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.     

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.     

Surface textured molybdenum doped zinc oxide thin films prepared for thin film solar cells using pulsed direct current magnetron sputtering

In this study, we examined the effect of etching on the electrical properties, transmittance, and scattering of visible light in molybdenum doped zinc oxide, ZnO:Mo (MZO) thin films prepared by pulsed direct current magnetron sputtering. We used two different etching solutions - KOH and HCl - to alter the surface texture of the MZO thin film so that it could trap light. The experimental results showed that an MZO film with a minimum resistivity of about 8.9 × 10^− 4 Ω cm and visible light transitivity of greater than 80% can be obtained without heating at a Mo content of 1.77 wt.%, sputtering power of 100 W, working pressure of 0.4 Pa, pulsed frequency of 10 kHz, and film thickness of 500 nm. To consider the effect of resistivity and optical diffuse transmittance, we performed etching of an 800 nm thick MZO thin film with 0.5 wt.% HCl for 3-6 s at 300 K. Consequently, we obtained a resistivity of 1.74-2.75 × 10^− 3 Ω cm, total transmittance at visible light of 67%-73%, diffuse transmittance at visible light of 25.1%-28.4%, haze value of 0.34-0.42, and thin film surface crater diameters of 220-350 nm.     

Advanced light trapping materials: Double layer ZnO:B based transparent conductive oxide

We present double layer structures consisting of ZnO:B/ZnO:B (BZO) and In₂O₃:Mo (IMO)/BZO films. The structure offers the unique opportunity of separating the conductivity of transparent conductive oxides from their light scattering behavior and allows their optimization for use in thin film solar cells. The layers serve as carrier transport and light trapping layers, respectively. BZO films were prepared by mid-frequency magnetic sputtering from a ZnO:B₂O₃ ceramic target. In order to enhance the conductivity of the BZO films, hydrogen was introduced into the sputtering atmosphere. Introducing hydrogen increased the mobility of the BZO-based double layer films to near 30 cm²/V•s. Efficient scattering was achieved by etching the film in dilute hydrochloric acid. IMO films were also tested as the transport layer. An unconventional surface morphology was obtained by etching the IMO/BZO double layer film. Using this cascading multilayer structure IMO/BZO film as the front contact in a-Si:H solar cell, 20.4% and 7.4% enhancements in short circuit current density were obtained compared to smooth IMO films and textured single layer BZO films.     

Texturization of ZnO:Al surface by reactive ion etching in SF<Subscript>6</Subscript>/Ar,CHF<Subscript>3</Subscript>/Ar plasma for application in thin film silicon solar cells

As-deposited sputtered ZnO:Al (AZO) thin films having high transparency (T?≥?85% at 550 nm of wavelength) and good electrical properties (ρ?=?2.59?×?10^?04 Ω cm) are etched to get suitable light trapping in thin film solar cells, using reactive ion etching method in sulfur hexafluoride–argon (SF₆/Ar) plasma and trifluoromethane–argon (CHF₃/Ar) plasma to texture their surface. Though the electrical properties of the films are not affected much by the etching process but significant increment in the average haze values in the wave length range of 350–1100 nm in the etched AZO films (19.21% for SF₆/Ar and 22.07% for CHF₃/Ar plasma etched) are found compared to as-deposited AZO films (5.61%). Increment in haze value is due to more scattering of light from the textured surface. These textured substrates are used as front transparent conducting oxide electrode for the fabrication of amorphous silicon solar cells. Solar cells fabricated on etched AZO substrates show 7.76% increase in conversion efficiency compared to as-deposited AZO substrates.     

Influence of rapid thermal annealing on surface texture-etched Al-doped ZnO films prepared by various magnetron sputtering methods

The influence of rapid thermal annealing (RTA) on surface texture formation as well as the light management obtainable by wet-chemically etching was investigated for transparent conducting Al-doped ZnO (AZO) thin films prepared by various types of magnetron sputtering deposition (MSD) with an oxide target. Texture-etched AZO films prepared by an r.f. (13.56 MHz) power-superimposed d.c. magnetron sputtering deposition (rf + dc-MSD) exhibited a higher haze value than found in equivalent films prepared by d.c. MSD. The order that the RTA treatment and the etching were conducted considerably affected the obtainable surface texture. Conducting the etching after a heat treatment with RTA in air resulted in larger etch pits as well as higher haze values than were obtained in AZO films that were etched before the RTA. A high haze value generally above 70% in the range from visible to near infrared (at wavelengths up to 1200 nm) was obtained in texture-etched AZO thin films that were prepared by rf + dc-MSD and etched after RTA at a temperature of 500 °C for 3 min.     

