Structural and optical characterization of Al-doped ZnO films prepared by thermal oxidation of evaporated Zn/Al multilayered films

Aluminum-doped zinc oxide (ZnO:Al) thin films (t = 68–138 nm) were prepared by thermal oxidation in air flow, at 720 K, of the multilayered metallic Zn/Al thin stacks deposited in vacuum onto glass substrates by physical vapor deposition. The effect of Al content (3.7–8.2 at.%) on the structural (crystallinity, texture, stress, surface morphology) and optical (transmittance, absorbance, energy band gap) characteristics of doped ZnO thin films was investigated. The X-ray diffraction spectra revealed that the Al-doped ZnO films have a hexagonal (wurtzite) structure with preferential orientation with c-axis perpendicular to the substrate surface. A tensile residual stress increasing with Al content was observed. The films showed a high transmittance (about 90%) in the visible and NIR regions. The optical band gap value was found to decrease with Al content from 3.22 eV to 3.18 eV. The results are discussed in correlation with structural characteristics and Al content in the films.     

Effect of heat treatment on microstructural and optical properties of CBD grown Al-doped ZnO thin films

Investigations on the effect of annealing temperature on the structural, optical properties and morphology of Al-doped ZnO thin films deposited on glass substrate by chemical bath deposition have been carried out. X-ray diffraction studies revealed that deposited films are in polycrystalline nature with hexagonal structure along the (0 0 2) crystallographic plane. Microstructural properties of films such as crystallite size, texture coefficient, stacking fault probability and microstrain were calculated from predominant (0 0 2) diffraction lines. The UV-Vis-NIR spectroscopy studies revealed that all the films have high optical transmittance (>60%) in the visible range. The optical band gap values are found to be in the range of 3.25-3.31 eV. Optical constants have been estimated and the values of n and k are found to increase with increase of heat treatment. The films have increased transmittance with increase of heat treatment. Al-doped ZnO thin films fabricated by this simple and economic chemical bath deposition technique without using any carrier gas are found to be good in structural and optical properties which are desirable for photovoltaic applications. Scanning electron microscopic images revealed that the hexagonal shaped grains that occupy the entire surface of the film with its near stoichiometric composition.     

Preparation and character of textured ZnO:Al thin films deposited on flexible substrates by RF magnetron sputtering

ZnO:Al thin films deposited on transparent TPT substrates by magnetron sputtering were etched in acetic acid solution. The effects of etching solution concentration and etching time on the structure and properties of ZnO:Al films were investigated. The obtained films had a hexagonal structure and a highly preferred orientation with the c-axis perpendicular to the substrate. The ZAO film etched in 1% acetic acid solution for 10 s had a pyramidal structure and an enhanced light scattering ability, the average transmittance and reflectance in the visible region were 72% and 26% respectively, the sheet resistance was 260 Ω/□. Both transmittance and reflectance of the films decreased as the etching solution concentration and etching time increasing. Etching had a negative effect on the conductive properties of ZAO films. The lowest sheet resistance was 120 Ω/□ for the ZAO film without etching.     

Structural, electrical and optical properties of ZnO:Al films deposited on flexible organic substrates for solar cell applications

Aluminum doped ZnO thin films (ZnO:Al) were deposited on glass and poly carbonate (PC) substrate by r.f. magnetron sputtering. In addition, the electrical, optical properties of the films prepared at various sputtering powers were investigated. The XRD measurements revealed that all of the obtained films were polycrystalline with the hexagonal structure and had a preferred orientation with the c-axis perpendicular to the substrate. The ZnO:Al films were increasingly dark gray colored as the sputter power increased, resulting in the loss of transmittance. High quality films with the resistivity as low as 9.7 × 10^− 4 Ω-cm and transmittance over 90% have been obtained by suitably controlling the r.f. power.     

Highly transparent conductive and near-infrared reflective ZnO:Al thin films

Al-doped ZnO (AZO) thin films have been prepared on glass substrates by pulsed laser deposition. The structural, optical, and electrical properties were strongly dependent on the growth temperatures. The lowest resistivity of 4.5 × 10⁻⁴ Ωcm was obtained at an optimized temperature of 350 °C. The AZO films deposited at 350 °C also had the high optical transmittance above 87% in the visible range and the low transmittance (<15% at 1500 nm) and high reflectance (∼50% at 2000 nm) in the near-IR region. The good IR-reflective properties of ZnO:Al films show that they are promising for near-IR reflecting mirrors and heat reflectors.     

