (oxidation temperature, oxidation time, heating rate) were used in order to prepare homogeneous films that can be used as gas sensors. Polycrystalline structure of the as-obtained films was confirmed by X-ray and electron diffraction investigations. The electrical conductivity of various thin film samples ranged between 0.84 and 6.44 (Ω cm)^− 1.Gas sensitivity to six different gasses (ammonia, methane, LPG, acetone, ethanol and formaldehyde) was evaluated and it was found that the highest sensitivity was obtained for ammonia.     

Effects of Al content on the properties of ZnO:Al films prepared by Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and ZnO co-sputtering

Aluminum doped zinc oxide (AZO) films were deposited on quartz substrates by radio-frequency magnetron co-sputtering method with ZnO and Al₂O₃ ceramic targets. The structural, optical and electrical properties of these films as a function of the Al content were investigated. XRD results reveal that the AZO films are wurtzite structure with (002) preferred orientation. The average transmittance of all the films is higher than 80% in a wide wavelength range from 400 to 1,500 nm. The band gap energy, calculated from their optical absorption spectra, is in the range of 3.50–3.66 eV depending on the Al content. Doping of Al³⁺ in the ZnO makes the film surface roughness decrease. The dopant Al³⁺ acts as electron donor by which the electrical conductivity and carrier concentration of the films are obviously increased until the Al³⁺ reaches its saturation content of about 4.50 at.%.     

Preparation and characterization of indium zinc oxide thin films by electron beam evaporation technique

In this work, the preparation of In₂O₃-ZnO thin films by electron beam evaporation technique on glass substrates is reported. Optical and electrical properties of these films were investigated. The effect of dopant amount and annealing temperature on the optical and electrical properties of In₂O₃-ZnO thin films was also studied. Different amount of ZnO was used as dopant and the films were annealed at different temperature. The results showed that the most crystalline, transparent and uniform films with lowest resistivity were obtained using 25 wt% of ZnO annealed at 500 °C.     

Improvement of electrical properties of V2O5 modified ZnO ceramics by Mn-doping for varistor applications

The dependence of microstructure, electrical properties, dielectric characteristics, and stability of conduction characteristics in ternary ZnO–V₂O₅–Mn₃O₄ system on the amount of Mn₃O₄ present in them was investigated. For all compositions studied, the microstructure of the ternary ZnO–V₂O₅–Mn₃O₄ system consisted of mainly ZnO grains and Zn₃(VO₄)₂ as a secondary phase. The incorporation of Mn₃O₄ to the binary ZnO–V₂O₅ system was found to restrict abnormal grain growth of ZnO. The breakdown field in the electric field–current density characteristics increased from 175 to 4,635 V/cm with the increase of Mn₃O₄ amount. The ternary system doped with 0.5 mol% Mn₃O₄ exhibited the highest non-ohmic properties, in which the non-ohmic coefficient is 22.4 and the leakage current density is 0.22 mA/cm². Furthermore, the sample doped with 0.5 mol% Mn₃O₄ was found to possess 0.43 × 10¹⁸/cm³ in donor density and 2.66 eV in barrier height.     

Preparation and properties of Y2O3-doped ZrO2 thin films by the sol–gel process

Y₂O₃-doped ZrO₂ (YZ) thin films were prepared on alumina substrates by the dip-coating process. The dip-coating solution consisted of a homogeneous sol, and was prepared by using the respective chlorides as raw materials, with ethylene glycol, 2-butanol and distilled water as solvents. The thin films containing 0–20 mol % Y₂O₃ were successfully produced by thermal treatment above 600 °C. The characterization for the film preparation was performed by means of thermogravimetric–differential thermal analysis for the thermal analysis, and scanning electron microscopy for the morphological analysis and thickness measurements. The properties of the films were characterized in terms of a study of the crystalline phase, the crystallite size, the microstructure and the electrical conductivity by using X-ray diffraction, scanning electron microscopy and the complex impedance techniques. In all YZ thin films, the tetragonal phase was stable at low temperatures as a result of the crystallite size effect. However, at higher temperatures, the tetragonal phase was transformed into either the monoclinic phase or the cubic phase, depending on the doping concentration. The YZ thin film of 8 mol% Y₂O₃ content was stabilized to almost cubic phase at 1000 °C. Resonable conductivity behaviour at YZ was observed for the YZ thin films. The electrical conductivity of YZ thin films was similar to the values of the sintered body. This revised version was published online in November 2006 with corrections to the Cover Date.     