Ion sputter etching of ZnO:Ga thin film surfaces

In this article the modification of surface morphology of ZnO:Ga (GZO) thin films by ion sputter etching is presented. GZO thin films were prepared at room temperature on Corning glass substrates by both normal and oblique angle RF diode sputtering from ZnO:2%Ga ceramic target in Ar gas. Ion sputter etching was performed by RF re-sputtering of GZO thin films on substrates. During RF sputter etching, Ar pressure of 1.3 Pa and RF power of 250 W were kept constant, only the time of sputter etching was changed. Ion sputter etching had remarkable influence on surface morphology of GZO thin films: increase of roughness R_q and the “homogenization” of film surfaces, i.e. skewness (R_sk) and spikiness (R_ku) parameters (R_sk ≈ 0/R_ku ≈ 3).Surface root-mean-square roughness (R_q) increased from 15.3 nm (after sputter deposition) to 29.1 nm (after ion sputter etching). For obliquely thin films increased from 16.5 nm (after sputter deposition) to 38.2 nm. Changes of these parameters R_q, R_sk, R_ku influenced optical properties of GZO films, increased Haze parameter up to values 7.7% and width of optical band gap 3.44 eV, respectively.     

High rate direct current magnetron sputtered and texture-etched zinc oxide films for silicon thin film solar cells

Aluminum-doped zinc oxide (AZO) films were prepared by in-line direct current (dc) magnetron sputtering on glass substrates. Four types of ceramic targets with 0.5 wt.% or 1 wt.% of aluminum oxide and different preparation methods, namely normal sintered, soft sintered and hot pressed, were employed. The influence of different target manufacturing processes, aluminum concentration and sputtering conditions on AZO films were investigated. Depending on the type of targets and deposition conditions, highly transparent films with low resistivity values in the range of 3.6-11 × 10^− 4 Ω cm were obtained. The etching behaviour in hydrochloric acid and the resulting light scattering properties of the AZO films were strongly influenced by the choice of the target and the deposition conditions. The most favourable films have been successfully applied in thin film solar cells with 1.1-μm microcrystalline silicon absorber layer leading to an initial efficiency of 7.8%.     

Modification of AZO thin-film properties by annealing and ion etching

Effects of annealing and ion etching on the structural, electrical and optical properties of sputtered ZnO:Al (AZO) thin films were investigated. The post-deposition annealing at temperatures T_A = 200-400 °C in the forming gas (80% N₂/20% H₂) for 1 h and ion RF-sputter etching after annealing were used. Ion-sputter etching rate was 7 nm/min. The surface topography changed noticeably after ion-sputter etching: the surface of the sample was rougher (R_a = 33 nm) in comparison with annealed sample only (R_a = 9 nm). After the post-deposition annealing temperature T_A = 400 °C and ion-sputter etching thin films have higher integral transmittance (in the range of λ = 400-1000 nm) than non-etched samples. The figure of merit (F) became higher with increase of annealing temperature and the maximum value was F = 8%/Ω at T_A = 400 °C (R_s = 10 Ω, T_int = 86%).     

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.     

As-grown textured zinc oxide films by ion beam treatment and magnetron sputtering

This work presents as-grown textured ZnO:Al films by rf magnetron sputtering initiated by pre-treatment of glass substrate with mixed argon and oxygen ions. A 650 nm thick of this film exhibits surface texture features with lateral size around 500 nm; the resistivity is below 5 × 10⁻⁴ Ω · cm and the transparency in the near-infrared spectral range is high (> 80% at 1000 nm). Microcrystalline silicon thin film solar cells grown on the textured glass exhibit excellent light trapping effect with a short circuit current density of 18.2 mA/cm².     

