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.     

Etching process optimization using NH4Cl aqueous solution to texture ZnO:Al films for efficient light trapping in flexible thin film solar cells

0.5 μm-thick aluminum-doped zinc oxide (ZnO:Al) films were deposited at 100 °C on polyethylene terephthalate substrates by Radio Frequency magnetron sputtering. The as-deposited films were compact and dense, showing grain sizes of 32.0 ± 6.4 nm and resistivities of (8.5 ± 0.7) × 10^− 4 Ω cm. The average transmittance in the visible wavelength range of the structure ZnO:Al/PET was around 77%. The capability of a novel two-step chemical etching using diluted NH₄Cl aqueous solution to achieve efficient textured surfaces for light trapping was analyzed. The results indicated that both the aqueous solution and the etching method resulted appropriated to obtain etched surfaces with a surface roughness of 32 ± 5 nm, haze factors at 500 nm of 9% and light scattering at angles up to 50°. To validate all these results, a commercially ITO coated PET substrate was used for comparison.     

Characterization of ZnO:Al thin films obtained by spray pyrolysis technique

Films of zinc oxide doped with Al (ZnO:Al) are prepared using the spray pyrolysis technique. The effect of doping Al on the physical properties of ZnO:Al is studied. In this study the polycrystalline ZnO:Al films with the different Al concentration ([Al]/[Zn] in the starting solution was varied from 0 to 0.6 wt.%) were prepared. These films were confirmed to show the high crystallinity by X-ray diffraction technique. The smallest sheet resistance value, around 207 Ω/□, was obtained using a [Al]/[Zn] ratio of 0.125 wt.% in starting solution. The optical transmittance was about 75% in visible range for the optimum film.     

湿法刻蚀对ZnO∶Al透明导电薄膜结构与性能的影响

室温下通过直流磁控溅射Al2O3掺杂3％(质量分数)的ZnO靶材制备了厚度约1μm、结晶度高、表面平整光滑的ZnO∶Al透明导电薄膜.研究盐酸、王水和草酸溶液对ZnO∶Al薄膜的湿化学刻蚀行为,分析刻蚀对薄膜微观结构、光刻图案、电学和光学性能的影响.结果表明,刻蚀对薄膜的结晶取向性无影响;经盐酸、王水和草酸刻蚀后薄膜的电阻率略有增大,从7.4mΩ·cm分别增大到8.7mnΩ· cm、8.8mQ·cm和8.6mΩ·cm;透光率略有下降,从80％分别下降到76％、77％和78％.0.5％的盐酸刻蚀可以获得结构良好的陷光结构.薄膜在盐酸中刻蚀速率快,易产生浮胶;在草酸中刻蚀图案清晰,但存在残留;在王水中刻蚀图案清晰且无残留.     

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.     

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.%.     

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.     

Optical and electrical properties of ZnO films deposited by activated reactive evaporation

ZnO films having good transmittance and conductivity were deposited by activated reactive evaporation of Zn metal on glass and Si substrates at room temperature. Optical constants and thickness of ZnO films deposited under different deposition conditions were determined both by spectroscopic ellipsometry (SE) and spectrophotometry. Structural studies showed that the films exhibited a polycrystalline wurtzite structure with the preferential oriented along the (002) plane. Electrical studies by four probe technique showed that the sheet resistance of the films varied from 10⁶ to 50 Ω/square depending upon the oxygen partial pressure used during deposition, and this sheet resistance value increased with time. The increase in sheet resistance with time was found to be dependent on the surface morphology of the film and on the substrate over which they were deposited.     

Electrical, structural and optical properties of fluorine-doped zinc oxide thin films: Effect of the solution aging time

In this paper ageing effects of the solution used to prepare fluorine-doped ZnO films by the spray pyrolysis technique were investigated, concerning its role on the structure, the electrical and optical properties of films produced. The data reveal that the sheet resistance of the ZnO:F thin film decreases with the age of the solution used, reaching a minimum of 24 Ω/□, after 15 days. On the other hand the optical transmittance increases for films deposited using 6 days aging solution, decreasing afterwards as the aging time increases, being the optical transmittance in the visible range below 55%, for films deposited from solutions 36 days in age. The X-ray diffraction spectra show that the aged films are polycrystalline in nature with a [100] predominant orientation. The data also show that the intensity of (100) peak increases as the time of solution age increases, which is related to an improvement of the film crystallinity.     

