Transport phenomena in high performance nanocrystalline ZnO:Ga films deposited by plasma-enhanced chemical vapor deposition

Nanocrystalline gallium doped zinc oxide (ZnO:Ga) thin films were synthesized by plasma-enhanced chemical vapor deposition (PECVD). A statistical design of experiments (DOE) was employed to optimize electrical conductivity. A carrier concentration of 5.5×10²⁰/cm³ and a mobility of 15 cm²/V s yielding a resistivity of 7.5×10⁻⁴ Ω cm resulted from the conditions of high pressure, rf power, and electrode gap. X-ray diffraction showed that gallium doping had a profound impact on film orientation. Atomic force microscopy (AFM) revealed that the films were nanostructured, with an average grain size of 80 nm and a surface roughness of ∼2 nm. This unique morphology benefited optical transmission, but limited electrical performance. Average transmission across the visible spectrum was ∼93% as scattering losses were minimized. Temperature dependent Hall and optical transmission measurements demonstrated that structural defects and ionized impurities were equal contributors to electron scattering.     

Optical constants and band edge of amorphous zinc oxide thin films

The optical characteristics of amorphous zinc oxide (a-ZnO) thin films grown by radio frequency reactive magnetron sputtering on various substrates at temperature < 325 K have been investigated in the spectral range 340-1600 nm. The amorphous nature of the a-ZnO films was verified by X-ray diffraction and the optical constants were obtained by analysis of the measured ellipsometric spectra using the Cauchy-Urbach model. Refractive indices and extinction coefficients of the films were determined to be in the range 1.67-1.93 and 3.9 × 10^− 8-0.32, respectively. The band edge of the films on Si (100) and quartz has been determined by spectroscopic ellipsometry (3.39 ± 0.05 eV) and spectrophotometric (3.35 ± 0.05 eV) methods, respectively. From the angle dependence of the p-polarized reflectivity we deduce a Brewster angle of 60.5°. Measurement of the polarized optical properties shows a high transmissivity (81%-99%) and low absorptivity (< 5%) in the visible and near infrared regions at different angles of incidence. Also, we found that there was a higher absorptivity for wavelength < 370 nm. This wavelength, ∼ 370 nm, therefore indicated that the band edge for a-ZnO thin films is about 3.35 eV.     

Preliminary studies on molybdenum-doped indium oxide thin films deposited by radio-frequency magnetron sputtering at room temperature

Thin films of molybdenum-doped indium oxide (IMO) were prepared by a 3-source, cylindrical radio-frequency magnetron sputtering at room temperature. The films were post-annealed and were characterized by their structural (X-ray diffraction) and optical (UV-VIS-NIR spectrophotometer) properties. The films were studied as a function of oxygen volume percentage (O₂ vol.%) ranging from 3.5 to 17.5. The structural studies revealed that the as-deposited amorphous films become crystalline on annealing. In most cases, the (222) reflection emerged as high intensive peak. The poor visible transmittance of the films as-deposited without oxygen was increased from ∼ 12% to over 80% on introducing oxygen (3.5 O₂ vol.%). For the films annealed in open air, the average visible transmittance in the wavelength ranging 400-800 nm was varied between 77 and 84%. The films annealed at high temperatures (> 300 °C) decreased the transmittance to as low as < 1%. The optical band gap of the as-deposited films increased from the range 3.83-3.90 to 3.85-3.98 eV on annealing at different conditions.     

Characterization of tin oxide thin films deposited by reactive sputtering

SnO_x Thin films deposited by reactive sputtering are characterized by conversion electron Mössbauer spectroscopy, X-ray diffraction, nuclear resonant scattering and Rutherford backscattering analyses and sheet resistance measurements. The samples were submitted to thermal annealing and exposed to butane gas. The highly disordered as-deposited thin film is modified under thermal processing and gas exposure, changing the oxygen vacancy concentration. This behaviour should affect the steady state response of tin oxide sensors.     

Nonlinear optical properties of laser deposited CuO thin films

In this work we investigate the third-order optical nonlinearities in CuO films by Z-scan method using a femtosecond laser (800 nm, 50 fs, 200 Hz). Single-phase CuO thin films have been obtained using pulsed laser deposition technique. The structure properties, surface image, optical transmittance and reflectance of the films were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and UV-vis spectroscopy. The Z-scan results show that laser-deposited CuO films exhibit large nonlinear refractive coefficient, n₂ = − 3.96 × 10^− 17 m²/W, and nonlinear absorption coefficient, β = − 1.69 × 10^− 10 m/W, respectively.     