Texturing of the back reflector for light trapping enhancement in micromorph thin film solar cells

The effects of textured back reflectors on light trapping in a-Si:H/μc-Si:H tandem cells are investigated with textured ZnO:Ga (GZO) back contacts obtained by surface wet etching. It is observed that rough back reflectors in fabricated tandem solar cells increase the short circuit current density of the bottom cells by 8%, which is attributed to light-trapping improvement. It is shown that enhanced longer wavelength light trapping is mainly attributable to improved light scattering at the back side by comparing identical a-Si:H/μc-Si:H tandem solar cells, both with a GZO back reflector but only one with a textured back reflector. The effectiveness of the textured GZO back reflector is also demonstrated in a textured a-Si:H/μc-Si:H tandem cell with a bottom cell thickness of 2 μm, which showed higher conversion efficiency than the reference cell.     

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.     

Effect of sol concentration on the structural, morphological, optical and photoluminescence properties of zirconia thin films

ZrO₂ thin films were deposited on quartz substrates from 10 wt.%, 20 wt.% and 40 wt.% solutions of Zirconium-n-butoxide in isopropanol by sol-gel dip-coating technique. Higher concentrated sols of 20 wt.% and 40 wt.% exhibited faster gelation, where as 10 wt.% sol remained stable for two months and films synthesized from this sol remained transparent and continuous even for 12 coatings. Ellipsometric study revealed that refractive index of the films increased with increase in sol concentration which is ascribed to the decrease in porosity. X-ray diffraction study showed that a tailoring of grain size from 7.9 to 39.2 nm is possible with increase in sol concentration. Atomic force microscopy studies showed a change in growth mode from vertical to lateral mode with increase in sol concentration. The film surface revealed positive skewness and high kurtosis values which make them favorable for tribological applications. The average optical transmittance in the visible region is highest (greater than 90%) for the film deposited from 10 wt.% sol. The optical band gap decreased from 5.74 to 5.62 eV with increase in the sol concentration. Photoluminescence (PL) spectra of the films exhibit an increase in the emission intensity with increase in sol concentration which substantiates better crystalline quality of the film deposited from 40 wt.% sol and increase in oxygen vacancies. The “Red shift” of the PL spectra with increase in sol concentration originates from the increase in the grain size with sol concentration which makes it suitable for generation of solid state lighting in light emitting diode.     

Optimization of textured structure on crystalline silicon wafer for heterojunction solar cell

Increasing the light scattering in monocrystalline silicon solar cells by surface texturing is an emerging field of practice in modern silicon photovoltaic. In this article, the surface micro-textures were performed on the monocrystalline silicon surface in potassium hydroxide solution without adding isopropyl alcohol. The parameters of the etching process such as concentration, time duration and temperature were examined to study the effects on shape and geometry of the microstructure. In addition, ray-tracing simulations of the light trapping were performed on these textured structures. The textured surfaces resemble the structures of uniform pyramids, mostly small pyramids, and mostly big pyramids. The simulation technique was applied in order to evaluate the light trapping effect by textured surfaces based on above pyramidal shape models. Afterwards, theoretical and experimental values of reflection data were compared. Such a simulation model was perceived as an effective tool for optimizing the micro structural shape, thus improving the light trapping. In this study, for solar cell applications, the double-side heterojunction solar cell with mostly big pyramids shape yielded an active area conversion efficiency of 16.3% with an open circuit voltage of 0.645 V, a short circuit current of 34.8 mA cm⁻² and a fill factor of 0.73.     

Tensile strain engineering of Si thin films using porous Si substrates

Highly tensile strained (up to 2.2%) thin monocrystalline silicon (mc-Si) films were fabricated by a simple and low-cost method based on the in-plane expansion of meso-porous silicon (PS) substrates upon low temperature oxidation. To control the film thickness below 100 nm, an original “two wafer” technique was employed during the porosification process. This method enables the fabrication of a 60 nm thick mc-Si films on 250 μm thick meso-porous silicon substrates over areas as large as 2 in. with a surface roughness and cleanliness comparable to that of standard Si wafers. Crack-free 60 nm thick Si films can be strained up to 1.2% by controlled low temperature oxidation of the PS substrate. Structural and strain analysis of the PS/mc-Si structures performed by transmission electron microscopy and micro-Raman scattering spectroscopy are reported.     

