Effects of oxygen partial pressure on doping properties of Ga-doped ZnO films prepared by ion-plating with traveling substrate

Polycrystalline Ga-doped ZnO (GZO) thin films were prepared by ion-plating on a traveling glass substrate at 200 °C. Effects of O₂ gas flow rate and Ga₂O₃ content in source on the electrical and structural properties of GZO films were investigated. GZO films having a low resistivity of 210^− 4 Ω cm order were obtained under the conditions of Ga₂O₃ contents of 3-5 wt.% and O₂ gas flow rates below 10 sccm. In particular, for GZO films prepared with a Ga₂O₃ content of 4 wt.% at an O₂ gas flow rate of 2.5 sccm, the lowest resistivity of 2.23 × 10^− 4 Ω cm was obtained; the carrier concentration and Hall mobility were 1.17 × 10²¹ cm^− 3 and 23.9 cm²/Vs, respectively. Excess Ga₂O₃ content in source (> 6 wt.%) cause deterioration both in crystallinity and in electric property most probably due to the solubility limit for Ga doping in ZnO at the glass substrate temperature of 200 °C. Excess O₂ gas flow rates (> 10 sccm) during the film growth also lower the electric properties of the GZO films.     

Fabrication and characterization of ITO thin films on heat-resistant transparent flexible clay films

Transparent conductive indium tin oxide (ITO) thin films were deposited on transparent flexible clay films with heat resistant and high gas barrier properties by rf magnetron sputtering. The electrical, structural, and optical properties of these films were examined as a function of deposition temperature. A lowest resistivity of 4.2 × 10^− 4 Ωcm and an average transmittance more than 90% in the visible region were obtained for the ITO thin films fabricated at deposition temperatures more than 300 °C. It was found that ITO thin films with low resistivity and high transparency can be achieved on transparent flexible clay film using conventional rf magnetron sputtering at high temperature, those characteristics are comparable to those of ITO thin films deposited on a glass substrate.     

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.     

Effects of oxygen partial pressure on film growth and electrical properties of undoped ZnO films with thickness below 100 nm

The dependences of electrical and structural properties on film thickness below 100 nm have been studied on polycrystalline undoped zinc oxide (ZnO) thin films on glass substrates at 200 °C prepared by plasma-assisted electron-beam deposition. From Hall effect measurements, we find that resistivity decreases from 0.47 to 0.02 Ω cm with increasing film thickness, whereas carrier concentration remains almost constant, 1.65-2.0 × 10¹⁹ cm^− 3, Hall mobility increases from 1.7 to 16.7 cm²/Vs with increasing film thickness. From both high-resolution out-of-plane and in-plane X-ray diffraction (XRD) data, we find substantial changes in the lattice parameters with increasing film thickness below 40 nm; a reduction in the lattice parameter of the a-axis and an increase in the lattice parameter of the c-axis. Williamson-Hall analysis reveals an increase in in-plane grain size with increasing film thickness. This indicates that the dominant scattering mechanism that determines electrical properties is a boundary scattering mechanism.     

Electrochemically deposited polypyrrole films and their characterization

Ionically conductive polypyrrole films have been deposited at 295 K from anhydrous acetonitrile, acetonitrile/H₂O and NaBF₄ aqueous solutions onto platinum, mild steel and stainless steel discs, using cyclic voltammetry, potentiostatic and galvanostatic techniques. Cyclic voltammetry of the polymer films has been studied as a function of water content of the acetonitrile solvent, polypyrrole concentration and potential sweep rate. Potentiostatic growth of thicker (< 30 micron) films on stainless steel allowed free-standing polypyrrole membranes to be produced. Well adherent and conductive films were deposited at constant potential in stirred solutions from acetonitrile electrolytes containing 1% (v/v) of water. The membrane resistivity of the reduced films in 0.5 mol dm^− 3 KCl_(aq) at 295 K was ≈ 1 × 10⁶ Ω cm, while the resistivity of the oxidised membrane was 2700 Ω cm.     

