Structure and properties of GZO thin films grown on ZnO buffer layers

Thin gallium-doped zinc oxide (in GZO the Ga₂O₃ contents are approximately 3 wt%) films having different ZnO buffer layers were deposited using radio frequency (rf) magnetron sputtering. The use of a grey-based Taguchi method to determine the processing parameters of ZnO buffer layer deposition has been studied by considering multiple performance characteristics. A Taguchi method with an L₉ orthogonal array, signal-to-noise (S/N) ratio, and analysis of variance (ANOVA) is employed to investigate the performance characteristics in the deposition operations. The effect and optimization of ZnO buffer deposition parameters (rf power, sputtering pressure, thickness, and annealing) on the structure, morphology, electrical resistivity, and optical transmittance of the GZO films are studied. Annealing treatment and reduction in thickness resulted in a decrease in root-mean-square (RMS) surface roughness of the ZnO buffer layer. Using the optimal ZnO buffer layer obtained by the application of the grey-based Taguchi method, the electrical resistivity of GZO films was decreased from 2.94×10⁻³ to 9.44×10⁻⁴ Ω cm and the optical transmittance in the visible region was slightly increased from 84.81% to 85.82%.     

Structural, electrical and optical properties of Ga-doped ZnO films on PET substrate

The effects of O₂ plasma pretreatment on the properties of Ga-doped ZnO films on PET substrate were studied. Ga-doped ZnO films were fabricated by RF magnetron sputtering process. To improve surface energy and adhesion of PET substrate, O₂ plasma pretreatment process was used prior to GZO sputtering. With increasing O₂ plasma treatment time, the contact angle decreases and the RMS surface roughness increases significantly. The transmittance of GZO films on PET substrate in a wavelength of 550 nm was 70-84%. With appropriate O₂ plasma treatment, the resistivity of GZO films on PET substrate was 3.4 × 10⁻³ Ω cm.     

Optimization of parameters for deposition of Ga-doped ZnO films by DC reactive magnetron sputtering using Taguchi method

Ga-doped ZnO (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. Taguchi method was used to find the optimal deposition parameters including oxygen partial pressure, argon partial pressure, substrate temperature, and sputtering power. By employing the analysis of variance, we found that the oxygen and argon partial pressures were the most influencing parameters on the electrical properties of ZnO:Ga films. Under the optimized deposition conditions, the ZnO:Ga films showed acceptable crystal quality, lowest electrical resistivity of 2.61 × 10⁻⁴ Ω cm, and high transmittance of 90% in the visible region.     

Effect of composition and deposition temperature on the characteristics of Ga doped ZnO thin films

ZnO films doped with Ga (GZO) of varying composition were prepared on Corning glass substrate by radio frequency magnetron sputtering at various deposition temperatures of room temperature, 150, 250 and 400 °C, and their temperature dependent photoelectric and structural properties were correlated with Ga composition. With increasing deposition temperature, the Ga content, at which the lowest electrical resistivity and the best crystallinity were observed, decreased. Films with optimal electrical resistivity of 2-3 × 10⁻⁴ Ω cm and with good crystallinity were obtained in the substrate temperature range from 150 to 250 °C, and the corresponding C_Ga/(C_Ga + C_Zn) atomic ratio was about 0.049. GZO films grown at room temperature had coarse columnar structure and low optical transmittance, while films deposited at 400 °C yielded the highest figure of merit (FOM) due to very low optical absorption despite rather moderate electrical resistivity slightly higher than 4 × 10⁻⁴ Ω cm. The optimum Ga content at which the maximum figure of merit was obtained decreased with increasing deposition temperature.     

Electrical and optical properties of Ga doped zinc oxide thin films deposited at room temperature by continuous composition spread

Ga doped ZnO (GZO) thin films were deposited on glass substrates at room temperature by continuous composition spread (CCS) method. CCS is thin films growth method of various Ga_xZn_1−xO(GZO) thin film compositions on a substrate, and evaluating critical properties as a function position, which is directly related to material composition. Various compositions of Ga doped ZnO deposited at room temperature were explored to find excellent electrical and optical properties. Optimized GZO thin films with a low resistivity of 1.46 × 10⁻³ Ω cm and an average transmittance above 90% in the 550 nm wavelength region were able to be formed at an Ar pressure of 2.66 Pa and a room temperature. Also, optimized composition of the GZO thin film which had the lowest resistivity and high transmittance was found at 0.8 wt.% Ga₂O₃ doped in ZnO.     

