Deposition of aluminum oxide-doped zinc oxide transparent nano-films on glass substrates for electrostatic discharge applications

Aluminum oxide-doped zinc oxide (ZnO:Al₂O₃) transparent thin films were deposited by DC magnetron sputtering on glass substrates; film thickness can be correlated with deposition time. The effect of ZnO:Al₂O₃ film thickness on electrical properties, ultraviolet (UV) transmission, surface morphology and structure, solvent resistance, and scratch hardness was investigated. The surface roughness and crystallite size of deposited films increased from 0.75 to 2.22 nm and from 14 to 57 nm, respectively, as the film thickness was increased from 18 to 112 nm. In contrast, the percent UV transmission (% T) of ZnO:Al₂O₃ deposited glass plates at a wavelength of 365 nm increased when the film thickness was decreased. The electrical properties of nano-film deposited glass plates such as electrical resistance, tribo-charge voltage, and decay time were in the range of electrostatic discharge (ESD) specifications. The ZnO:Al₂O₃ nano-film deposited glass substrate possessed good acetone and iso-propanol resistance as well as high scratch hardness. This work opens up the possibility of using the ZnO:Al₂O₃ transparent ultra-thin film on glass substrate in ESD applications based on their excellent properties in terms of the relatively thin and adjustable ZnO:Al₂O₃ film thickness needed.     

The effects of carrier gas and substrate temperature on ZnO films prepared by ultrasonic spray pyrolysis

ZnO films were deposited on glass substrates in the temperature range of 350–470 °C under an atmosphere of compressed air or nitrogen (N₂) by using ultrasonic spray pyrolysis technique. Structural, electrical and optical properties of the ZnO films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical two-probe and optical transmittance measurements. The ZnO films deposited in the range of 350–430 °C were polycrystalline with the wurtzite hexagonal structure having preferred orientation depending on the substrate temperature. The ZnO films deposited below 400 °C had a preferred (100) orientation while those deposited above 400 °C mostly had a preferred (002) orientation. The resistivity values of ZnO films depended on the types of carrier gas. The ZnO thin films deposited under N₂ atmosphere in the range of 370–410 °C showed dense surface morphologies and resistivity values of 0.6–1.1 Ω-cm, a few orders of magnitude lower than those deposited under compressed air. Hydrogen substition in ZnO possibly contributed to decreasing resistivity in ZnO thin films deposited under N₂ gas. The Hall measurements showed that the behavior of ZnO films deposited at 410 °C under the N₂ atmosphere was n-type with a carrier density of 8.9–9.2×10¹⁶ cm^-3 and mobility of ～70 cm²/Vs. ZnO thin films showed transmission values at 550 nm wavelength in a range of 70–80%. The values of band gaps extrapolated from the transmission results showed bandgap shrinkage in an order of milli electron volts in ZnO films deposited under N₂ compared to those deposited under compressed air. The calculation showed that the bandgap reduction was possibly a result of carrier–carrier interactions.     

Effects of the substrate temperature and solution molarity on the structural opto-electric properties of ZnO thin films deposited by spray pyrolysis

Zinc oxide (ZnO) was largely studied in various applications such as photovoltaic conversion, optoelectronics and piezoelectric, because of its interesting physical properties (morphological, structural, optical and electrical). The present work deals with the preparation of zinc oxide thin films (ZnO) deposited by the spray pyrolysis method. The starting solution was zinc chloride (ZnCl₂). Effects of solution molarity and substrate temperature on films properties were investigated. All films deposited were characterized by various techniques such as X-ray diffraction for structural characterizations, profilometry for thickness measurements, UV–vis transmission spectrophotometry for optical properties and the four probes conductivity measurements for electrical characterization. The X-ray diffraction (XRD) patterns show that the films deposited are polycrystalline with (0 0 2) plan as preferential orientation. The UV–vis spectroscopy confirms the possibility of good transparent ZnO thin films deposition with an average transmission of about ∼85% in the visible region. However, the measured electrical resistivities of the deposited films were in the order of 10⁴ Ω cm     

