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 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.     

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.     

On the structure and characterization of Al, Sc-co-doped ZnO-films varying with 0-2.37 wt.% Sc contents

Thin films of Al, Sc-co-doped ZnO varying with Sc-contents were sputtered on the glass substrate. X-ray diffraction (XRD) of the films revealed wurtzite crystals that were confirmed through the analysis of high resolution transmission electron microscopy (HRTEM). With increasing the Sc-content from 0 to 2.37 wt.% in the films, the optical energy band gap (Eg) was estimated to decrease from 3.25 to 3.20 eV, and the electrical resistivity (Ω cm) decreased from 3.8 × 10^− 3 to 1.3 × 10^− 3. The decrease in resistivity may be ascribed to electrons tunneling through the horizontal stacking faults induced by Sc-dopants in the films.     

Optical and photoconductivity properties of ZnO thin films grown by pulsed filtered cathodic vacuum arc deposition

High quality transparent conductive ZnO thin films with various thicknesses were prepared by pulsed filtered cathodic vacuum arc deposition (PFCVAD) system on glass substrates at room temperature.The high quality of the ZnO thin films was verified by X-ray diffraction and optical measurements. XRD analysis revealed that all films had a strong ZnO (200) peak, indicating c-axis orientation. The ZnO thin films are very transparent (92%) in the near vis regions. For the ZnO thin films deposited at a pressure of 0.086 Pa (6.5 × 10⁻⁴ Torr) optical energy band gap decreased from 3.21 eV to 3.19 eV with increasing the thickness. Urbach tail energy also decreased as the film thickness increased.Spectral dependence of the photoconductivity was obtained from measurements of the samples deposited at various thicknesses. Photoconductivities were observed at energies lower than energy gap which indicates the existence of energy states in the forbidden gap. Photoconductivities of ZnO thin films increase with energy of the light and reach its maximum value at around 2.32 eV. Above this value surface recombination becomes dominant process and reduces the photocurrent. The photoconductivity increases with decreasing the film thickness.     

ZnO thin films prepared by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on soda lime glass substrates by pulsed laser deposition (PLD) in an oxygen-reactive atmosphere. The structural, optical, and electrical properties of the as-prepared thin films were studied in dependence of substrate temperature and oxygen pressure. High quality polycrystalline ZnO films with hexagonal wurtzite structure were deposited at substrate temperatures of 100 and 300 °C. The RMS roughness of the deposited oxide films was found to be in the range 2-9 nm and was only slightly dependent on substrate temperature and oxygen pressure. Electrical measurements indicated a decrease of film resistivity with the increase of substrate temperature and the decrease of oxygen pressure. The ZnO films exhibited high transmittance of 90% and their energy band gap and thickness were in the range 3.26-3.30 eV and 256-627 nm, respectively.     

Study on the Hall-effect and photoluminescence of N-doped p-type ZnO thin films

N-doped, p-type ZnO thin films have been grown by plasma-assisted metal-organic chemical vapor deposition method. The results under optimized growth conditions included a resistivity of 1.72 Ω cm, a Hall mobility of 1.59 cm²/V s, and a hole concentration of 2.29 × 10¹⁸ cm^− 3, and were consistently reproducible. A N-related free-to-neutral-acceptor emission and an associated phonon replica were evident in room temperature photoluminescence spectra, from which the N acceptor energy level in ZnO was estimated to be 180 meV above the valence band maximum.     

Characterizations of gallium-doped ZnO films on glass substrate prepared by atmospheric pressure metal-organic chemical vapor deposition