Low-temperature deposition of transparent conducting ZnO:Zr films on PET substrates by DC magnetron sputtering

Transparent conducting zirconium-doped zinc oxide (ZnO:Zr) films were firstly deposited on polyethylene terephthalate (PET) substrates with ZnO buffer layers by DC magnetron sputtering at room temperature. Dependence of physical properties of ZnO:Zr films on deposition pressure was systematically studied. All the deposited films were polycrystalline and (1 0 0) oriented. When deposition pressure increases from 1 to 2.5 Pa, the crystallinity of the films improves and the resistivity decreases. While deposition pressure increases from 2.5 to 3.5 Pa, the crystallinity of the films deteriorates and the resistivity increases. The lowest resistivity of 1.8 × 10⁻³ Ω cm was obtained for the films deposited at the optimum deposition pressure of 2.5 Pa. All the films present a high transmittance of above 86% in the wavelength range of the visible spectrum.     

Preparation and characterization of n-type conductive (Al, Co) co-doped ZnO thin films deposited by sputtering from aerogel nanopowders

Highly transparent, n-type conducting ZnO thin films were obtained by low temperature magnetron sputtering of (Co, Al) co-doped ZnO nanocrystalline aerogels. The nanoparticles of ∼30 nm size were synthesized by a sol-gel method using supercritical drying in ethyl alcohol. The structural, optical and electrical properties of the films were investigated. The ZnO films were polycrystalline textured, preferentially oriented with the (0 0 2) crystallographic direction normal to the film plane. The films show within the visible wavelength region an optical transmittance of more than 90% and a low electrical resistivity of 3.5 × 10⁻⁴ Ω cm at room temperature.     

Properties of dc magnetron sputtered Cu2O films prepared at different sputtering pressures

The sputtering pressures maintained during the deposition of Cu₂O films, by dc reactive magnetron sputtering, influence the structural, electrical and optical properties. The crystalline orientation mainly depends on the sputtering pressure. The films deposited at a sputtering pressure of 4 Pa showed single-phase Cu₂O films along (1 1 1) direction. The electrical resistivity of the films increased from 1.1 × 10¹ Ω cm to 3.2 × 10³ Ω cm. The transmittance of the films increased from 69% to 88% with the increase of sputtering pressure from 2.5 Pa to 8 Pa.     

Effect of mesh patterning with UV pulsed-laser on optical and electrical properties of ZnO/Ag-Ti thin films

In this study, the ZnO/Ag-Ti structure for transparence conducting oxide (TCO) is investigated by optimizing the thickness of the Ag-Ti alloy and ZnO layers. The Ag-Ti thin film is deposited by DC magnetron sputtering and its thicknesses is well controlled. The ZnO thin film is prepared by sol-gel method using zinc acetate as cation source, 2-methoxiethanol as solvent and monoethanolamine as solution stabilizer. The ZnO film deposition is performed by spin-coating technique and dried at 150 °C on Corning 1737 glass. Due to the conductivity of ZnO/Ag-Ti is dominated by Ag-Ti, the sheet resistance of ZnO/Ag-Ti decrease dramatically as the thickness of Ag-Ti layer increases. However, the transmittances of ZnO/Ag-Ti become unacceptable for TCO application after the thickness of Ag-Ti layer beyond 6 nm. The as-deposited ZnO/Ag-Ti structure has the optical transmittance of 83% @ 500 nm and the low resistivity of 1.2 × 10⁻⁵ Ω-cm. Furthermore, for improving the optical and electrical properties of ZnO/Ag-Ti, the thermal treatment using laser is adopted. Experimental results indicate that the transmittance of ZnO/Ag-Ti is improved from 83% to 89% @ 500 nm with resistivity of 1.02 × 10⁻⁵ Ω-cm after laser drilling. The optical spectrum, the resistance, and the morphology of the ZnO/Ag-Ti will be reported in the study.     