Texture optimization process of ZnO:Al thin films using NH4Cl aqueous solution for applications as antireflective coating in thin film solar cells

ZnO:Al thin films varying the thickness from 80 to 110 nm were deposited on polished float zone < 100 > Si wafers by radio frequency magnetron sputtering at 100 °C. To texturize these surfaces with the aim of being used as antireflective coating, a wet etching process based on NH₄Cl was applied. Taking into account that the layer thickness was small, the control of the etch parameters such as etchant concentration and etching time was evaluated as a function of the textured film properties. An appropriate control of the etching rate to adjust the final thickness to the 80 nm required for the application was realized. Using NH₄Cl concentrations of 10 wt.% and short times of up to 25 s, an increase of the film roughness up to a factor of 5.6 of the as-deposited films was achieved. These optimized textured films showed weighted reflectance values below 15% and considerable better electrical properties than the as-deposited 80 nm-thick ZnO:Al films.     

Transparent conducting Sc-codoped AZO film prepared from ZnO:Al-Sc by RF-DC sputtering

Al and Sc-codoped zinc oxide (also expressed as Sc-codoped AZO or ZnO:Al-Sc) films were sputtered on STN glass using RF power sources on ZnO and DC power sources on Al-1.7wt.% Sc alloy. X-ray diffraction (XRD) of the codoped films displayed that they are crystalline and textured at (002) and (103). Examination through transmission electron microscopy (TEM) depicted that these films consists of columnar grains. X-ray photoelectron spectroscopy (XPS) analysis of the films indicated that the O1s comprises O(I), O(II), O(III), and O(IV). The component O(I) centered at 530.00 ± 0.15eV was attributable to Sc₂O₃; the O(III) at 531.25 ± 0.20eV was to the oxygen deficient regions within the matrix of ZnO. The transmittance of visible light (i.e., wavelength in the range from 400 to 800nm) for the film was higher than 80%. The electrical resistivity is lower (1.76 < 2.81Ω-cm), the corrosion-resistance in 3.5% NaCl solution is better for the codoped film in comparison with the usual AZO. Heat treatment of the films (at 200-400°C for 1h) improved the optical transmittance, electrical conductivity, and corrosion-resistance in saline solution.     

Tungsten-doped ZnO transparent conducting films deposited by direct current magnetron sputtering

Highly conducting and transparent thin films of tungsten-doped ZnO (ZnO:W) were prepared on glass substrates by direct current (DC) magnetron sputtering at low temperature. The effect of film thickness on the structural, electrical and optical properties of ZnO:W films was investigated. All the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. The electrical resistivity first decreases with film thickness, and then increases with further increase in film thickness. The lowest resistivity achieved was 6.97 × 10⁻⁴ Ω cm for a thickness of 332 nm with a Hall mobility of 6.7 cm² V⁻¹ s⁻¹ and a carrier concentration of 1.35 × 10²¹ cm⁻³. However, the average transmittance of the films does not change much with an increase in film thickness, and all the deposited films show a high transmittance of approximately 90% in the visible range.     

Optimization of ZnO/Ag/ZnO multilayer electrodes obtained by Ion Beam Sputtering for optoelectronic devices

We investigated the electrical and optical properties of ZnO/Ag/ZnO multi-layer electrodes obtained by ion beam sputtering for flexible optoelectronic devices. This multi-layer structure has the advantage of adjusting the layer thickness to favor antireflection and the surface plasmon resonance of the metallic layer. Inserting a thin (Ag) metallic layer between two (ZnO) oxide layers decreases the sheet resistance while widening the optical transmittance window in the visible. We found that the optimal electrode is made up of a 10 nm thin Ag layer between two 35 nm and 20 nm thick ZnO layers, which resulted in a low sheet resistance (R_sq = 6 Ω/square), a high transmittance (T ≥ 80% in the visible) and the highest figure of merit of 1.65 × 10^-2 square/Ω.     

Discharge power dependence of structural and electrical properties of Al-doped ZnO conducting film by magnetron sputtering (for PDP)

In order to investigate the possible application of ZnO films as a transparent conducting oxide (TCO) electrode for AC PDP, ZnO:Al films were prepared by DC magnetron sputtering method. The effects of discharge power and doping concentration on the structural and electrical properties of ZnO films were mainly studied experimentally. Five-inch PDP cells using either a ZnO:Al or indium tin oxide (ITO) electrode were also fabricated separately under the same manufacturing conditions. The luminous properties of both the PDP cells were measured and compared with each other.By doping the ZnO target with 2 wt% of Al₂O₃, the film deposited at a discharge power of 40 W resulted in the minimum resistivity of 8.5 × 10⁻⁴ Ω-cm and a transmittance of 91.7%. However, a high doping concentration of 3 wt% of Al₂O₃ and excessive sputtering power over 40 W may induce high defect density and limit the growth of small grains. Although the luminance and luminous efficiency of the cell using ZnO:Al are lower than those of the cell with the ITO electrode by about 10%, these values are sufficient enough to be considered for the normal operation of AC PDP.     

