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.     

Porous nanostructured ZnO films deposited by picosecond laser ablation

Porous nanostructured polycrystalline ZnO films, free of large particulates, were deposited by picosecond laser ablation. Using a Zn target, zinc oxide films were deposited on indium tin oxide (ITO) substrates using a picosecond Nd:YVO₄ laser (8 ps, 50 kHz, 532 nm, 0.17 J/cm²) in an oxygen atmosphere at room temperature (RT). The morpho-structural characteristics of ZnO films deposited at different oxygen pressures (150–900 mTorr) and gas flow rates (0.25 and 10 sccm) were studied. The post-deposition influence of annealing (250–550 °C) in oxygen on the film characteristics was also investigated. At RT, a mixture of Zn and ZnO formed. At substrate temperatures above 350 °C, the films were completely oxidized, containing a ZnO wurtzite phase with crystallite sizes of 12.2–40.1 nm. At pressures of up to 450 mTorr, the porous films consisted of well-distinguished primary nanoparticles with average sizes of 45–58 nm, while at higher pressures, larger clusters (3.1–14.7 μm) were dominant, leading to thicker films; higher flow rates favored clustering.     

Mn-doped ZnO transparent conducting films deposited by DC magnetron sputtering

Mn-doped zinc oxide (ZnO:Mn) thin films with low resistivity and relatively high transparency were firstly prepared on glass substrate by direct current (DC) magnetron sputtering at room temperature. Influence of film thickness on the properties of ZnO:Mn films was investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) show that all the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. As the thickness increases from 144 to 479 nm, the crystallite size increases while the electrical resistivity decreases. However, as the thickness increases from 479 to 783 nm, the crystallite size decreases and the electrical resistivity increases. When film thickness is 479 nm, the deposited films have the lowest resistivity of 2.1 × 10^− 4 Ω cm and a relatively high transmittance of above 84% in the visible range.     

Structural,electrical and photoluminescence properties of ZnO:Al films grown on MgO(0 0 1) by direct current magnetron sputtering with the oblique target

ZnO:Al films were deposited on MgO(0 0 1) substrates at 300 K and 673 K by direct current magnetron sputtering with the oblique target. The Ar pressure was adjusted to 0.4 Pa and 1.2 Pa, respectively. All the films have a wurtzite structure and a c-axis orientation in the film growth direction. The films deposited at 300 K initially grow with thin columnar grains and subsequently grow with large granular grains on the thin columnar grains. However, the films grown at 673 K consist mainly of dense columnar grains perpendicular to the substrate surface. The ZnO:Al film deposited at 673 K and 0.4 Pa has the lowest resistivity, the highest free electron concentration and Hall's mobility. A temperature dependence of the resistivity within 5–300 K reveals that the films grown at 300 K exhibit a semiconducting behavior and those grown at 673 K show a metal–semiconductor transition. The carrier transport mechanism is Mott's variable range hopping in the temperature range below 90 K for all the films and thermally activated band conduction above 215 K for the films grown at 300 K. Room temperature photoluminescence spectra for wavelengths between 300 nm and 800 nm reveal mainly blue-green emissions centered at 452 nm, 475 nm and 515 nm.     

Substrate temperature dependence of the properties of Ga-doped ZnO films deposited by DC reactive magnetron sputtering

Ga-doped zinc oxide (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. The influence of substrate temperature on the structural, electrical, and optical properties of ZnO:Ga films was investigated. The X-ray diffraction (XRD) studies show that higher temperature helps to promote Ga substitution more easily. The film deposited at 350 °C has the optimal crystal quality. The morphology of the films is strongly related to the substrate temperature. The film deposited is dense and flat with a columnar structure in the cross-section morphology. The transmittance of the ZnO:Ga thin films is over 90%. The lowest resistivity of the ZnO:Ga film is 4.48×10⁻⁴ Ω cm, for a film which was deposited at the substrate temperature of 300 °C.     

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.     