Ga-doped zinc oxide (ZnO:Ga) films were grown on glass substrate by atmospheric pressure metal-organic chemical vapor deposition (AP-MOCVD) using diethylzinc and water as reactant gases and triethyl gallium (TEG) as an n-type dopant gas. The structural, electrical and optical properties of ZnO:Ga films obtained at various flow rates of TEG ranging from 1.5 to 10 sccm were investigated. X-ray diffraction patterns and scanning electron microscopy images indicated that Ga-doping plays an important role in forming microstructures in ZnO films. A smooth surface with a predominant orientation of (101) was obtained for the ZnO:Ga film grown at a flow rate of TEG = 7.5 sccm. Moreover, a lowest resistivity of 3.6 × 10^− 4 Ω cm and a highest mobility of 30.4 cm² V^− 1 s^− 1 were presented by the same sample, as evaluated by Hall measurement. Otherwise, as the flow rate of TEG was increased, the average transmittance of ZnO:Ga films increased from 75% to more than 85% in the wavelength range of 400-800 nm, simultaneously with a blue-shift in the absorption edge. The results obtained suggest that low-resistivity and high-transparency ZnO films can be obtained by AP-MOCVD using Ga-doping sufficiently to make the films grow degenerate and effect the Burstein-Moss shift to raise the band-gap energy from 3.26 to 3.71 eV.     

Effect of process conditions on the optoelectronic characteristics of ZnO:Mo thin films prepared by pulsed direct current magnetron sputtering

The purpose of this study is to use pulsed magnetron sputtering to deposit transparent conductive ZnO:Mo (MZO) film on a Corning 1737 glass substrate. Various process parameters, including power, work pressure, pulsed frequency, film thickness, and substrate temperature, were analyzed for their effects on the microstructure and optoelectronic characteristics of MZO thin film. Experimental results show that MZO film with a low resistivity of approximately 8.9 × 10^− 4 Ω cm and a visible light transitivity of greater than 80% can be obtained using a Mo content of 1.77 wt.%, sputtering power of 100 W, work pressure of 0.4 Pa, pulsed frequency of 10 kHz, and film thickness of 500 nm without heating. The value of optical band gap of MZO increased upon increasing the crystallinity of the MZO thin film, and the range of the optical band gap of MZO thin film is from 3.30 to 3.35 eV.     

Optical and electrical properties of electron-irradiated Cu(In,Ga)Se2 solar cells

The optical and electrical properties of electron-irradiated Cu(In,Ga)Se₂ (CIGS) solar cells and the thin films that composed the CIGS solar cell structure were investigated. The transmittance of indium tin oxide (ITO), ZnO:Al, ZnO:Ga, undoped ZnO, and CdS thin films did not change for a fluence of up to 1.5 × 10¹⁸ cm^− 2. However, the resistivity of ZnO:Al and ZnO:Ga, which are generally used as window layers for CIGS solar cells, increased with increasing irradiation fluence. For CIGS thin films, the photoluminescence peak intensity due to Cu-related point defects, which do not significantly affect solar cell performance, increased with increasing electron irradiation. In CIGS solar cells, decreasing J_SC and increasing R_s reflected the influence of irradiated ZnO:Al, and decreasing V_OC and increasing R_sh mainly tended to reflect the pn-interface properties. These results may indicate that the surface ZnO:Al thin film and several heterojunctions tend to degrade easily by electron irradiation as compared with the bulk of semiconductor-composed 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.     

Modification of optical and electrical properties of ITO using a thin Al capping layer

In this study, the work function, transmittance, and resistivity of indium tin oxide (ITO) thin films were successfully modified by depositing an Al capping layer on top of ITO with subsequent thermal annealing. The 5 nm thick Al layer was deposited by a conventional dc magnetron sputtering method and the layer was converted into an aluminum oxinitride by subjecting the sample to rapid thermal annealing (RTA) under a nitrogen atmosphere. The films exhibited a high transmittance of 86% on average within the visible wavelength region with an average resistivity value of 7.9 × 10^− 4 Ω cm. Heat-treating the Al/ITO films via RTA resulted in the decrease of the optical band gap from that of bare ITO. In addition, the films showed red-shift phenomena due to their decreased band gaps when the heat-treatment temperature was increased. The resultant electrical and optical characteristics can be explained by the formation of aluminum oxinitride on the surface of the ITO films. The work function of the heat-treated films increased by up to 0.26 eV from that of a bare ITO film. The increase of the work function predicts the reduction of the hole-injection barrier in organic light-emitting diode (OLED) devices and the eventual use of these films could provide much improved efficiency of devices.     