Characterization of AZO/p-Si heterojunction prepared by DC magnetron sputtering

Al-doped ZnO (AZO) film was deposited by direct-current (DC) magnetron sputtering on p-Si (1 0 0) wafer to fabricate Al-doped n-ZnO/p-Si heterojunctions. The microstructural, optical and electrical properties of the AZO film were characterized by XRD, SEM; UV–vis spectrophotometer; four-point probe and Hall effect measurement, respectively. Results show that the AZO film is of good quality. The electrical junction properties were investigated by I–V measurement, which reveals that the heterojunction shows rectifying behavior under a dark condition. The ideality factor and the saturation current of this diode are 20.1 and 1.19×10⁻⁴ A, respectively. The value of I_F/I_R (I_F and I_R stand for forward and reverse current, respectively) at 5 V is found to be as high as 19.7. It shows fairly good rectifying behavior, indicating formation of a diode between AZO and p-Si. High photocurrent is obtained under a reverse bias when the crystalline quality of AZO film is good enough to transmit light into p-Si.     

Optimization of N2/Ar gas flow ratio for the realization of nitrogen-doped p-type ZnCdO thin films synthesized by RF magnetron sputtering

Nitrogen doped ZnCdO films [ZCO:N] have been grown on quartz substrates by radio frequency (RF) reactive magnetron sputtering technique, and the effect of the ratio of nitrogen to argon gas flow [N₂:Ar] on their electrical, microstructure and optical properties were investigated by Hall effect, energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscope (TEM), optical absorbance and photoluminescence (PL) measurements. The results indicate that all the ZCO:N films are of hexagonal wurtzite structure with highly (002) preferential orientation. As the N₂:Ar increases from 0:1 to 4:1, the absorption edge for the samples exhibits blue shift. Hall effect measurement results indicate that the N₂:Ar exerts an immense influence on the p-type conduction conversion for ZCO:N film. It is found that ZCO:N film deposited at the N₂:Ar of 1:2 shows the optimal p-type behavior, which has a carrier concentration of 1.10×10¹⁷ cm⁻³, a mobility of 3.28 cm²V⁻¹s⁻¹ and a resistivity of 17.3 Ω cm. Compared with the other samples, ZCO:N film fabricated at the relatively lower N₂:Ar possesses the superior crystal quality, luminescent and electrical properties. Additionally, a possible mechanism of p-type conduction for ZCO:N film was discussed in this work.     

Effect of different sputtering gas mixtures on the structural,electrical, and optical properties of p-type NiO thin films

We investigated how mixtures of Ar and O₂ or N₂ gases affect the structural, electrical and optical properties of RF-magnetron-sputtered NiO films. It is shown that the addition of O₂ gas to Ar ambient (namely, Ar:O₂=2:1 to 1:2) slightly reduces the (2 0 0) texturing of the NiO films. The introduction of N₂ gas (from 0 to 2 sccm) to Ar:O₂ (2:1) mixture enhances the (2 0 0) texturing, while the addition of N₂ gas (from 0 to 2 sccm) to Ar ambient slightly weakens the (1 1 1) texturing. The deposition rate is reduced from 6.1 to 1.5 nm/min when O₂ gas is added to Ar ambient. The addition of N₂ gas to the Ar:O₂ (2:1) mixture slightly increases the deposition rate from 1.8 to 2.6 nm/min, whereas adding N₂ gas to Ar only ambient somewhat reduces the rate from 6.1 to 4.4 nm/min. The carrier concentration of the films is increased and the mobility is decreased as the O₂ flow rate in the Ar:O₂ mixture is increased. The addition of N₂ gas to the Ar:O₂ (2:1) mixture increases the resistivity of the films, while adding N₂ gas to Ar ambient decreases the resistivity. The transmittance and optical bandgap of the films are reduced (from 58.4 to 45.5% at 550 nm and from 3.5 to 3.3 eV, respectively) with increasing O₂ flow to Ar ambient. When N₂ gas is added to the Ar:O₂ (2:1) mixture, the transmittance in the visible wavelength range increases from 58.4 to 71.3% and the optical bandgap increases from 3.5 to 3.6 eV. However, adding N₂ gas to the Ar only ambient results in decrease in the transmittance in the visible wavelength region (from 69.3 to 56%) and the optical bandgap (from 3.7 to 3.5 eV).     