Low temperature annealing effects on the structure and optical properties of ZnO films grown by pulsed laser deposition

ZnO thin films were deposited on glass substrates at room temperature (RT) ∼500 °C by pulsed laser deposition (PLD) technique and then were annealed at 150-450 °C in air. The effects of annealing temperature on the microstructure and optical properties of the thin films deposited at each substrate temperature were investigated by XRD, SEM, transmittance spectra, and photoluminescence (PL). The results showed that the c-axis orientation of ZnO thin films was not destroyed by annealing treatments; the grain size increased and stress relaxed for the films deposited at 200-500 °C, and thin films densified for the films deposited at RT with increasing annealing temperature. The transmittance spectra indicated that E_g of thin films showed a decreased trend with annealing temperature. From the PL measurements, there was a general trend, that is UV emission enhanced with lower annealing temperature and disappeared at higher annealing temperature for the films deposited at 200-500 °C; no UV emission was observed for the films deposited at RT regardless of annealing treatment. Improvement of grain size and stoichiometric ratio with annealing temperature can be attributed to the enhancement of UV emission, but the adsorbed oxygen species on the surface and grain boundary of films are thought to contribute the annihilation of UV emission. It seems that annealing at lower temperature in air is an effective method to improve the UV emission for thin films deposited on glass substrate at substrate temperature above RT.     

Effect of spatial relationship between arc plasma and substrate on the properties of transparent conducting Ga-doped ZnO thin films prepared by vacuum arc plasma evaporation

The effect of the spatial relationship between the arc plasma flow and the substrate surface on the resulting film thickness and electrical properties is investigated in transparent conducting Ga-doped ZnO (GZO) thin films deposited by a vacuum arc plasma evaporation (VAPE) method. It was found that the resulting electrical properties of GZO thin films produced by a VAPE deposition on a fixed substrate were considerably dependent on both the film thickness and the location on the substrate surface, extending from the area nearest the arc plasma source to that at the opposite end of the substrate in a direction parallel to the arc plasma flow; with GZO thin films deposited with various thicknesses in the range from 20 to 200 nm, the films exhibited a thickness dependence of resistivity that was considerably affected by the location on the substrate surface. The variation of resistivity relative to the location on the substrate surface was related to that of carrier concentration, which is mainly attributed to the distribution of the amount of oxygen reaching the substrate surface. In GZO thin films deposited with a thickness of 30-40 nm at a substrate temperature of 250 °C, a resistivity as low as 4 × 10^− 4 Ω cm was obtained in the area of the substrate nearest the arc plasma source.     

Deposition of Al-doped ZnO films on polyethylene naphthalate substrate with radio frequency magnetron sputtering

100 nm Al-doped ZnO (AZO) thin films were deposited on polyethylene naphthalate (PEN) substrates with radio frequency magnetron sputtering using 2 wt.% Al-doped ZnO target at various deposition conditions including sputtering power, target to substrate distance, working pressure and substrate temperature. When the sputtering power, target to substrate distance and working pressure were decreased, the resistivity was decreased due to the improvement of crystallinity with larger grain size. As the substrate temperature was increased from 25 to 120 °C, AZO films showed lower electrical resistivity and better optical transmittance due to the significant improvement of the crystallinity. 2 wt.% Al-doped ZnO films deposited on glass and PEN substrates at sputtering power of 25 W, target to substrate distance of 6.8 cm, working pressure of 0.4 Pa and substrate temperature of 120 °C showed the lowest resistivity (5.12 × 10^− 3 Ω cm on PEN substrate, 3.85 × 10^− 3 Ω cm on glass substrate) and high average transmittance (> 90% in both substrates). AZO films deposited on PEN substrate showed similar electrical and optical properties like AZO films deposited on glass substrates.     