Fabrication of TiO2 nanotubes by anodization of Ti thin films for VOC sensing

Ti thin films were anodized in aqueous HF (0.5 wt.%) and in polar organic (0.5 wt.% NH₄F + ethylene glycol) electrolytes to form TiO₂ nanotube arrays. Ti thin films were deposited on microscope glass substrates and then anodized. Anodization was performed at potentials ranging from 5 V to 20 V for the aqueous HF and from 20 V to 60 V for the polar organic electrolytes over the temperatures range from 0 to 20 °C. The TiO₂ nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX). It has been observed that anodization of the deposited Ti thin films with aqueous HF solution at 0 °C resulted in nanotube-type structures with diameters in the range of 30-80 nm for an applied voltage of 10 V. In addition, the nanotube-type structure is observed for polar organic electrolyte at room temperature at the anodization voltage higher than 40 V. The volatile organic compound (VOC) sensing properties of TiO₂ nanotubes fabricated using different electrolytes were investigated at 200 °C. The maximum sensor response is obtained for carbon tetrachloride. The sensor response is dependent on porosity of TiO₂. The highest sensor response is observed for TiO₂ nanotubes which are synthesized using aqueous HF electrolyte and have very high porosity.     

Natively textured surface aluminum-doped zinc oxide transparent conductive layers for thin film solar cells via pulsed direct-current reactive magnetron sputtering

Natively textured surface aluminum-doped zinc oxide (ZnO:Al) layers for thin film solar cells were directly deposited without any surface treatments via pulsed direct-current reactive magnetron sputtering on glass substrates. Such an in-situ texturing method for sputtered ZnO:Al thin films has the advantages of efficiently reducing production costs and dramatically saving time in photovoltaic industrial processing. High purity metallic Zn-Al (purity: 99.999%, Al 2.0 wt.%) target and oxygen (purity: 99.999%) were used as source materials. During the reactive sputtering process, the oxygen gas flow rate was controlled using plasma emission monitoring. The performance of the textured surface ZnO:Al transparent conductive oxides (TCOs) thin films can be modified by changing the number of deposition rounds (i.e. thin-film thicknesses). The initially milky ZnO:Al TCO thin films deposited at a substrate temperature of ~ 553 K exhibit rough crater-like surface morphology with high transparencies (T ~ 80-85% in visible range) and excellent electrical properties (ρ ~ 3.4 × 10^− 4 Ω cm). Finally, the textured-surface ZnO:Al TCO thin films were preliminarily applied in pin-type silicon thin film solar cells.     

Low-damage surface modification of polymethylmethacrylate with argon-oxygen mixture plasmas driven by multiple low-inductance antenna units

Surface modification of polymethylmethacrylate (PMMA) films has been investigated with argon-oxygen mixture plasmas sustained with multiple low-inductance antenna units. PMMA films were exposed to argon-oxygen mixture (20%) plasmas on a water-cooled substrate holder. Average ion energies bombarding onto the PMMA films was estimated to be as low as 6 eV, which was evaluated from the gap between plasma potential and floating potential. The etching depth of PMMA surface increased linearly with increasing plasma-exposure time and the etching rate was 170 nm/min. Surface roughness of PMMA slightly increased from 0.3 nm to 1.4 nm with increasing exposure time. Hard X-ray photoelectron spectroscopy (HXPES) was carried out to examine chemical bonding states of the PMMA surface in deeper regions (about 54 nm) as compared with those observed in shallower regions (27 nm).     

Synthesis of YAG:Ce/TiO2 nanocomposite films

Our work is devoted to the development of YAG:Ce³⁺ phosphor nanoparticle-based converter layer for white LEDs. To avoid losses due to scattering effects, the strategy is to control separately the down-conversion and the extraction of light instead of using micron-sized luminescent particles acting simultaneously as both converter and scatterer. YAG:Ce nanoparticles were synthesized by a glycothermal method in autoclave at low temperature (300 °C). Y₃Al₅O₁₂ garnet phase with a crystallite size of 25 nm was obtained, as verified by X-ray diffraction and electron microscopy. The quantum yield of nanoparticles is 55%. The colloidal nanoparticles are finally incorporated into a sol-gel matrix of TiO₂. The small difference in refractive index between particles and matrix and the nanosize of the particles contribute to the transparency of the converter films. The surface of these layers can be periodically patterned by soft nano-imprint lithography. The diffraction due to the obtained photonic crystal at the surface may offer the opportunity to compensate the absence of scattering to extract the converted light.