Microstructural and optical properties of Ga-doped ZnO semiconductor thin films prepared by sol-gel process

Transparent thin films of Ga-doped ZnO (GZO), with Ga dopant levels that varied from 0 to 7 at.%, were deposited onto alkali-free glass substrates by a sol-gel process. Each spin-coated film was preheated at 300 °C for 10 min, and then annealed at 500 °C for 1 h under air ambiance. The effects of Ga dopant concentrations on crystallinity levels, microstructures, optical properties, and electrical resistivities of these ZnO thin films were systematically investigated. Photoluminescence spectra of GZO thin films were examined at room temperature. XRD results revealed that the undoped ZnO thin films exhibited a preferred orientation along the (002) plane and that the ZnO thin films doped with Ga showed degraded crystallinity. Experimental results also showed that Ga doping of ZnO thin films could markedly decrease surface roughness, improve transparency in the visible range, and produce finer microstructures than those of undoped ZnO thin films. The most promising films for transparent thin film transistor (TTFT) application produced in this study, were the 3 and 5 at.% Ga-doped ZnO thin films, both of which exhibited an average transmittance of 90.6% and an RMS roughness value of about 2.0 nm.     

Textured surface boron-doped ZnO transparent conductive oxides on polyethylene terephthalate substrates for Si-based thin film solar cells

Textured surface boron-doped zinc oxide (ZnO:B) thin films were directly grown via low pressure metal organic chemical vapor deposition (LP-MOCVD) on polyethylene terephthalate (PET) flexible substrates at low temperatures and high-efficiency flexible polymer silicon (Si) based thin film solar cells were obtained. High purity diethylzinc and water vapors were used as source materials, and diborane was used as an n-type dopant gas. P-i-n silicon layers were fabricated at ~ 398 K by plasma enhanced chemical vapor deposition. These textured surface ZnO:B thin films on PET substrates (PET/ZnO:B) exhibit rough pyramid-like morphology with high transparencies (T ~ 80%) and excellent electrical properties (Rs ~ 10 Ω at d ~ 1500 nm). Finally, the PET/ZnO:B thin films were applied in flexible p-i-n type silicon thin film solar cells (device structure: PET/ZnO:B/p-i-n a-Si:H/Al) with a high conversion efficiency of 6.32% (short-circuit current density J_SC = 10.62 mA/cm², open-circuit voltage V_OC = 0.93 V and fill factor = 64%).     

Dependence of the electrical and optical properties on the bias voltage for ZnO:Al films deposited by r.f. magnetron sputtering

Aluminum-doped zinc oxide (ZnO:Al) thin films were deposited on glass, polycarbonate (PC), and polyethylene terephthalate (PET) substrates by r.f. magnetron sputtering. The substrate dc bias voltage varied from 0 V to 50 V. Structural, electrical and optical properties of the films were investigated. The deposition rate of ZnO:Al films on glass substrate initially increased with the bias voltage, and then decreased with further increasing bias voltage. It was found that the best films on glass substrate with a low as 6.2 × 10^− 4 Ω cm and an average transmittance over 80% at the wavelength range of 500-900 nm can be obtained by applying the bias voltage of 30 V. The properties of the films deposited on polymer substrate, such as PC and PET, have a similar tendency, with slightly inferior values to those on glass substrate.     

Deposition of Al doped ZnO layers with various electrical types by atomic layer deposition

AlZnO thin films with various Al/Zn composition ratios were deposited by atomic layer deposition (ALD) at 200 °C. The effect of the composition of the AlZnO films on their electrical and optical characteristics was investigated. The AlZnO films with an Al content of up to 10 at.% showed high conductivity, while further increasing in the Al content resulted in the abrupt formation of an insulating oxide film. The lowest electrical resistivity of the ALD-deposited AlZnO film was 6.5 × 10^− 4 [Ω cm] at 5 at.% Al. The AlZnO films with up to 5 at.% Al exhibited crystalline phases and a near-band-edge emission. With increasing Al content, the optical band edge showed a blue shift, and a sudden shift associated with an insulating bandgap was observed in the AlZnO films containing 20 at.% Al.     

