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.     

Preparation and electrochemical performance of copper foam-supported amorphous silicon thin films for rechargeable lithium-ion batteries

Amorphous Si thin films, which have been deposited on copper foam by radio-frequency (rf) magnetron sputtering, are employed as anode materials of rechargeable lithium-ion batteries. The morphologies and structures of the as-prepared Si thin films are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray powder diffraction (XRD). Electrochemical performance of lithium-ion batteries with the as-prepared Si films as the anode materials is investigated by cyclic voltammetry and charge-discharge measurements. The results show that the electrode properties of the prepared amorphous Si films are greatly affected by the deposition temperature. The film electrode deposited at an optimum temperature of 300 °C can deliver a specific capacity of ∼2900 mAh/g and a coulombic efficiency above 95% at charge/discharge current density of 0.2C after 30 cycles. The Li⁺ diffusion coefficiency in copper foam-supported Si thin films is determined to be 2.36 × 10⁻⁹ cm²/s.     

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.     

Use of the magnetron-sputtering technique for the control of the properties of indium tin oxide thin films

Indium tin oxide films were made with their stoichiometry controlled to give optimum electrical and optical properties. They were deposited by d.c. magnetron sputtering on glass substrates at room temperature. The mechanical properties of these films were also studied. The initial experiments show the dependence of resistivity on film thickness. The controlled processes gave a resistivity of about 10⁻⁵ Ωm and visible transmission of about 85%. The performance of ITO films can be increased by annealing the films in argon ambient.     

Study on adhesion and electro-optical properties of ITO films on flexible PET substrate

High-quality ITO films on flexible PET substrate were prepared by RF magnetron sputtering at low deposition temperature with different Ar gas sputtering pressure.Adhesion and electro-optical properties of ITO films were investigated as a function of Ar partial pressure.The sputtering conditions provide very uniform ITO films with high transparency (＞85% in 400-760 nm spectra) and low electrical resistivity (1.408×10-3-1.956×10-3 Ω·cm).Scratch test experiments indicate that there is a good adhesion property between ITO films and PET substrate, the critical characteristic load increases from 16.5 to 23.2 N with increasing Ar sputtering pressure from 0.2 to 1.4 Pa.     

AC powered reactive magnetron deposition of indium tin oxide (ITO) films from a metallic target

Transparent highly conductive indium tin oxide (ITO) films for low cost applications were deposited by a reactive dual magnetron sputter process using metallic targets. The magnetrons were equipped with rectangular (130 × 400 mm²) In:Sn targets (90 wt.% In/10 wt.% Sn). A sine wave power supply was used at a frequency of about 70 kHz. All experiments were done in the transition mode at a constant argon flow of 40 sccm and an oxygen flow varied between 35 and 70 sccm. The total pressure was kept constant at 0.4 Pa.The films were deposited onto silicon and float glass substrates which were either moved in an oscillatory manner (dynamic deposition) or fixed in front of the targets (static mode) during deposition. A dynamic deposition rate of about 100 nm × m/min was obtained at an average power of 2 kW/cathode. The film thickness was adjusted to 500 nm. At an optimised Ar/O₂ gas flow ratio of 0.6 we found an electrical resistivity as low as 1.2 × 10^− 3 Ω cm. The refractive index of these films was about 2.05 indicating a dense film structure, while the optical absorption of k = 10^− 2 qualifies these ITO films for many low cost applications. Moreover, the film structure and texture were investigated by XRD methods.Applying a static deposition we have achieved a lower electrical resistivity with a minimum value of 6 × 10^− 4 Ω cm. In this case, the resistivity and the transparency, respectively, were not constant over the substrate but depend on the lateral position in front of the target. To explain this inhomogeneity we have performed spatially resolved deposition rate and Langmuir probe measurements and related their results to film structure and properties. In order to improve the film properties at dynamic deposition the growth conditions have to be homogenised at all substrate positions.     

P-type transparent conducting SnO2:Zn film derived from thermal diffusion of Zn/SnO2/Zn multilayer thin films

Highly transparent, p-type conducting SnO₂:Zn thin films are prepared from the thermal diffusion of a sandwich structure of Zn/SnO₂/Zn multilayer thin films deposited on quartz glass substrate by direct current (DC) and radio frequency (RF) magnetron sputtering using Zn and SnO₂ targets. The deposited films were annealed at various temperatures for thermal diffusion. The effect of annealing temperature and time on the structural, electrical and optical performances of SnO₂:Zn films was studied. XRD results show that all p-type conducting films possessed polycrystalline SnO₂ with tetragonal rutile structure. Hall effect results indicate that the treatment at 400 °C for 6 h was the optimum annealing parameters for p-type SnO₂:Zn films which have relatively high hole concentration and low resistivity of 2.389 × 10¹⁷ cm^− 3 and 7.436 Ω cm, respectively. The average transmission of the p-type SnO₂:Zn films was above 80% in the visible light range.     