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.     

Thin films of thermoelectric compound Mg2Sn deposited by co-sputtering assisted by multi-dipolar microwave plasma

Magnesium stannide (Mg₂Sn) thin films doped with Ag intended for thermoelectric applications are deposited on both silicon and glass substrates at room temperature by plasma assisted co-sputtering. Characterization by scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction confirms the formation of fine-grained polycrystalline thin films with thickness of 1-3 μm. Stoichiometry, microstructure and crystal structure of thin films are found to vary with target biasing and the distance from targets to substrate. Measurements of electrical resistivity and Seebeck coefficient at room temperature show the maximum power factor of ∼5.0 × 10⁻³ W K⁻² m⁻¹ for stoichiometric Mg₂Sn thin films doped with ∼1 at.% Ag.     

A study on crystallization, optical and electrical properties of the advanced ZITO thin films using co-sputtering system

Multi-functions (conductor, semiconductor and insulator) ZnInSnO (ZITO) transparent oxide thin films have been obtained by a co-sputtering system using ITO target and ZnO target with oxygen gas contents (0-8%). The ZITO film containing a small ITO content had the lowest resistivity (good electron mobility) and higher optical transmittance. In addition, the influences of thermal treatments (post-annealing and substrate temperature) on electrical properties and optical transmittance of ZITO films were studied. Photoluminescence (PL) of the ZITO film confirmed the contribution of ITO content and oxygen gas content on the photo-emission. The ZITO film with zinc atomic concentration of 58 at.% was a good candidate for TCO material (3.08 × 10⁻⁴ Ω cm). Under the substrate temperature of 100 °C or post-annealing temperature of 200 °C, the properties of ZITO film could be improved.     

Study of post annealing influence on structural, chemical and electrical properties of ZTO thin films

Zinc-Tin-Oxide (ZTO) thin films were deposited on glass substrate with varying concentrations (ZnO:SnO₂; 100:0, 90:10, 70:30 and 50:50 wt.%) at room temperature by flash evaporation technique. These deposited ZTO films were annealed at 450 °C in vacuum. These films were characterized to study the effect of annealing and addition of SnO₂ concentration on the structural, chemical and electrical properties. The XRD analysis indicates that crystallization of the ZTO films strongly depends on the concentration of SnO₂ and post annealing where annealed films showed polycrystalline nature. Atomic force microscopy (AFM) images manifest the surface morphology of these ZTO thin films. The XPS core level spectra of Zn(2p), O(1s) and Sn(3d) have been deconvoluted into their Gaussian component to evaluate the chemical changes, while valence band spectra reveal the electronic structures of these films. A small shift in Zn(2p) and Sn(3d) core level towards higher binding energy and O(1s) core level towards lower binding energy have been observed. The minimum electrical resistivity (ρ ≈ 3.69 × 10⁻² Ω-cm), maximum carrier concentration (n ≈ 3.26 × 10¹⁹ cm⁻³) and Hall mobility (μ ≈ 5.2 cm² v⁻¹ s⁻¹) were obtained for as-prepared ZTO (50:50) film thereafter move towards lowest resistivity (ρ ≈ 1.12 × 10⁻³ Ω-cm), highest carrier concentration (n ≈ 2.96 × 10²⁰ cm⁻³) and mobility (μ ≈ 18.8 cm² v⁻¹ s⁻¹) for annealed ZTO (50:50) thin film.     

Fabrication and properties of p-type K doped Zn1−xMgxO thin film

A series of K doped Zn_1−xMg_xO thin films have been prepared by pulsed laser deposition (PLD). Hall-effect measurements indicate that the films exhibit stable p-type behavior with duration of at least six months. The band gap of the K doped Zn_1−xMg_xO films undergoes a blueshift due to the Mg incorporation. However, photoluminescence (PL) results reveal that the crystallinity decreased with the increasing of Mg content. The fabricated K doped p-type Zn_0.95Mg_0.05O thin film exhibits good electrical properties, with resistivity of 15.21 Ω cm and hole concentration of 5.54 × 10¹⁸ cm⁻³. Furthermore, a simple ZnO-based p-n heterojunction was prepared by deposition of a K-doped p-type Zn_0.95Mg_0.05O layer on Ga-doped n-type ZnO thin film with low resistivity. The p-n diode heterostructure exhibits typical rectification behavior of p-n junctions.     