Effect of GZO thickness and annealing temperature on the structural,electrical and optical properties of GZO/Ag/GZO sandwich films

The GZO/Ag/GZO sandwich films were deposited on glass substrates by RF magnetron sputtering of Ga-doped ZnO (GZO) and ion-beam sputtering of Ag at room temperature. The effect of GZO thickness and annealing temperature on the structural, electrical and optical properties of these sandwich films was investigated. The microstructures of the films were studied by X-ray diffraction (XRD). X-ray diffraction measurements indicate that the GZO layers in the sandwich films are polycrystalline with the ZnO hexagonal structure and have a preferred orientation with the c-axis perpendicular to the substrates. For the sandwich film with upper and under GZO thickness of 40 and 30 nm, respectively, it owns the maximum figure of merit of 5.3 × 10⁻² Ω⁻¹ with a resistivity of 5.6 × 10⁻⁵ Ω cm and an average transmittance of 90.7%. The electrical property of the sandwich films is improved by post annealing in vacuum. Comparing with the as-deposited sandwich film, the film annealed in vacuum has a remarkable 42.8% decrease in resistivity. The sandwich film annealed at the temperature of 350 °C in vacuum shows a sheet resistance of 5 Ω/sq and a transmittance of 92.7%, and the figure of merit achieved is 9.3 × 10⁻² Ω⁻¹.     

Transparent conductive ZnO:Al films grown by atomic layer deposition for Si-wire-based solar cells

Structural, electrical, and optical properties of atomic layer-controlled Al-doped ZnO (ZnO:Al) films grown by atomic layer deposition (ALD) on glass substrates were characterized at various growth temperatures for use as transparent electrodes. The Al atomic content in ZnO:Al films increased due to the reduced ZnO film growth rate with increasing temperature. The preferred orientation of ZnO:Al films was changed, and the optimum condition for best crystallinity was identified by varying the growth temperature. Furthermore, the carrier concentration of free electron was increased by substituting the Zn sites with Al atoms in the crystal, resulting from monolayer growth based on alternate self-limiting surface chemical reactions. The electrical resistivity of ZnO:Al film grown by ALD at 225 °C reached the lowest value of 8.45 × 10⁻⁴ Ω cm, with a carrier mobility of 9.00 cm² V⁻¹ s⁻¹ and optical transmittance of ∼93%. This result demonstrates that ZnO:Al films grown by ALD possess excellent potential for applications in electronic devices and displays as transparent electrodes and surface passivation layers.     

The influence of titanium on the properties of zinc oxide films deposited by radio frequency magnetron sputtering

TiO₂-doped zinc oxide thin films were deposited on glass substrates by radio frequency (RF) magnetron sputtering with TiO₂-doped ZnO targets in an argon atmosphere. The structural properties of TiO₂-doped ZnO films doped with different TiO₂ contents were investigated. The experimental results show that polycrystalline TiO₂-doped ZnO films had the (0 0 2) preferred orientation. The deposition parameters such as the working pressure and substrate temperature of TiO₂-doped ZnO films were also investigated. The crystalline structure of the TiO₂-doped ZnO films gradually improved as the working pressure was lowered and the substrate temperature was raised. The lowest electrical resistivity for the TiO₂-doped ZnO films was obtained when the Ti addition was 1.34 wt%; its value was 2.50 × 10⁻³ Ω cm, smaller than that found in previous studies. The transmittance of the TiO₂-doped ZnO films in the visible wavelength range was more than 80%. The optical energy gap was related to the carrier concentration, and was in the range of 3.30-3.48 eV.     