Characterization of (Al, Si)N films deposited by balanced magnetron sputtering

Hard and transparent nanocomposite (Al, Si)N films are attractive for optical applications. In this paper, experimental results will be reported on nanocomposite (Al, Si)N films prepared by balanced magnetron sputtering. Microstructure and properties of the films were systematically characterized as a function of Si content of the films. It is shown that the (Al, Si)N films are transparent and exhibit no absorption in a wide range of wavelengths from ~ 0.3 to ~ 9 µm, i.e. from ultraviolet to mid-infrared region. Maximum hardness exceeding 25 GPa has been obtained when the Si content of the films is above 25 at.% and the microstructure of the films undergoes a transformation from nanocrystalline to amorphous states. It is demonstrated that the microstructure detail of the films is different, as compared with that of the films prepared by using unbalanced magnetron sputtering, and the reasons for this discrepancy is discussed.     

Deposition by magnetron sputtering and characterization of indium tin oxide thin films

In this work the properties of indium tin oxide (ITO) films deposed on glass substrates by magnetron sputtering technique in the temperature range below 200 °C are studied by various methods. The physical properties of ITO thin films have been investigated using optical transmittance, photoluminescence, atomic force microscopy, ellipsometry, Hall-effect and four point probe methods. It is established that properties of ITO layers depend drastically on the temperature and oxygen partial pressure during the deposition process and exhibit some peculiarities of the surface morphology. It is found that the band gap energy of this material varies in the energy range from 4.1 to 4.4 eV and depends on the growth conditions. It is suggested that local deviations from the stoichiometry and defects are the main physical reasons of Burstein-Moss shift of the optical band gap.     

Crystallization of amorphous indium zinc oxide thin films produced by radio-frequency magnetron sputtering

In this work we studied indium zinc oxide (IZO) thin films deposited by r.f. magnetron sputtering at room temperature. The films were annealed at high temperature (1100 K) in vacuum, and the oxygen exodiffusion was monitored in-situ. The results showed three main peaks, one at approximately 600 K, other at approximately 850 K and the last one at 940 K, which are probably from oxygen bonded in the film surface and in the bulk, respectively. The initial amorphous structure becomes microcrystalline, according to the X-ray diffraction. The electrical conductivity of the films decreases (about 3 orders of magnitude), after the annealing treatment.This behavior could be explained by the crystallization of the structure, which affects the transport mechanism. Apart from the changes in the material structure, a small variation was observed on the absorption coefficient.     

Plasma influence on the properties and structure of indium tin oxide films produced by reactive middle frequency pulsed magnetron sputtering

Reactive pulsed magnetron sputtering was used to produce conductive and transparent tin-doped indium oxide (ITO) films with low thickness inhomogeneity. Due to the parallel operation of two magnetrons, the deposition system allows in situ investigations of the plasma influence on the film properties. The distribution of the film resistivity, refractive index, structure and stoichiometry along the substrate are presented and related to the spatial distribution of the plasma flow escaping the magnetrons, and the substrate temperature. A higher plasma flow likely causes a localized relaxation of the distorted In-O bonds in amorphous phase which prevails in ITO films prepared at unheated substrates. This leads to a decrease of the film resistivity due to free electrons density and mobility enhancement. The free electron density increase is caused likely by generation of oxygen vacancies. Deposition on a heated substrate (T_s / T_m = 0.3) leads to a change of the film growth mode due to enhanced surface diffusion of the adatoms which results in a textured low resistivity film. This also causes significant improvements of the homogeneity of the film properties that is important for ITO applications.     

Dielectric oxynitride LaTiOxNy thin films deposited by reactive radio-frequency sputtering

LaTiO_xN_y thin films have been deposited by RF sputtering on (001) Nb-doped SrTiO₃ and (001) MgO single-crystalline substrates at high temperature (T_S = 800 °C) under different nitrogen ratios in the plasma (vol.% N₂ = 0, 25, 71). The band gaps ranged from E_g = 3.30 eV for the epitaxial transparent film containing no nitrogen to E_g = 2.65 eV for the textured coloured film containing a moderate amount of nitrogen. Dielectric characterization in the frequency range [100 Hz-1 MHz], using a metal-insulator-metal structure, has shown a stable permittivity and loss tangent of the epitaxial low-nitrided LaTiO_xN_y film with values of ε′ = 135 and tanδ = 1.2 10^− 2 at 100 kHz (RT).     

Heat treatable indium tin oxide films deposited with high power pulse magnetron sputtering

In this study, indium tin oxide (ITO) films were prepared by high power pulse magnetron sputtering [D. J. Christie, F. Tomasel, W. D. Sproul, D. C. Carter, J. Vac. Sci. Technol. A, 22 (2004) 1415. [1]] without substrate heating. The ITO films were deposited from a ceramic target at a deposition rate of approx. 5.5 nm?m/min kW. Afterwards, the ITO films were covered with a siliconoxynitride film sputtered from a silicon alloy target in order to prevent oxidation of the ITO film during annealing at 650 °C for 10 min in air. The optical and electrical properties as well as the texture and morphology of these films were investigated before and after annealing. Mechanical durability of the annealed films was evaluated at different test conditions. The results were compared with state-of-the art ITO films which were obtained at optimized direct current magnetron sputtering conditions.     