Characteristics of ITO films deposited on a PET substrate under various deposition conditions

ITO films, with a thickness of 150 nm to 160 nm, were deposited on an unheated hard coated PET substrate or non-alkali glass substrate via dc magnetron sputtering. Depositions were carried out under the following various conditions: total gas pressure (P_tot), dc sputtering power, target — substrate (T-S) distance, and O₂ or H₂ addition ratio. The ITO coated on the PET substrate showed relatively lower resistivity than that of the ITO coated on a glass substrate. Relatively small changes in the resistance (ΔR/R₀=0.4) of the films were obtained for each deposition condition for the ITO/PET deposited under a sputtering power of 70 W, P_tot of 0.5 Pa, and T-S of 50 mm. It has been confirmed that the results of the electrical property showed concurrence with the results of the bending test. Specifically, the films that have a good electrical property showed only a small change in resistance to the increasing cycle number for each deposition condition. Therefore, it can be assumed that the increased resistance of the ITO films could be due to the formation of micro defects such as micro-cracks and the micro detachment of the ITO film from the flexible PET substrate.     

Deposition of dense and smooth Ti films using ECR plasma-assisted magnetron sputtering

We report high quality Ti films grown in a novel electron cyclotron resonance (ECR) plasma-assisted magnetron sputtering (PMS) deposition system. The films are compared with films deposited by conventional direct current (DC) magnetron sputtering. Using ECR-PMS, the argon plasma bombardment energy and Ti film deposition rate can be controlled separately, with the substrate bias voltage under feedback control. Results from SEM, AFM, XRD and PAS (scanning electron microscopy, atomic force microscopy, X-ray diffraction and positron annihilation spectroscopy) show that the properties of Ti films prepared by ECR-PMS are greatly improved compared with conventional sputtering. SEM and AFM confirmed that ECR-PMS Ti films have a dense, smooth, mirror-like surface. Increasing the substrate bias of the ECR plasma from − 23 V to − 120 V while keeping a fixed sputtering bias voltage of − 40 V, the intensity of the (100) reflection of Ti film was a little strengthened, but (002) remained strongly preferred orientation. The XRD peak broadening of ECR-PMS Ti films is more than for conventional magnetron sputtering, due to grain refinement induced by Ar ion bombardment. Doppler broadening of PAS analysis reveals that the Ti films have fewer vacancy defects compared with films prepared by the conventional magnetron.     

Fabricating TiO2 Photocatalysts by rf Reactive Magnetron Sputtering at Varied Oxygen Partial Pressures

Titanium dioxide (TiO₂) thin films were fabricated onto non-alkali glass substrates by rf reactive magnetron sputtering at room temperature using Ti-metal target at varied oxygen partial pressure [O₂/(Ar + O₂)]. The sputtering deposition was performed under an rf power of 200 W. The target to substrate distance was kept at 80 mm, and the total gas pressure was 10 mTorr after 2 h of deposition. It was found that the crystalline structure, surface morphology, and photocatalytic activities of the TiO₂ thin films were affected by the oxygen partial pressure during deposition. The XRD patterns exhibited a broad-hump shape indicating the amorphous structure of TiO₂ thin films. The thin films deposited at a relatively high value of oxygen partial pressure (70%) had a good photo-induced decomposition of methylene blue (MB), photo-induced hydrophilicity, and had a small grain size.     

Preparation and properties of tungsten-doped indium oxide thin films

Tungsten-doped indium oxide (IWO) thin films were deposited on glass substrate by DC reactive magnetron sputtering. The effects of sputtering power and growth temperature on the structure, surface morphology, optical and electrical properties of IWO thin films were investigated. The thickness and surface morphology of the films are both closely dependent on the sputtering power and the substrate temperature. The transparency of the films decreases with the increase of the sputtering power but is not seriously influenced by substrate temperature. All the IWO thin film samples have high transmittance in near-infrared spectral range. With either the sputtering power or the growth temperature increases, the resistivity of the film decreases at the beginning and increases after the optimum parameters. The as-deposited IWO films with minimum resistivity of 6. 4× 10-4 Ω·cm were obtained at a growth temperature of 225 ℃ and sputtering power of 40 W, with carrier mobility of 33. 0 cm2· V-1·s-1 and carrier concentration of 2. 8× 1020 cm-3 and the average transmittance of about 81％ in near-infrared region and about 87％ in visible region.     

The effect of film composition on the structure and mechanical properties of NiTi shape memory thin films

Shape memory NiTi-based thin films approximately 2 μm thick were deposited onto Si (100) substrates at room temperature by simultaneous DC magnetron sputter deposition from separate elemental Ni and Ti targets. The effect of composition on film structure, surface morphology, transformation temperature and mechanical behavior was studied using variable temperature X-ray diffraction, atomic force microscopy, electrical resistivity, and nanoindentation. The films showed the expected shape memory and superelasticity behavior corresponding to the different film compositions, comparable with bulk properties. The transformation from the low temperature martensitic phase to the high temperature parent phase takes place above room temperature in Ti-rich and near-equiatomic films, and below room temperature in Ni-rich films. Mechanical properties of films investigated at room temperature by a series of nanoindentations at mN loads (indentation depth < 200 nm) with a spherical indenter demonstrate superelasticity in Ni-rich material and martensitic deformation for Ti-rich and near-equiatomic compositions.     