Influence of Sn content on properties of ZnO:SnO2 thin films deposited by ultrasonic spray pyrolysis

The present work is devoted to the preparation of zinc oxide (ZnO): tin oxide (SnO₂) thin films by ultrasonic spray technique. A set of films are deposited using a solution formed with zinc acetate and tin chloride salts mixture with varied weight ratio R=[Sn/(Zn+Sn)]. The ratio R is varied from 0 to 100% in order to investigate the influence of Sn concentration on the physical properties of ZnO:SnO₂ films. The X rays diffraction (XRD) analysis indicated that films are composed of ZnO and SnO₂ distinct phases without any alloys or spinnel phase formations. The average grain size of crystallites varies with the ratio R from 17 to 20 nm for SnO₂ and from 24 to 40 nm for ZnO. The obtained films are highly transparent with a transmission coefficient equal to 80%. An increase in Sn concentration increases both the effective band gap energy from 3.2 to 4.01 eV and the photoluminescence intensity peak assigned defects to SnO₂. The films electrical characterization indicated that films are resistive. Their resistivities vary between 1.2×10² and 3.3×10⁴ (Ω cm). The higher resistivity is measured in film deposited with a ratio R equal to 50%.     

Structural and Electrical Properties of Atomic Layer Deposited Al‐Doped ZnO Films

Structural and electrical properties of Al‐doped ZnO (AZO) films deposited by atomic layer deposition (ALD) are investigated to study the extrinsic doping mechanism of a transparent conducting oxide. ALD‐AZO films exhibit a unique layer‐by‐layer structure consisting of a ZnO matrix and Al₂O₃ dopant layers, as determined by transmission electron microscopy analysis. In these layered AZO films, a single Al₂O₃ dopant layer deposited during one ALD cycle could provide ≈4.5 × 10¹³ cm^?2 free electrons to the ZnO. The effective field model for doping is suggested to explain the decrease in the carrier concentration of ALD‐AZO films when the interval between the Al₂O₃ layers is reduced to less than ≈2.6 nm (>3.4 at% Al). By correlating the electrical and structural properties, an extrinsic doping mechanism of ALD‐AZO films is proposed in which the incorporated Al atoms take oxygen from the ZnO matrix and form doubly charged donors, such as oxygen vacancies or zinc interstitials.     

Influence of working pressure on the structural,optical and electrical properties of sputter deposited AZO thin films

Highly oriented crystalline aluminum doped zinc oxide (AZO) films were sputter deposited on glass substrates and a systematic investigation on the as deposited and etched films was reported for its further application in silicon thin film solar cell. Influence of the deposition pressure (from 2 to 8 mTorr) and post-annealing temperature (at 400 °C for 5 min) on the structural, optical and electrical properties of the as-deposited and etched samples were analyzed. The optimum condition for its reproducibility and large area deposition is determined and found that the depositions made at 8 mTorr at 200 W having the distance from source to substrate of 9 cm. All the AZO films exhibited a c-axis preferred orientation perpendicular to the substrate and their crystallinity was improved after annealing. From the XRD pattern the grain size, stress and strain of the films were evaluated and there is no drastic variation. Optical transmittance, resistivity, Hall mobility and carrier concentration for the as deposited and etched-annealed films were found to improve from 79 to 82%; 2.97 to 3.14×10⁻⁴ Ω cm; 25 to 38 cm²/V s; 8.39 to 5.96×10²⁰/cm³ respectively. Based on the triangle diagram between figure of merit and Hall mobility, we obtained a balance of point between the electrical and optical properties to select the deposition condition of film for device application.     