Effect of annealing temperature on ZnO:Al/p-Si heterojunctions

Al-doped, zinc oxide (ZnO:Al) films with a 1.2 at.% Al concentration were deposited on p-type silicon wafers using a sol-gel dip coating technique to produce a ZnO:Al/p-Si heterojunction. Following deposition and subsequent drying processes, the films were annealed in vacuum at five different temperatures between 550 and 900 °C for 1 h. The resistivity of the films decreased with increasing annealing temperature, and an annealing temperature of 700 °C provided controlled current flow through the ZnO:Al/p-Si heterojunction up to 20 V. The ZnO:Al film deposited on a p-type silicon wafer with 1.2 at.% Al concentration was concluded to have the potential for use in electronic devices as a diode after annealing at 700 °C.     

Growth behaviors and characteristics of low temperature spin-sprayed ZnO and Al-doped ZnO microstructures

The influence of growth parameters of the spin-spray technique upon the microstructure and electrical and optical properties of ZnO and Al-doped ZnO microstructures was investigated. This investigation was carried out by varying the pH and concentration of the solutions utilized. With increasing pH from 9 to 12, the ZnO films changed from membrane-like microstructures at a pH of 9 to single crystal ZnO rods with hexagonal ends at the pH of 10, and to polycrystal ZnO needle-like tips with random crystalline orientation at the pH of 12. Varying the concentration of the solution brought about a dramatic change in the crystal growth behavior and crystalline orientation, with the least concentration producing rods more uniform and oriented in the c-axis direction. The optical absorption dependence of the ZnO microstructures was also studied by ultraviolet visible spectrophotometer. This investigation will enable optimized low temperature (<100 °C) fabrication of ZnO films by the spin-spray technique with controllable microstructure and properties based on their processing conditions. Furthermore, the influence of Al doping on the electric property, optical property microstructures of the Al-doped ZnO thin films was examined. Increase in Al concentration from 0 to 2 % further reduced the resistivity of the ZnO films by 3 orders of magnitudes from 3.4 × 10⁴ to 14 Ω cm; while the Hall mobility increases from 1 to 140 cm²/V s at the same time. The optical photoluminescence measurement of Al-doped ZnO thin films in ultra violet (UV) was also demonstrated.     

Effect of the [Al/Zn] ratio in the starting solution and deposition temperature on the physical properties of sprayed ZnO:Al thin films

Aluminum-doped zinc oxide thin films (ZnO:Al) were deposited on sodocalcic glass substrates by the chemical spray technique, using zinc acetate and aluminum pentanedionate as precursors. The effect of the [Al/Zn] ratio in the starting solution, as well as the substrate temperature, on the physical characteristic of ZnO:Al thin films was analyzed. We have found that the addition of Al to the starting solution decreases the electrical resistivity of the films until a minimum value, located between 2 and 3 at.%; a further increase in the [Al/Zn] ratio leads to an increase in the resistivity. A similar resistivity tendency with the substrate temperature was encountered, namely, as the substrate temperature is increased, a minimum value of around 475 °C in almost all the cases, was obtained. At higher deposition temperatures the film resistivity suffers an increase. After a vacuum-thermal treatment, performed at 400 °C for 1 h, the films showed a resistivity decrease about one order of magnitude, reaching a minimum value, for the films deposited at 475 °C, of 4.3 × 10^− 3 Ω cm.The film morphology is strongly affected by the [Al/Zn] ratio in the starting solution. X-ray analysis shows a (002) preferential growth in all the films. As the substrate temperature increases it is observed a slight increase in the transmittance as well as a shift in the band gap of the ZnO:Al thin films.     

Al-doped ZnO films by pulsed laser deposition at room temperature

Polycrystalline Al-doped ZnO films with good photoluminescence property were successfully deposited on quartz glass substrates by pulsed laser deposition (PLD) at room temperature. The films were obtained by ablating a metallic target (Zn:Al 3 wt%) at various laser energy densities (1.0-2.1 J/cm²) in oxygen atmosphere (9 Pa). The structure of the films was characterized by XRD. Ultraviolet photoluminescence centered at 359-361 nm was observed in the room temperature PL spectra of the Al-doped ZnO films.     

Structures and properties of the Al-doped ZnO thin films prepared by radio frequency magnetron sputtering

Al-doped ZnO thin films were deposited by radio frequency magnetron sputtering using a ZnO target with 2 wt.% Al₂O₃. The structures and properties of the films were characterized by the thin film X-ray diffraction, high resolution transmission electron microscopy, Hall system and ultraviolet/visible/near-infrared spectrophotometer. The Al-doped ZnO film with high crystalline quality and good properties was obtained at the sputtering power of 100 W, working pressure of 0.3 Pa and substrate temperature of 250 °C. The results of further structure analysis show that the interplanar spacings d are enlarged in other directions besides the direction perpendicular to the substrate. Apart from the film stress, the doping concentration and the doping site of Al play an important role in the variation of lattice parameters. When the doping concentration of Al is more than 1.5 wt.%, part of Al atoms are incorporated in the interstitial site, which leads to the increase of lattice parameters. This viewpoint is also proved by the first principle calculations.     