Transparent conducting oxide films of heavily Nb-doped titania by reactive co-sputtering

Niobium-doped titania (TNO) films of various Nb content were deposited on glass and silicon substrates by reactive co-sputtering of Ti and Nb metal targets. Nb content in the TNO films was varied from 0 to ∼13 at.% (atomic percent), corresponding to Ti_1−xNb_xO₂ with x = 0-0.52, by modulating the Nb target power from 0 to 150 W (Watts). The influence of ion bombardment on the TNO films was investigated by applying an RF substrate bias from 0 to 25 W. The as-deposited TNO films were all amorphous and insulating, but after annealing at 600 °C for 1 h in hydrogen, they became crystalline and conductive. The annealed films crystallized into either pure anatase or mixed anatase and rutile structures. The as-deposited and the annealed films were transparent, with an average transmittance above 70%. Anatase TNO film (Ti_1−0.39Nb_0.39O₂) with Nb 9.7 at.% exhibited a dramatically reduced resistivity of 9.2 × 10⁻⁴ Ω cm, a carrier density of 6.6 × 10²¹ cm⁻³ and a carrier mobility around 1.0 cm² V⁻¹ s⁻¹. In contrast, the mixed-phase Ti_1−0.39Nb_0.39O₂ showed a higher resistivity of 1.2 × 10⁻¹ Ω cm. This work demonstrates that the anatase phase, oxygen vacancies, and Nb dopants are all important factors in achieving high conductivities in TNO films.     

Modification of the electrical properties of polyimide by irradiation with 80 keV Xe ions

We modify the electrical properties of polyimide (PI) films by irradiation with 80 keV Xe ions. The surface resistivity of irradiated PI film at room temperature decreases remarkably from 1.2 × 10¹⁴ Ω/□ for virgin PI film to 3.15 × 10⁶ Ω/□ for PI film irradiated by 5.0 × 10¹⁶ ions/cm², and the temperature dependence of the resistivity of the treated films is well-fit using Mott's Equation. The irradiated PI film structure is studied using Raman spectroscopy, X-ray diffraction, and Rutherford Backscattering Spectrometry. The concentration of O in the irradiated layer decreases with increasing fluence, while the variation of N concentration is negligible. Graphite-like carbon-rich phases are created in the irradiated layers, leading to the modification of the electrical properties.     

Influence of EDTA concentration on the structure and properties of SnS films prepared by electro-deposition

Tin sulfide (SnS) thin films were deposited onto indium tin oxide (ITO) glass substrates by cathodic electro-deposition from aqueous solution containing ethylene diamine tetraacetate acid (EDTA). Because EDTA can slow the deposition rate of Sn through formation of Sn chelates, it is possible to obtain stoichiometric SnS films with good quality by adding EDTA to the deposition bath. The deposited films were characterized with X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy (Raman), and ultraviolet-visible-near infrared (UV-VIS-NIR) spectrophotometer. The as-deposited films are mainly polycrystalline SnS with orthorhombic crystalline structure, and they show good uniformity and surface coverage with root mean square (RMS) roughness of 45.36-62.39 nm and grain sizes of 100-300 nm. Raman microscopy shows that the films have bands at around 190 and 218 cm^− 1 belonging to A_g mode of SnS. The concentration ratio of EDTA and Sn²⁺ (EDTA/Sn²⁺) has some influence on the structure, phase, Raman shift and optical properties of the deposited films. When the EDTA/Sn²⁺ is less than 0.5, the films have a Raman shift at around 306 cm^− 1 due to Sn₂S₃. XPS analysis also shows that there exists a Sn₂S₃ phase in the deposited films. When the EDTA/Sn²⁺ equals 1/1, there is only the SnS phase in the deposited films. With an increase of the EDTA/Sn²⁺ from 0.1 to 1, the direct band gap of the films is decreased from 1.75 eV to 1.43 eV. Therefore EDTA/Sn²⁺ = 1/1 is good for depositing SnS films.     