Investigation on a source of dominant donor in vanadium-doped ZnO films grown by reactive RF magnetron sputtering

The influences of O₂ gas addition in argon plasma on reactive RF magnetron sputtering deposition of vanadium-doped ZnO (VZO) films were examined. ZnO or VZO films with vanadium concentration of 2 at% were deposited on a quartz substrate. Vanadium doping caused oxygen deficiency in ZnO and formed a large number of zinc interstitials (Zn_i), oxygen vacancies (V_O), and zinc vacancies (V_Zn). Carrier density of VZO decreased from 9×10²⁰ to 9×10¹⁸ cm⁻³ between O₂ partial pressure ratio (α_O2) of 0.6% and 1.0% in spite of the increase in valence number of vanadium. This result suggests that Zn_i is the dominant donor in VZO since Zn_i is a shallow-level defect. Average optical transmittance (T_v) at wavelength between 450 and 800 nm of VZO was 61% while that of ZnO was 82% without oxygen addition. Although the optical transmittance of VZO was largely deteriorated by optical absorption of V_O, T_v of VZO improved by oxygen addition and reached 85% at α_O2 of 1.0% via suppression of V_O formation.     

Effect of NaOH solution on surface textured ZnO: Al films prepared by pulsed direct current magnetron sputtering

Transparent conducting Al-doped ZnO (ZnO:Al, AZO) thin films were prepared at substrate temperature of 270 °C by pulsed direct current magnetron sputtering. NaOH solution (5 wt%) was employed to etch the AZO films at room temperature, and the surface textured AZO films were obtained successfully. The relationship between the surface textured structures and the etching process controlled by etching time was discussed. The textured morphology of the etched AZO films became clear as increasing the etching time, and the AZO film etched for 30 min exhibited uniformly and distinctly crater-like surface textured structure. Correspondingly, the haze and the resistivity increased with the increasing etching time. And the resistivity of the AZO film etched for 30 min was 3.2×10⁻³ Ω cm.     

8 MeV electron beam induced modifications in the structural,optical and electrical properties of Al doped ZnO thin film

The influence of high energy (8 MeV) electron irradiation, with different dose rates (0 kGy, 1 kGy, 5 kGy, 10 kGy), on the structural, optical and electrical properties of sol-gel spin coated Al-doped ZnO (AZO) thin films have been studied. The X-ray diffraction curve displays the coating of c-axis oriented films under the state of compressive stress. A further analysis reveals that the interstitial sites were occupied by the Al in AZO upon electron irradiation. With the increase in irradiation dose, the energy gap of the film shows a redshift due to the enhanced localized states in the band structure. An increment in the values of refractive index of the films after irradiation is attributed to their enhanced optical density. Steady state luminescence spectra reveal the presence of zinc interstitial and oxygen interstitial defects in the irradiated film. Time-resolved photoluminescence (PL) measurement shows that the dominant defect related recombination mechanism in the irradiated films is arising due to the increased dangling bonds and defect related transitions. The increase in sheet resistance upon electron irradiation is attributed to decreasing carrier concentration in the film. The irradiated AZO film may be useful for space applications and in the radiation environment.     

Magnetron-sputtered high performance Y-doped ZnO thin film transistors fabricated at room temperature

In this report, sputtered-grown undoped ZnO and Y-doped ZnO (ZnO:Y) thin film transistors (TFTs) are presented. Both undoped ZnO and ZnO:Y thin films exhibited highly preferred c-axis oriented (002) diffraction peaks. The ZnO:Y thin film crystallinity was improved with an increase of (002) peak intensity and grain size. The electrical properties of ZnO:Y TFTs were significantly enhanced relative to undoped ZnO TFTs. ZnO:Y TFTs exhibited excellent performance with high mobility of 38.79 cm² V⁻¹ s⁻¹, small subthreshold swing of 0.15 V/decade, and high I_on/I_off current ratio of the order of 8.17 × 10⁷. The O_1s X-ray photoelectron spectra (XPS) showed oxygen vacancy-related defects present in the ZnO:Y TFTs, which contributed to enhancing the mobility of the TFTs.     