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 processing of high conductivity and high transparency indium–tin-oxide/Ag alloy/indium–tin-oxide multilayered thin films

Indium–tin-oxide (ITO) thin films and ITO/Ag alloy/ITO multilayered thin films were deposited on glass substrates using a vertical in-line multilayer sputtering system. Ceramic ITO targets were used for the deposition of ITO layers at low substrate temperature of 100 °C. It was observed that the sheet resistance and light transmission of ITO films were affected by the oxygen pressure significantly. The ITO/Ag alloy/ITO multilayered thin films made in the present work had a low sheet resistance (6.9 Ω/□) and a high transmission (87.1%) at 550 nm. Atomic force microscopy (AFM) investigation showed that through selecting proper processing parameters, the surface roughness could be significantly reduced. The surfaces of ITO films were found very smooth by using pulsed-direct current (pulsed-dc) sputtering with introduction of H₂O. The work functions of the ITO films and ITO/Ag alloy/ITO multilayered films were increased with oxygen plasma treatment.     

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.     

Dual-magnetron open field sputtering system for sideways deposition of thin films

A dual-magnetron system for deposition inside tubular substrates has been developed. The two magnetrons are facing each other and have opposing magnetic fields forcing electrons and thereby also ionized material to be transported radially towards the substrate. The depositions were made employing direct current magnetron sputtering (DCMS) and high power impulse magnetron sputtering (HiPIMS). To optimize the deposition rate, the system was characterized at different separation distances between the magnetrons under the same sputtering conditions. The deposition rate is found to increase with increasing separation distance independent of discharge technique. The emission spectrum from the HiPIMS plasma shows a highly ionized fraction of the sputtered material. The electron densities of the order of 10¹⁶ m^− 3 and 10¹⁸ m^− 3 have been determined in the DCMS and the HiPIMS plasma discharges respectively. The results demonstrate a successful implementation of the concept of sideways deposition of thin films providing a solution for coating complex shaped surfaces.     

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.     

Synthesis of layered birnessite-type manganese oxide thin films on plastic substrates by chemical bath deposition for flexible transparent supercapacitors

Layered birnessite-type manganese oxide thin films are successfully fabricated on indium tin oxide coated polyethylene terephthalate substrates for flexible transparent supercapacitors by a facile, effective and inexpensive chemical bath deposition technology from an alkaline KMnO₄ aqueous solution at room temperature. The effects of deposition conditions, including KMnO₄ concentration, initial molar ratio of NH₃·H₂O and KMnO₄, bath temperature, and reaction time, on the electrochemical properties of MnO₂ thin films are investigated. Layered birnessite-type MnO₂ thin films deposited under optimum conditions display three-dimensional porous morphology, high hydrophilicity, and a transmittance of 77.4% at 550 nm. A special capacitance of 229.2 F g⁻¹ and a capacitance retention ratio of 83% are obtained from the films after 1000 cycles at 10 mV s⁻¹ in 1 M Na₂SO₄. Compressive and tensile bending tests show that as-prepared MnO₂ thin film electrodes possess excellent mechanical flexibility and electrochemical stability.     

Preparation and characteristics of indium tin oxide (ITO) thin films at low temperature by r.f. magnetron sputtering

Low resistivity and highly transparent ITO conducting films for solar cell applications were fabricated at low temperature by r.f. Magnetron sputtering. ITO films were deposited on glass and silicon substrate. Electrical, optical, structural and morphological properties of the ITO films were investigated in terms of the preparation conditions. The annealing treatment has improved the properties of the ITO films at different degree. The maximum transmittance of the obtained ITO films in the visible range is over 92%, and the low resistivity for the ITO films are about 3.85×10-4Ω·cm at 80℃, 80 W after annealing.     

Exploring the potential of high power impulse magnetron sputtering for growth of diamond-like carbon films

Amorphous carbon films are deposited employing high power impulse magnetron sputtering (HiPIMS) at pulsing frequencies of 250 Hz and 1 kHz. Films are also deposited by direct current magnetron sputtering (dcMS), for reference. In both HiPIMS and dcMS cases, unipolar pulsed negative bias voltages up to 150 V are applied to the substrate to tune the energy of the positively charged ions that bombard the growing film. Plasma analysis reveals that HiPIMS leads to generation of a larger number of ions with larger average energies, as compared to dcMS. At the same time, the plasma composition is not affected, with Ar⁺ ions being the dominant ionized species at all deposition conditions. Analysis of the film properties shows that HiPIMS allows for growth of amorphous carbon films with sp³ bond fraction up to 45% and density up to 2.2 g cm^− 3. The corresponding values achieved by dcMS are 30% and 2.05 g cm^− 3, respectively. The larger fraction of sp³ bonds and mass density found in films grown by HiPIMS are explained in light of the more intense ion irradiation provided by the HiPIMS discharge as compared to the dcMS one.