Thermal stability of Ta-Si-N nanocomposite thin films at different nitrogen flow ratios

Ta-Si-N thin films were applied as diffusion barriers for Cu interconnections or hard coatings in mechanical application. The resistivity, hardness and thermal stability were the important issues in the interconnections and hard coatings, respectively. In this paper, we investigated the relationship between the microstructures, resistivity, nanohardness and thermal stability of the Ta-Si-N thin films at different nitrogen flow ratios of 0-30% (N₂% = N₂ / (Ar + N₂) × 100%) by magnetron reactive co-sputtering. The Ta-Si-N films were annealed at 600, 750 and 900 °C at about 6 × 10⁻³ Pa for 1 h, respectively, to examine their thermal stability. The microstructures of Ta-Si-N films at low N₂% of 2-10% still retained the amorphous-like phase with nanocrystalline grains in an amorphous matrix at annealing of 600-900 °C. The nanohardness of amorphous-like Ta-Si-N film at N₂% of 3% was measured to be 15.2 GPa much higher than that of polycrystalline film of 10.1 GPa at N₂% of 20%. The average nanohardness of both films is stable up to 900 °C and varied in the range of 0.43-0.83 GPa. The resistivity of the as-deposited Ta-Si-N films increase with increasing N₂ flow rate. It is small around 220-540 μΩ cm for low N₂% of 2-10% while it increases abruptly to about 7700-43,000 μΩ cm at high N₂% of 20-30%. The best thermal stability of resistivity of Ta-Si-N film occurs at the N₂% of 2% in the range of 220 to 250 μΩ cm from RT to 900 °C.     

A study of suppression effect of oxygen contamination by bias voltage in reactively sputtered ZrN films

A scrupulous cleaning and degreasing of the deposition chamber allows to make a ZrN film with stoichiometry of 1.3 and to achieve a level of oxygen contamination equal to 5%. This film exhibits a low number of carriers estimated at N* = 3 × 10²¹ cm^− 3 and with a very high electrical resistivity value of about 10⁵ μΩ·m. This result points the way for further improvements in the quality of the material.This amount of oxygen contamination may be reduced in conditions in which only the oxygen will be removed without disturbing the zirconium presence in the film. A bias voltage value between 8 eV and 20 eV reduces the oxygen contamination.The ionic assistance is often proposed as a mean to minimize the oxygen contamination. However, one must consider the negative phenomena as re-sputtering, ion implantation, atom displacement and stress generation that introduce defects in the film and affect its properties. This work proposes a very low bias voltage value to control oxygen contamination. The bias voltage value is chosen higher than the nitrogen sputtering threshold energy and lower than the argon sputtering threshold energy. The re-sputtering phenomenon, far from being a problem, can be used to achieve the stoichiometry if one starts from a nitrogen-rich compound. In this way, ZrN_x is grown with x about 1, with an effective free electron concentration N* = 8.9 × 10²¹ cm^− 3. Furthermore its resistivity value is about 2 μΩ·m and the oxygen Secondary Ion Mass Spectrometry (SIMS) signal is similar to the noise signal.     