Highly conductive and transparent laser ablated nanostructured Al: ZnO thin films

Al doped ZnO thin films are prepared by pulsed laser deposition on quartz substrate at substrate temperature 873 K under a background oxygen pressure of 0.02 mbar. The films are systematically analyzed using X-ray diffraction, atomic force microscopy, micro-Raman spectroscopy, UV-vis spectroscopy, photoluminescence spectroscopy, z-scan and temperature-dependent electrical resistivity measurements in the temperature range 70-300 K. XRD patterns show that all the films are well crystallized with hexagonal wurtzite structure with preferred orientation along (0 0 2) plane. Particle size calculations based on XRD analysis show that all the films are nanocrystalline in nature with the size of the quantum dots ranging from 8 to 17 nm. The presence of high frequency E₂ mode and longitudinal optical A₁ (LO) modes in the Raman spectra suggest a hexagonal wurtzite structure for the films. AFM analysis reveals the agglomerated growth mode in the doped films and it reduces the nucleation barrier of ZnO by Al doping. The 1% Al doped ZnO film presents high transmittance of ∼75% in the visible and near infrared region and low dc electrical resistivity of 5.94 × 10⁻⁶ Ω m. PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. Nonlinear optical measurements using the z-scan technique shows optical limiting behavior for the 5% Al doped ZnO film.     

Influence of post-annealing on the properties of Sc-doped ZnO transparent conductive films deposited by radio-frequency sputtering

Sc-doped ZnO transparent conductive films are deposited on glass substrates by radio-frequency sputtering. The influence of post-annealing on the structural, morphologic, electrical, and optical properties of the films is investigated by energy dispersion X-ray spectroscopy, X-ray diffraction, Hall measurement, and optical transmission spectroscopy. The experimental results show that these films are polycrystalline with a preferred [0 0 1] orientation. The lowest resistivity of 2.6 × 10⁻⁴ Ω cm is obtained from the film annealed at 500 °C. The average optical transmittance of the films is over 90%. These results suggest that Sc-doped ZnO is a good candidate for fabricating high performance transparent conductive films.     

Characteristics of ZnO:Al thin films co-doped with hydrogen and fluorine

Fluorine and hydrogen co-doped ZnO:Al (AZO) films were prepared by radio frequency (rf) magnetron sputtering of ZnO targets containing 1 wt.% Al₂O₃ on Corning glass at substrate temperature of 150 °C with Ar/CF₄/H₂ gas mixtures, and the structural, electrical and optical properties of the as-deposited and the vacuum-annealed films were investigated. In as-deposited state, films with fairly low resistivity of 3.9-4 × 10⁻⁴ Ω cm and very low absorption coefficient below 900 cm⁻¹ when averaged in 400-800 nm could be fabricated. After vacuum-heating at 300 °C, the minimum resistivity of 2.9 × 10⁻⁴ Ω cm combined with low absorption loss in visible region, which enabled the figure of merit to uplift as high as 4 Ω⁻¹, could be obtained for vacuum-annealed film. It was shown that, unlike hydrogenated ZnO films which resulted in degradation upon heating in vacuum at moderately high temperature, films with fluorine addition could yield improved electrical properties mostly due to enhanced Hall mobility while preserving carrier concentration level. Furthermore, stability in oxidizing environment could be improved by fluorine addition, which was ascribed to the filling effect of dangling bonds at the grain boundaries. These results showed that co-doping of hydrogen and fluorine into AZO films with low Al concentration could be remarkably compatible with thin film solar cell applications.     

Surface textured ZnO:Al thin films by pulsed DC magnetron sputtering for thin film solar cells applications

Transparent conducting thin films of ZnO:Al (Al-doped ZnO, AZO) were prepared via pulsed DC magnetron sputtering with good transparency and relatively lower resistivity. The AZO films with 800 nm in thickness were deposited on soda-lime glass substrates keeping at 473 K under 0.4 Pa working pressure, 150 W power, 100 μs duty time, 5 μs pulse reverse time, 10 kHz pulse frequency and 95% duty cycle. The as-deposited AZO thin films has resistivity of 6.39 × 10⁻⁴ Ω cm measured at room temperature with average visible optical transmittance, T_total of 81.9% under which the carrier concentration and mobility were 1.95 × 10²¹ cm⁻³ and 5.02 cm² V⁻¹ s⁻¹, respectively. The films were further etched in different aqueous solutions, 0.5% HCl, 5% oxalic acid, 33% KOH, to conform light scattering properties. The resultant films etched in 0.5% HCl solution for 30 s exhibited high T_total = 78.4% with haze value, H_T = 0.1 and good electrical properties, ρ = 8.5 × 10⁻⁴ Ω cm while those etched in 5% oxalic acid for 150 s had desirable H_T = 0.2 and relatively low electrical resistivity, ρ = 7.9 × 10⁻⁴ Ω cm. However, the visible transmittance, T_total was declined to 72.1%.     