Novel synthesis of aligned Zinc oxide nanorods on a glass substrate by sonicated sol-gel immersion

For the first time, aligned ZnO nanorod structured thin films have been synthesized on a glass substrate, which had been coated with an Al-doped ZnO thin film, using the sonicated sol-gel immersion method. These nanorods were found to have an average diameter of 100 nm and an average length of 500 nm, with hexagonal wurtzite phase grew preferentially along the c-axis direction. A sharp ultra-violet (UV) emission centred at 383 nm corresponding to the free exciton recombination was observed in a room temperature photoluminescence (PL) spectrum. The prepared ZnO nanorod structured thin film is transparent in the visible region with an average transmittance of 78% in the 400-800 nm wavelength range and high absorbance properties in the UV region (< 400 nm). The results indicate that the prepared ZnO nanorods are suitable for ultra-violet photoconductive sensor applications.     

Synthesis and properties of close packed ZnO:Al submicro-rods deposited by pulsed laser ablation

Al-doped ZnO (AZO) semiconducting thin films consisting of perpendicularly aligned submicro-rods were deposited on silicon substrate by conventional pulsed laser ablation. No catalyst was used in this process. It was found that the rod structure can be grown at relatively high oxygen pressures (1-20 Torr) and relatively high substrate temperatures (550-700 °C). Low resistivity and high carrier concentration can be obtained in these Al-doped ZnO rods with relatively high Al concentrations. Increasing Al doping reduces the electric resistivity and increase carrier concentration. The photoluminescence property measurement indicates an increased UV emission with a small amount Al doping and reduced UV emission with further increase of Al concentration.     

ZnO棒晶阵列薄膜的水溶液法生长

采用低温水溶液法, 在涂覆ZnO种子层的ITO基底上制备了高度取向的ZnO棒晶阵列, 考察了棒晶的生长过程以及生长液浓度、生长时间对薄膜形貌的影响. 用扫描电子显微镜(SEM),X射线衍射(XRD), 场发射扫描显微镜(FESEM)以及高分辨透射电镜(HRTEM)对ZnO纳米棒的结构和形貌进行了表征. 结果表明, ZnO薄膜的形貌强烈依赖于生长溶液的浓度和生长时间, ZnO棒是单晶, 属于六方纤锌矿结构, 具有沿(002)晶面择优生长的特征, 生长方式为层层台阶生长, 反应时间达到48h后, 通过二次生长形成特殊的板状晶.     

Filtered vacuum arc deposition of transparent conducting Al-doped ZnO films

Transparent conducting ZnO:Al and ZnO films of 380-800 nm thickness were deposited on glass substrates by filtered vacuum arc deposition (FVAD), using a cylindrical Zn cathode doped with 5-6 at.% Al or a pure Zn cathode in oxygen background gas with pressure P = 0.4-0.93 Pa. The crystalline structure, composition and electrical and optical properties of the films were studied as functions of P. The films were stored under ambient air conditions and the variation of their resistance as function of storage time was monitored over a period of several months.The Al concentration in the film was found to be 0.006-0.008 at.%, i.e., a few orders of magnitude lower than that in the cathode material. However, this low Al content influenced the film resistivity, ρ, and its stability. The resistivity of as-deposited ZnO:Al films, ρ = (6-8) × 10^− 3 Ω cm, was independent of P and lower by a factor of 2 in comparison to that of the ZnO films deposited by the same FVAD system. The ρ of ZnO films 60 days after deposition increased by a factor of ∼ 7 with respect to as-deposited films. The ZnO:Al films deposited with P = 0.47-0.6 Pa were more stable, their ρ first slowly increased during the storage time (1.1-1.4 times with respect to as-deposited films), and then stabilized after 30-45 days.     

Influence of working pressure on ZnO:Al films from tube targets for silicon thin film solar cells

Mid-frequency magnetron sputtering of aluminum doped zinc oxide films (ZnO:Al) from tube ceramic targets has been investigated for silicon based thin film solar cell applications. The influence of working pressure on structural, electrical, and optical properties of sputtered ZnO:Al films was studied. ZnO:Al thin films with a minimum resistivity of 3.4 × 10⁻⁴ Ω cm, high mobility of 50 cm²/Vs, and high optical transmission close to 90% in visible spectrum region were achieved. The surface texture of ZnO:Al films after a chemical etching step was investigated. A gradual increase in feature sizes (diameter and depth) was observed with increasing sputter pressure. Silicon based thin film solar cells were prepared using the etched ZnO:Al films as front contacts. Energy conversion efficiencies of up to 10.2% were obtained for amorphous/microcrystalline silicon tandem solar cells.     