Ultraflat indium tin oxide films prepared by ion beam sputtering

Indium tin oxide (ITO) films with a smooth surface (root-mean-square roughness; R_rms=0.40 nm) were made using a combination of the deposition conditions in the ion beam-sputtering method. Sheet resistance was 13.8 Ω/sq for a 150-nm-thick film grown at 150 °C. Oxygen was fed into the growth chamber during film growth up to 15 nm, after which, the oxygen was turned off throughout the rest of the deposition. The surface of the films became smooth with the addition of ambient oxygen but electrical resistance increased. In films grown at 150 °C with no oxygen present, a rough surface (R_rms=2.1 nm) and low sheet resistance (14.4 Ω/sq) were observed. A flat surface (R_rms=0.5 nm) with high sheet resistance (41 Ω/sq) was obtained in the films grown with ambient oxygen throughout the film growth. Surface morphology and microstructure of the films were determined by the deposition conditions at the beginning of the growth. Therefore, fabrication of ITO films with a smooth surface and high electrical conductivity was possible by combining experimental conditions.     

Effects of target bias voltage on indium tin oxide films deposited by high target utilisation sputtering

Indium tin oxide (ITO) films were deposited by reactive High Target Utilisation Sputtering (HiTUS) onto glass and polyimide substrates. The ion plasma was generated by an RF power source while the target bias voltage was varied from 300 V to 500 V using a separate DC power supply. The deposition rate, at constant target power, increased with DC target voltage due to increased ion energy reaching 34 nm/min at 500 V. All the films were polycrystalline and showed strong (400) and (222) reflections with the relative strength of latter increasing with target bias voltage. The resistivity was lowest at 500 V with values of 1.8 × 10^− 4 Ω cm and 2.4 × 10^− 4 Ω cm on glass and polyimide, respectively but was still less than 5 × 10^− 4 Ω cm at 400 V. All films were highly transparent to visible light, (> 80%) but the NIR transmittance decreased with increasing target voltage due to higher free carrier absorption. Therefore, ITO films can be deposited onto semiconductor layers such as in solar cells, with minimal ion damage while maintaining low resistivity.     

Photoelectrochemical properties of nitrogen-doped indium tin oxide thin films prepared by reactive DC magnetron sputtering

Nitrogen-doped indium tin oxide (N-ITO) thin films are deposited on unheated ITO glass substrates in this study. The structural properties of the N-ITO thin films, determined by X-ray diffraction (XRD) and Raman scattering, show that the indium nitride (InN) phase is liable to form in N-ITO films prepared in 20% N₂. A broad XRD peak around 2θ = 33° and Raman peak around 490 cm^− 1 are assigned to the InN phase, but no such peak is observed from the ITO film. Hence, the bandgap is narrowed by N-doping for absorbing light of longer wavelengths of ~ 500 nm. However, under illumination by ultraviolet, the N-ITO film prepared in 20% N₂ exhibits the least photocurrent response, which is less than one third that of the N-ITO catalyst that was doped in 16.4% N₂. This result is attributed mostly to the fact that the valence and conduction band potentials are not positioned properly between the newly formed InN and host ITO phases, rendering inefficient inter-semiconductor electron transfer. Therefore, higher N-doped samples exhibit a lower photocurrent response. Interestingly, the N-ITO film prepared in 16.4% N₂ exhibits the highest photocurrent density of about 165.5 μA/cm² at an applied bias of 1.2 V. This implies that the N-ITO films should be prepared at a low N₂ ratio to ensure a favorable photoelectrochemical activity.     

Growth and characterization of indium tin oxide thin films deposited on PET substrates

Transparent and conductive indium tin oxide (ITO) thin films were deposited onto polyethylene terephthalate (PET) by d.c. magnetron sputtering as the front and back electrical contact for applications in flexible displays and optoelectronic devices. In addition, ITO powder was used for sputter target in order to reduce the cost and time of the film formation processes. As the sputtering power and pressure increased, the electrical conductivity of ITO films decreased. The films were increasingly dark gray colored as the sputtering power increased, resulting in the loss of transmittance of the films. When the pressure during deposition was higher, however, the optical transmittance improved at visible region of light. ITO films deposited onto PET have shown similar optical transmittance and electrical resistivity, in comparison with films onto glass substrate. High quality films with resistivity as low as 2.5 × 10^− 3 Ω cm and transmittance over 80% have been obtained on to PET substrate by suitably controlling the deposition parameters.     