Inkjet-printing of indium tin oxide (ITO) films for transparent conducting electrodes

Indium-tin-oxide (ITO) films have been prepared by inkjet-printing using ITO nanoparticle inks. The electrical and optical properties of the ITO films were investigated in order to understand the effects of annealing temperatures under microwave. The decrease in the sheet resistance and resistivity of the inkjet-printed ITO films was observed as the annealing temperature increases. The film annealed at 400 °C showed the sheet resistance of 517 Ω/sq with the film thickness of ∼580 nm. The optical transmittance of the films remained constant regardless of their annealing temperatures. In order to further reduce the sheet resistance of the films, Ag-grid was printed in between two layers of inkjet-printed ITO. With 3 mm Ag-grid line-to-line pitch, the Ag-grid inserted ITO film has the sheet resistance of 3.4 Ω/sq and the transmittance of 84% after annealing at 200 °C under microwave.     

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.     

Thermally stable transparent conducting and highly infrared reflective Ga-doped ZnO thin films by metal organic chemical vapor deposition

Highly transparent conductive Ga-doped ZnO (GZO) thin films have been prepared on glass substrates by metal organic chemical vapor deposition. The effect of Ga doping on the structural, electrical and optical properties of GZO films has been systematically investigated. Under the optimum Ga doping concentration (∼4.9 at.%), c-axis textured GZO film with the lowest resistivity of 3.6 × 10⁻⁴ Ω cm and high visible transmittance of 90% has been achieved. The film also exhibits low transmittance (<1% at 2500 nm) and high reflectance (>70% at 2500 nm) to the infrared radiation. Furthermore, our developed GZO thin film can well retain the highly transparent conductive performance in oxidation ambient at elevated temperature (up to 500 °C).     

Etching processes of transparent carbon nanotube thin films using laser technologies

Carbon nanotubes (CNTs) have potential as a transparent conductive material with good mechanical and electrical properties. However, carbon nanotube thin film deposition and etching processes are very difficult to pattern the electrode. In this study, transparent CNT film with a binder is coated on a PET flexible substrate. The transmittance and sheet resistance of carbon nanotube film are 84% and 1000 Ω/□, respectively. The etching process of carbon nanotube film on flexible substrates was investigated using 355 nm and 1064 nm laser sources. Experimental results show that carbon nanotube film can be ablated using laser technology. With the 355 nm UV laser, the minimum etched line width was 20 μm with a low amount of recast material of the ablated sections. The optimal conditions of laser ablation were determined for carbon nanotube film.     

Solution processed Al doped ZnO film fabrication through electrohydrodynamic atomization

In this study, highly transparent, 250 nm thick films of Aluminum doped Zinc-oxide (ZnO:Al) are achieved on glass substrates at ambient conditions through a solution processing technique called electrohydrodynamic atomization. A 10 wt.% monodispersed solution containing 6% ZnO:Al nanoparticles (ZnO/Al₂O₃) in ethanol has been synthesized first and then used in the deposition process as the working solution. Pure and uniform transparent films with an average transmittance of 93% have been deposited with crystal structure exhibiting both zincite and gahnite phases. Surface composition purity has been confirmed using X-ray photoelectron spectroscopy technique and the clear indication of Zn-2p and Al-2p peaks confirms surface integrity. Fourier Transform Infrared analysis further confirms the presence of aluminum in the samples. The electrical properties are studied by recording and analyzing the current-voltage (I-V) measurements and the resistivity has been estimated from the slope of the IV-curve which is approximately 25 mΩ.cm. The layer roughness has been characterized using atomic force microscopy.     

Aluminium doped zinc oxide sputtered from rotatable dual magnetrons for thin film silicon solar cells

This study addresses the electrical and optical properties as well as the surface structure after wet-chemical etching of mid-frequency magnetron sputtered aluminium doped zinc oxide (ZnO:Al) films on glass substrates from rotatable ceramic targets. Etching of an as-deposited ZnO:Al film in acid leads to rough surfaces with various feature sizes. The influence of working pressure and substrate temperature on the surface topography after etching was investigated. It was found that the growth model which Kluth et al. applied to films sputtered in radio frequency mode from planar ceramic target can be transferred to film growth from tube target. Furthermore, the influence of Ar gas flow and discharge power on the film properties was investigated. We achieved low resistivity of about 5.4 × 10^− 4 Ω·cm at high growth rates of 120 nm·m/min. Finally, surface textured ZnO:Al films were applied as substrates for microcrystalline silicon solar cells and high efficiencies of up to 8.49% were obtained.