Studies on the effect of hydrogen doping during deposition of Al:ZnO films using RF magnetron sputtering

Aluminum doped ZnO (ZnO:Al) films were deposited using rf magnetron sputtering in the presence of hydrogen gas in the chamber. A comparative study of the films deposited with and without hydrogen was performed. The XPS studies indicated that the decrease in resistivity of ZnO:Al films with the introduction of hydrogen gas is attributed to the reduced adsorption of oxygen species in the film grain boundaries. The average percentage transmission in the visible region of the films was around 92–95% and band gap was found to be about in the range of 3.15–3.17 eV. The lowest resistivity of 1.8 × 10⁻⁴ Ω cm was achieved for the ZnO:Al film deposited with hydrogen.     

Low temperature pH dependent synthesis of flower-like ZnO nanostructures with enhanced photocatalytic activity

In the present study we have synthesized flower-like ZnO nanostructures comprising of nanobelts of 20 nm width by template and surfactant free low-temperature (4 °C) aqueous solution route. The ZnO nanostructures exhibit flower-like morphology, having crystalline hexagonal wurtzite structure with (0 0 1) orientation. The flowers with size between 600 and 700 nm consist of ZnO units having crystallite size of ∼40 nm. Chemical and structural characterization reveals a significant role of precursor:ligand molar ratio, pH, and temperature in the formation of single-step flower-like ZnO at low temperature. Plausible growth mechanism for the formation of flower-like structure has been discussed in detail. Photoluminescence studies confirm formation of ZnO with the defects in crystal structure. The flower-like ZnO nanostructures exhibit enhanced photochemical degradation of methylene blue (MB) with the increased concentration of ligand, indicating attribution of structural features in the photocatalytic properties.     

Ethylene glycol assisted hydrothermal synthesis of flower like ZnO architectures

We describe a simple route to flower like ZnO architectures, based on the decomposition of zinc acetate precursor in water-ethylene glycol solution at 140-160 °C for 1d through hydrothermal method. The PXRD pattern reveals that the ZnO crystals are of hexagonal wurtzite structure. Ethylene glycol plays a key role on the morphology control of ZnO crystals. The SEM images of ZnO products prepared at 140 °C and 160 °C mainly exhibit flower like architecture composed of many rods. Whereas, the product prepared at 180 °C shows bunches accompanying a few number of free rods. TEM results reveal that the rods resemble swords with decrease in size from one end to another. From Raman spectrum, the peaks at 437 cm^− 1, 382 cm^− 1 and 411 cm^− 1 correspond to E₂ (high), A₁ (TO) and E₁ (TO) of ZnO crystals respectively. The photoluminescence spectrum exhibits strong UV emission at ~ 397 nm, which comes from recombination of exciton. The possible mechanism for the formation of flower like ZnO architecture is proposed.     

Study of ZnO sol-gel films: Effect of annealing

Thin films of zinc oxide were deposited by spin coating method on different substrates. The obtained samples were thermally treated at temperatures from 400 °C up to 850 °C. The structural study was performed by XRD and FTIR techniques in order to observe the effect of the annealing temperatures. The sol-gel ZnO films showed polycrystalline hexagonal structure. The optical transmittance reached 91% and it diminished with increasing annealing temperatures.     

Development of two-step etching approach for aluminium doped zinc oxide using a combination of standard HCl and NH4Cl etch steps

An etching method for ZnO:Al films deposited by radio-frequency sputtering is presented. The method is developed to achieve appropriate surface morphology for efficient light scattering. This etching method consists of a first step where the sample is dipped in standard diluted HCl (0.5 wt.%) for 40 s (the “standard Jülich” etch process) and a subsequent step where a NH₄Cl aqueous solution with concentrations ranging from 2 to 20 wt.% is used. The introduction of the second step leads to a slight modification of the surface feature shape and an increase in the surface roughness of up to around 37% in relation with that obtained using only the first step. High haze values are also obtained, reaching up to 93% at 550 nm and strong light scattering into angles above 50° at 632 nm. On the other hand, the resistivity of the textured films remains low enough for cell application, being ranged from 6 to 13 Ω/sqr depending on the NH₄Cl concentration used. Finally, in order to assess the role of the features obtained on the surface as effective light trapping, the textured films are applied as front contact in silicon thin film solar cells.