Highly conducting indium tin oxide (ITO) thin films deposited by pulsed laser ablation

Highly conducting and transparent indium tin oxide (ITO) thin films were prepared on SiO₂ glass and silicon substrates by pulsed laser ablation (PLA) from a 90 wt.% In₂O₃-10 wt.% SnO₂ sintered ceramic target. The growths of ITO films under different oxygen pressures (P_O2) ranging from 1×10⁻⁴–5×10⁻² Torr at low substrate temperatures (T_s) between room temperature (RT) and 200°C were investigated. The opto-electrical properties of the films were found to be strongly dependent on the P_O2 during the film deposition. Under a P_O2 of 1×10⁻² Torr, ITO films with low resistivity of 5.35×10⁻⁴ and 1.75×10⁻⁴ Ω cm were obtained at RT (25°C) and 200°C, respectively. The films exhibited high carrier density and reasonably high Hall mobility at the optimal P_O2 region of 1×10⁻² to 1.5×10⁻² Torr. Optical transmittance in excess of 87% in the visible region of the solar spectrum was displayed by the films deposited at Po₂≥1×10⁻² Torr and it was significantly reduced as the P_O2 decreases.     

Temperature effect on structure and surface morphology of indium tin oxide films deposited by reactive ion-beam sputtering

Indium tin oxide (ITO) films were deposited by reactive ion-beam sputtering. The relationship among the surface morphology, the resistivity ρ of the films, the substrate temperature T_S and the film thickness t_F was investigated. The heat power from the ion source during the sputtering was 265 W. T_S increased from 30 to 145 °C with an increase of t_F. The films thinner than 187 nm at T_S lower than 120 °C were amorphous, the film surface was as smooth as the substrate. The films deposited at T_S in the range between 135 and 145 °C were polycrystalline. So, the films thicker than 375 nm were in a multilayer structure of a polycrystalline layer on an amorphous layer. The surface of the polycrystalline films became rough. ρ of the films suddenly decreased at t_F of 375 nm, where the structure of the films changed. Next, the amorphous films with t_F of 39 nm were annealed in the atmosphere. The film structure changed to a polycrystalline structure at annealing temperature T_A of 350 °C. However, the surface roughness of all the films was almost same. As a result, the substrate temperature during the sputtering was important for the deposition of the films with a very smooth surface.     

Remote plasma sputtering of indium tin oxide thin films for large area flexible electronics

Indium tin oxide (ITO) thin films with a specific resistivity of 3.5 × 10^− 4 Ω cm and average visible light transmission (VLT) of 90% have been reactively sputtered onto A4 Polyethylene terephthalate (PET), glass and silicon substrates using a remote plasma sputtering system.This system offers independent control of the plasma density and the target power enabling the effect of the plasma on ITO properties to be studied. Characterization of ITO on glass and silicon has shown that increasing the plasma density gives rise to a decrease in the specific resistivity and an increase in the optical band gap of the ITO films. Samples deposited at plasma powers of 1.5 kW, 2.0 kW and 2.5 kW and optimized oxygen flow rates exhibited specific resistivity values of 3.8 × 10^− 4 Ω cm, 3.7 × 10^− 4 Ω cm and 3.5 × 10^− 4 Ω cm and optical gaps of 3.48 eV, 3.51 eV and 3.78 eV respectively.The increase in plasma density also influenced the crystalline texture and the VLT increased from 70 to 95%, indicating that more oxygen is being incorporated into the growing film. It has been shown that the remote plasma sputter technique can be used in an in-line process to produce uniform ITO coatings on PET with specific resistivities of between 3.5 × 10^− 4 and 4.5 × 10^− 4 Ω cm and optical transmission of greater than 85% over substrate widths of up to 30 cm.     

Properties of indium oxide/tin oxide multilayered films prepared by ion-beam sputtering

The preparation and characterization of indium oxide (InO _x )/tin oxide (SnO _y ) multilayered films deposited by ion-beam sputtering are described and compared with indium tin oxide (ITO) films. The structure and the optoelectrical properties of the films are studied in relation to the layered structures and the post-deposition annealing. Low-angle X-ray diffraction analysis showed that most films retained the regular layered structures even after annealing at 500° C for 16 h. As an example, we obtained a resistivity of 6×10^–4 cm and a transparency of about 85% in the visible range at a thickness of 110 nm in a multilayered film of InO _x (2.0 nm)/SnO _y (0.2 nm)×50 pairs when annealed at 300° C for 0.5 h in air. Hall coefficient measurements showed that this film had a mobility of 17 cm² V^–1 sec^–1 and a carrier concentration (electron density) of 5×10²⁰ cm^–3.