Substitution mechanism of Ga for Zn site depending on deposition temperature for transparent conducting oxides

High quality transparent conductive gallium-doped zinc oxide (GZO) thin films were deposited on glass substrates using rf-magnetron sputtering system at the temperature ranging from room temperature (RT) to 500 °C. The temperature-dependence of Ga doping effect on the structural, optical and electrical properties in ZnO has been investigated. For the GZO thin films deposited at over 200 °C, (103) orientation was strongly observed by X-ray diffraction analysis, which is attributed to the substitution of Ga elements into Zn site. X-ray photoelectron spectroscopy measurements have confirmed that oxygen vacancies were generated at the temperature higher than 300 °C. This might be due to the effective substitution of Ga³⁺ for Zn site at higher temperature. It was also found that the optical band gap increases with deposition temperature. The optical transmittance of GZO thin films was above 87% in the visible region. The GZO thin films grown at 500 °C showed a low electrical resistivity of 4.50 × 10^?4 Ω cm, a carrier concentration of 6.38 × 10²⁰ cm^?3 and a carrier mobility of 21.69 cm²/V.     

Growth characteristics and properties of ZnO:Ga thin films prepared by pulsed DC magnetron sputtering

Transparent conductive ZnO:Ga thin films were deposited on Corning 1737 glass substrate by pulsed direct current (DC) magnetron sputtering. The effects of process parameters, namely pulse frequency and film thickness on the structural and optoelectronic properties of ZnO:Ga thin films are evaluated. It shows that highly c-axis (0 0 2) oriented polycrystalline films with good visible transparency and electrical conductivity were prepared at a pulsed frequency of 10 kHz. Increasing the film thickness also enlarged the grain size and carrier mobility which will subsequently lead to the decrease in resistivity. In summary, ZnO:Ga thin film with the lowest electrical resistivity of 2.01 × 10⁻⁴ Ω cm was obtained at a pulse frequency of 10 kHz with 500 nm in thickness. The surface RMS (root mean square) roughness of the film is 2.9 nm with visible transmittance around 86% and optical band gap of 3.83 eV.     

Influence of the grain boundary barrier height on the electrical properties of Gallium doped ZnO thin films

The pulsed laser deposition (PLD) technique is used to deposit Gallium doped zinc oxide (GZO) thin films on glass substrates at 250 with different Gallium (Ga) doping concentration of 0, 1.0, 3.0 and 5.0%. The influence of Ga doping concentration on structure, chemical atomic compositions, electrical and optical properties was investigated by XRD, XPS, Hall measurement and UV spectrophotometer, respectively. The relationship between electrical properties and Ga doping concentration was clarified by analyzing the chemical element compositions and the chemical states on the GZO films. It is found that the carrier concentrations and oxygen vacancies in the GZO films increase with increasing Ga doping concentration. The lowest resistivity (3.63 × 10⁻⁴ Ω cm) and barrier height of grain boundaries (14 mV) were obtained with 3% Ga doping. In particular, we suppose the band gap of 5% Ga doping sample larger than that of 3% Ga doping sample is due to the quantum size effect from the amorphous structure rather than Moss-Burstein shift.     

Room temperature growth and properties of ZnO films by pulsed laser deposition

ZnO thin films were prepared by pulsed laser deposition at room temperature on glass substrates with oxygen pressures of 10-30 Pa. The structural, electrical, and optical properties of ZnO films were studied in detail. ZnO films had an acceptable crystal quality with high c-axis orientation and smooth surface. The resistivity was in the 10² Ω cm order for ZnO films, with the electron concentration of 10¹⁶-10¹⁷ cm⁻³. All the films showed a high visible transmittance ∼90% and a high UV absorption about 90-100%. The UV emission ∼390 nm was observed in the photoluminescence spectra. The oxygen pressures in the 10-30 Pa range were suitable for room temperature growth of high-quality ZnO films.