Pulsed laser deposition of anatase and rutile TiO2 thin films

The investigation deals with the preparation of both anatase and rutile thin films from a sintered rutile target of TiO₂ by pulsed laser ablation technique. Microstructural characterization of the sintered target was carried out using X-ray diffraction and AC impedance spectroscopy. Thin films of titania were deposited on (111) Si substrates at 673 K in the laser energy range 200-600 mJ/pulse at two different conditions: (i) deposition at 3.5 × 10^− 5 mbar of oxygen, and (ii) deposition at an oxygen partial pressure of 0.1 mbar. The influence of laser energy and oxygen addition on the film growth has been studied. X-ray diffraction analysis of the films indicated that the films are single phasic and nano crystalline. Titania films deposited in the energy range 200-600 mJ/pulse at a base pressure of 5 × 10^− 5 mbar are rutile with particle sizes in the range 5-10 nm, whereas the films formed at the oxygen partial pressure 0.1 mbar are anatase with particle sizes in the range 10-24 nm. In addition, at higher energies, a significant amount of particulates of titania are found on the surface of the films. The change in the microstructural features of the films as a function of laser energy and oxygen addition is discussed in relation with the interaction of the ablated species with the background gas.     

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.     

Optical and electrical properties of zinc oxide thin films with low resistivity via Li-N dual-acceptor doping

Zinc oxide thin films with low resistivity have been deposited on glass substrates by Li-N dual-acceptor doping method via a modified successive ionic layer adsorption and reaction process. The thin films were systematically characterized via scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction, ultraviolet-visible spectrophotometry and fluorescence spectrophotometry. The resistivity of zinc oxide film was found to be 1.04 Ω cm with a Hall mobility of 0.749 cm² V⁻¹ s⁻¹ and carrier concentration of 8.02 × 10¹⁸ cm⁻³. The Li-N dual-acceptor doped zinc oxide films showed good crystallinity with prior c-axis orientation, and high transmittance of about 80% in visible range. Moreover, the effects of Li doping level and other parameters on crystallinity, electrical and ultraviolet emission of zinc oxide films were investigated.     

Low temperature processed highly conducting, transparent, and wide bandgap Gd doped CdO thin films for transparent electronics

Gadolinium (Gd) doped cadmium oxide (CdO) thin films are grown at low temperature (100 °C) using pulsed laser deposition technique. The effect of oxygen partial pressures on structural, optical, and electrical properties is studied. X-ray diffraction studies reveal that these films are polycrystalline in nature with preferred orientation along (1 1 1) direction. Atomic force microscopy studies show that these films are very smooth with maximum root mean square roughness of 0.77 nm. These films are highly transparent and transparency of the films increases with increase in oxygen partial pressure. We observe an increase in optical bandgap of CdO films by Gd doping. The maximum optical band gap of 3.4 eV is observed for films grown at 1 × 10⁻⁵ mbar. The electrical resistivity of the films first decreases and then increases with increase in oxygen partial pressure. The lowest electrical resistivity of 2.71 × 10⁻⁵ Ω cm and highest mobility of 258 cm²/Vs is observed. These low temperature processed highly conducting, transparent, and wide bandgap semiconducting films could be used for flexible optoelectronic applications.     

Low temperature sputter deposition of SnOx:Sb films for transparent conducting oxide applications

SnO_x:Sb films have been prepared by reactive dc magnetron sputtering from a metallic target, with the aim of evaluating the potential of SnO_x:Sb as an attractive low-cost alternative to In₂O₃:Sn (ITO) for TCO applications. The deposition was performed without any additional heating of the substrates. The films were subsequently analysed regarding their optical, electrical and structural properties. Our results show that there is only a narrow process window for the sputter deposition of transparent and conducting tin oxide films at low temperature. A sharp minimum in resistivity of 4.9 mΩ cm is observed at an oxygen content of approximately 17% in the sputtering gas. Under these deposition conditions, the SnO₂:Sb films turn out to be both highly transparent and crystalline. At lower oxygen content (10-15%) the SnO_x:Sb films are substoichiometric, as revealed by Rutherford backscattering, and show a low transmission and high resistivity due to numerous defects and the presence of the SnO phase. At higher oxygen content (> 17%) excess oxygen is incorporated into the films, which is attributed to an increase of oxygen ion bombardment. This leads to a degradation of the electrical properties and a decrease of the density of the films, whilst the optical transmittance slightly improves.