Effects of annealing on the characteristics of ZnO films deposited in various O2/(O2+Ar) ratios

C-axis oriented ZnO films are deposited on polished diamond substrates in various O₂/(O₂+Ar) ratios using the radio frequency (RF) magnetron sputtering technique and are subsequently annealed in oxygen ambience under the same conditions. Structural, morphologic and electrical properties of ZnO films are characterized by X-ray diffraction (XRD), high-resistance instrument, energy dispersive X-ray spectroscopy (EDS) and scanning electronic microscopy (SEM). As the O₂/(O₂+Ar) ratio increasing from 1/12 to 5/12, the crystallinity of the as grown ZnO films becomes better and the electrical resistivity increases slowly. After annealing, the ZnO films deposited in O₂/(O₂+Ar) =1/12 and 3/12 are improved greatly in crystallinity, and their electrical resistivity is enhanced by two orders of magnitude, while those deposited in O₂/(O₂+Ar) =5/12 are scarcely changed in crystallinity, and their resistivity is only increased by one order. In addition, the ZnO films deposited in O₂/(O₂+Ar) =3/12 and annealed in oxygen are with the best crystal quality and the highest resistivity.     

Tuning optical,electrical and magnetic properties of fiber structured ZnO film by deposition temperature and precursor concentration

Highly transparent ZnO films were deposited on glass substrates using zinc acetate solution through cost effective spray pyrolysis method. A comprehensive study was carried out to understand the effects of deposition temperature and precursor concentrations on structure, surface morphology, optical, electrical and magnetic properties of the deposited films. All deposited films were polycrystalline in nature with hexagonal wurtzite structure. The films were preferentially oriented along (1 0 1) plane up to 723 K beyond which orientation changed to (0 0 2) plane. Irrespective of precursor concentration used, the films deposited at 673 K and 723 K showed fibrous structure. The films deposited at higher temperature led to enhanced transmittance and optical energy band gap. With higher precursor concentrations the transmittance decreased while the band gap increased. Photoluminescence studies revealed the presence of various defects leading to emission in the visible region apart from band to band transition near UV region. Lowest electrical resistivity was obtained for films deposited at 723 K which is of the order 10² Ω cm. At room temperature, all deposited films were diamagnetic while they were paramagnetic at 5 K.     

Improvement in crystal quality of ZnO film on Si substrate by using a homo-buffer layer

ZnO thin films without and with a homo-buffer layer have been prepared on Si(1 1 1) substrates by pulsed laser deposition (PLD) under various conditions. Photoluminescence (PL) measurement indicates that the optical quality of ZnO thin film is dramatically improved by introducing oxygen into the growth chamber. The sample deposited at 60 Pa possesses the best optical properties among the oxygen pressure range studied. X-ray diffraction (XRD) results show that the films directly deposited on Si are of polycrystalline ZnO structures. A low-temperature (500 °C) deposited ZnO buffer layer was used to enhance the crystal quality of the ZnO film. Compared to the film without the buffer layer, the film with the buffer layer exhibits aligned spotty reflection high-energy electron diffraction (RHEED) pattern and stronger near-band-edge emission (NBE) with a smaller full-width at half-maximum (FWHM) of 98 meV. The structural properties of ZnO buffer layers grown at different temperatures were investigated by RHEED patterns. It is suggested that the present characteristics of the ZnO epilayer may be raised further by elevating the growth temperature of buffer layer to 600 °C.     