The fabrication and application of ZnO:Al thin films in low-frequency inductively coupled plasma fabricated silicon solar cell

A home-made radio frequency magnetron sputtering is used to systematically study the structural, electrical, and optical properties of aluminum doped zinc oxide (ZnO:Al) thin films. The intensity of the (002) peak exhibits a remarkable enhancement with increasing film thickness. Upon optimization, we achieved low resistivity of 4.2 × 10^− 4 Ω cm and high transmittance of ~ 88% for ZnO:Al films. Based on the present experimental data, the carrier transport mechanism is discussed. It is found that the grain boundary scattering needs to be considered because the mean free path of free carrier is comparable to the grain size. The 80 nm-ZnO:Al thin films are then deposited onto low-frequency inductively coupled plasma fabricated silicon solar cells to assess the effect of ZnO:Al thin films on the performance of the solar cells. Optimized ZnO:Al thin films are identified as transparent and conductive oxide thin film layers.     

Structural, optical and electrical properties of Al-doped ZnO microrods prepared by spray pyrolysis

Al-doped ZnO thin films were obtained on glass substrates by spray pyrolysis in air atmosphere. The molar ratio of Al in the spray solution was changed in the range of 0-20 at.% in steps of 5 at.%. X-ray diffraction patterns of the films showed that the undoped and Al-doped ZnO films exhibited hexagonal wurtzite crystal structure with a preferred orientation along (002) direction. Surface morphology of the films obtained by scanning electron microscopy revealed that pure ZnO film grew as quasi-aligned hexagonal shaped microrods with diameters varying between 0.7 and 1.3 μm. However, Al doping resulted in pronounced changes in the morphology of the films such as the reduction in the rod diameter and deterioration in the surface quality of the rods. Nevertheless, the morphology of Al-doped samples still remained rod-like with a hexagonal cross-section. Flower-like structures in the films were observed due to rods slanting to each other when spray solution contained 20 at.% Al. Optical studies indicated that films had a low transmittance and the band gap decreased from 3.15 to 3.10 eV with the increasing Al molar ratio in the spray solution from 0 to 20 at.%.     

Compact and vertically-aligned ZnO nanorod thin films by the low-temperature solution method

Highly c-axis-oriented ZnO nanorod thin films were obtained on silica glass substrates by a simple solution-growth technique. The most compact and vertically-aligned ZnO nanorod thin film with the thickness of ∼ 800 nm and average hexagonal grain size of ∼ 200 nm exhibits the average visible transmittance 85%, refractive index 1.74, packing density 0.84, and energy band gap 3.31 eV, and it was fabricated under the optimum parameters: 0.05 M, 75 °C, 6 h, multiple-stepwise, and ZnO seed layer with an average grain size of ∼ 20 nm. The photoluminescence spectrum indicates that the densest ZnO nanorod thin film possesses lots of oxygen vacancies and interstitials. As we demonstrate here, the solution-growth technique was used to produce high-quality and dense ZnO nanorod thin films, and is an easily controlled, low-temperature, low-cost, and large-scale process for the fabrication of optical-grade thin films.     

Electrical and optical properties of ZnO:Al thin films grown by magnetron sputtering

The properties of transparent conductive ZnO:Al thin films grown by R.F. magnetron sputtering method are investigated. The working pressure (argon gas) is changed from 2.5 to 40.0 mTorr to study its influence on the characteristics of ZnO:Al thin films. The ZnO:Al thin films have better texture due to the increase in the surface mobility, which resulted from the increase in the mean free path of sputtering gas under lower working pressure. The microstructure of ZnO:Al films is found to be affected obviously by changing the working pressure. It is shown that the grain size of ZnO:Al thin films decreases with the increase of working pressure. The X-ray diffraction patterns indicate that the poor crystallized structure of ZnO:Al films is obtained at higher working pressure. Except 40 mTorr, the highly (002)-oriented ZnO:Al thin films can be found at the measured range of working pressure. Moreover, the growth rate of the films decreases from 1.5 to 0.5 nm/min as the working pressure increases from 2.5 to 40.0 mTorr. The results of optical transmittance measurement of ZnO:Al thin films reveal a high transmittance (>80%) in visible region and exhibit a sharp absorption edge at wavelength about 350 nm.