Synthesis of manganese–zinc ferrite by powder mixing using ferric oxide from a steel mill acid recovery unit

With the aim of producing fine-grained manganese–zinc (Mn–Zn) ferrite at the end of a calcination process at moderate temperatures, this study consisted, at first, of an “electrochemically designed” powder mixing by wet-ball milling a mixture of manganese (MnO₂), zinc (ZnO), and iron (Fe₂O₃ granules produced by an acid recovery unit of a Brazilian steelmaker, milled to fine sizes using alkaline media) –based raw materials. This mixing/milling resulted in improved size reduction when compared to milling without any alkali addition. Further, noticeable size reduction was achieved when elemental Zn was used in place of ZnO, especially when ammonia was used as the medium. Calcination of the alkaline-milled mixture of MnO₂ + ZnO + Fe₂O₃ at 1200 °C allowed obtaining well-crystallized single-phase Mn–Zn ferrite, whereas calcination of the MnO₂ + ZnO + Fe₂O₃ mill-mixed in 100% NH₄OH at 1200 °C produced the highest saturation magnetization in the as-calcined state.     

Advanced light trapping materials: Double layer ZnO:B based transparent conductive oxide

We present double layer structures consisting of ZnO:B/ZnO:B (BZO) and In₂O₃:Mo (IMO)/BZO films. The structure offers the unique opportunity of separating the conductivity of transparent conductive oxides from their light scattering behavior and allows their optimization for use in thin film solar cells. The layers serve as carrier transport and light trapping layers, respectively. BZO films were prepared by mid-frequency magnetic sputtering from a ZnO:B₂O₃ ceramic target. In order to enhance the conductivity of the BZO films, hydrogen was introduced into the sputtering atmosphere. Introducing hydrogen increased the mobility of the BZO-based double layer films to near 30 cm²/V•s. Efficient scattering was achieved by etching the film in dilute hydrochloric acid. IMO films were also tested as the transport layer. An unconventional surface morphology was obtained by etching the IMO/BZO double layer film. Using this cascading multilayer structure IMO/BZO film as the front contact in a-Si:H solar cell, 20.4% and 7.4% enhancements in short circuit current density were obtained compared to smooth IMO films and textured single layer BZO films.     

A study of crystallographic phases in non-stoichiometric (oxygen deficiency) indium oxide thin films

Indium oxide is a well-known transparent conductive oxide (TCO) in its stoichiometric composition (In₂O₃). Its electrical and optical properties are strongly influenced by the chemical composition. This work focuses on an experimental investigation of the crystallographic phases in non-stoichiometric (oxygen deficiency) compositions of indium oxide thin films. The thin films were deposited at 300 °C by reactive sputtering of pure indium target at different oxygen gas flow rates on Si substrates. Two different phases are identified only in the non-stoichiometric compositions: metallic indium- and crystalline indium-rich oxide. The metallic indium phase appears as nano-crystals, a few nano-meters in diameter, evenly dispersed and occupies only 1 vol. % of the film. These metallic nano-particles have a negligible effect on the optical transparency and electrical conductivity of the films. The indium-rich oxide (In_xO_y) phase which occupies about 99 vol. % of the film has the bixbyite crystallographic structure and average grain size of about 50 nm. This phase has a pronounced effect on improving the TCO figure-of-merit (FM) relative to stoichiometric crystalline In₂O₃ films due to a higher increase of the electrical conductivity than the decrease of the optical transparency.     

Structural,optical and microscopic properties of chemically deposited In<Subscript>2</Subscript>Se<Subscript>3</Subscript> thin films

Solar cell technologically important binary indium selenide thin film has been developed by relatively simple chemical method. The reaction between indium chloride, tartaric acid, hydrazine hydrate and sodium selenosulphate in an aqueous alkaline medium at room temperature gives deposits In₂Se₃ thin film. Various preparative parameters are discussed. The as grown films were found to be transparent, uniform, well adherent, red in color. The prepared films were studied using X-ray diffraction, scanning electron microscopy, atomic absorption spectroscopy, Energy dispersive atomic X-ray diffraction, optical absorption and electrical conductivity properties. The direct optical band gap value E_g for the films was found to be as the order of 2.35 eV at room temperature and having specific electrical conductivity of the order of 10⁻² (Ω cm)⁻¹ showing n-type conduction mechanism. The utility of the adapted technique is discussed from the point of view of applications considering the optoelectric and structural data obtained.