Enhancement in optical characteristics of c-axis-oriented radio frequency–sputtered ZnO thin films through growth ambient and annealing temperature optimization

High-quality radio frequency–sputtered ZnO were grown on Si substrates at 400 °C at various partial gas pressures (Ar/Ar+O2). Subsequently, to remove as-grown defects, high temperature annealing from 700 to 900 °C on as-grown samples in constant oxygen flow for 10 s was performed. X-ray diffraction study confirmed the formation of highly crystalline films with a dominant peak at (002). The sample grown in 50% Ar and 50% O₂ ambient exhibited the lowest linewidth (2θ=~0.2728°) and highest stoichiometry. Grain size of the as grown samples decreased with increase in the partial pressure of oxygen till a certain ratio (1:1), and photoluminescence (PL) improved with increase in annealing temperature. Low-temperature (18 K) PL measurements showed a near-band-edge emission peak at 3.37 eV, and the highest peak intensity (more than six orders compared to others with narrow linewidth of ~0.01272 eV) was exhibited by the sample annealed at 900 °C and was six orders higher than that of the as-grown sample. All as-grown samples exhibited dominant visible-range peaks due to emission from defect states.     

Thermal annealing effect on zinc nitride thin films deposited by reactive rf-magnetron sputtering process

Zinc nitride films were deposited by reactive radio-frequency magnetron sputtering using a zinc target in a nitrogen and argon plasma. The deposited films were annealed in either air or O₂ at 300 °C to investigate the annealing effect on the microstructure, optical properties, and electronic characteristics of zinc nitride films. It was found that the annealing process decreased the crystallinity of zinc nitride films. It was also found that the optical band gap decreased from 1.33 eV to 1.14 eV after annealing. The analysis of film composition suggested that the concentration of oxygen increased slightly after annealing. Although the conduction type of both as-deposited and annealed films were n-type, the annealed films exhibited a higher resistivity, lower carrier concentration and lower mobility than the as-deposited films. Also, it was found that the as-deposited films did not exhibit any photoconducting behavior whereas the annealed films exhibited a pronounced photoconducting behavior.     

Thickness-dependent optoelectronic properties of CuCr0.93Mg0.07O2 thin films deposited by reactive magnetron sputtering

CuCr_0.93Mg_0.07O₂ thin films were successfully deposited by DC reactive magnetron sputtering at 1123 K from metallic targets. The influence of film thickness on the structural and optoelectronic properties of the films was investigated. X-ray diffraction (XRD) results revealed that all the films had a delafossite structure with no other phases. The optical and electrical properties were investigated by UV–VIS spectrophotometer and Hall measurement, respectively. It was found that the optoelectronic properties exhibited a thickness-dependent behavior. The optical band gap and the average transmittance of the films showed a monotonous decrease with respect to the increase in thickness. The average transmittance in the visible region decreased from 67% to 47% as the thickness increased from ~70 nm to ~280 nm. Simultaneously, the conductivity of the films fell from 1.40 S∙cm⁻¹ to 0.27 S∙cm⁻¹. According to Haacke's figure of merit (FOM), a film with a maximum FOM value of about 1.72×10⁻⁷ Ω⁻¹ can be achieved when the thickness is about 70 nm (σ≈ 1.40 S·cm⁻¹ and T_av. ≈67%).     

Effect of substrate temperature on the properties of ZnO thin films prepared by spray pyrolysis

Sprayed ZnO films were grown on glass at different substrate temperatures from 200 °C to 500 °C and their structural, optical and electrical properties were investigated. All films are polycrystalline with hexagonal wurtzite structure. ZnO films at substrate temperatures above 400 °C appear to be better crystalized with (002) plane as preferential orientation. Optical transmission spectrum shows that ZnO films have high transmission (above 80%) in visible region for substrate temperatures above 400 °C. Photoluminescence spectra at room temperature show an ultraviolet emission and two visible emissions at 2.82 eV and 2.37 eV. The resistivity of ZnO films increases with increasing substrate temperatures (above 400 °C). The ZnO film deposited at 400 °C shows highest figure of merit.