Effect of the oxygen pressure on the photoluminescence properties of ZnO thin films by PLD

ZnO thin films on Si(111) substrate were deposited by laser ablation of Zn target in oxygen reactive atmosphere; Nd-YAG laser with wavelength of 1064 nm was used as laser source. The experiments were performed at laser energy density of 31 J/cm², substrate temperature of 400 °C and various oxygen pressures (5–65 Pa). X-ray diffraction was applied to characterize the structure of the deposited ZnO films and the optical properties of the ZnO thin films were characterized by photoluminescence with an Ar ion laser as a light source using an excitation wavelength of 325 nm. The influence of the oxygen pressure on the structural and optical properties of ZnO thin films was investigated. It was found that ZnO film with random growth grains can be obtained under the condition of oxygen pressure 5–65 Pa. It will be clearly shown that the grain size and the formation of intrinsic defects depend on the oxygen partial pressure and that high optical quality of the ZnO films is obtained under low oxygen pressure (5 Pa, 11 Pa) conditions.     

AFM surface analysis of ZnO layers prepared by pulsed laser deposition at different oxygen pressures

Polycrystalline thin films of zinc oxide were deposited by pulsed laser deposition onto silicon substrates at different oxygen partial pressures in the range of 1-35 Pa. For ablation of the sintered zinc oxide target a pulsed Nd:YAG laser was used. Other processing parameters such as laser pulse energy, pulse repetition rate, substrate temperature and deposition pressure were identical. The effect of oxygen pressure on the structural properties of the films was systematically studied by using atomic force microscopy. The surface morphology, average roughness S_a, root mean square S_q, and mean size of grains on selected places with 2 × 2 μm² area of prepared samples were evaluated. Detailed structural analysis confirmed that partial oxygen pressure leads to the modification of surface morphology. Mean grain size in height and lateral direction decreases with raising oxygen pressure from 1 to 5 Pa while the further increase of oxygen pressure from 5 to 35 Pa results in grain size enlargement. The zinc oxide film formed at oxygen partial pressure 5 Pa shows smallest values of evaluated parameters (S_a = 0.6 nm, S_q = 0.7 nm and mean size of grains 50 nm).     

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.     

Femtosecond laser deposited zinc oxide film and its optical properties

Zinc oxide (ZnO) thin films have been grown on Si (100) substrates using a femto-second pulsed laser deposition (fsPLD) technique. The effects of substrate temperature and laser energy on the structural, surface morphological and optical properties of the films are discussed. The X-ray diffraction results show that the films are highly c-axis oriented when grown at 80 °C and (103)-oriented at 500 °C. In the laser energy range of 1.0 mJ-2.0 mJ, the c-axis orientation increases and the mean grain size decreases for the films deposited at 80 °C. The field emission scanning electron microscopy indicates that the films have a typical hexagonal structure. The optical transmissivity results show that the transmittance increases with the increasing substrate temperature. In addition, the photoluminescence spectra excited with 325 nm light at room temperature are studied. The structural properties of ZnO films grown using nanosecond (KrF) laser are also discussed.     

Pulsed electron beam deposition of transparent conducting Al-doped ZnO films

Good quality transparent conducting Al-doped ZnO films were deposited on quartz substrates from a high purity target using pulsed electron deposition (PED). Two series of films were made, one deposited at room temperature but at four pressures, viz., 0.7, 1.3, 2.0 and 2.7 Pa of oxygen and one deposited at 1.3 Pa oxygen pressure but at the substrate temperature ranged from room temperature to 600 °C. In order to evaluate the effect of substrate temperature and oxygen pressure on the properties of obtained films, various characterization techniques were employed including X-ray diffraction, stylus profiler, scanning electron microscope, optical spectrophotometer and electrical resistivity. For the first series films, the optimal oxygen pressure of 1.3 Pa was found to bring about the appropriate energetic deposition atoms which results in the best crystallinity. For the second series films, the lowest resistivity was obtained in the film grown at 400 °C. An attempt was made to reduce the resistivity by lowering the oxygen pressure to 0.5 Pa which was the lower limit of working pressure of the PED system. The obtained results indicate that PED is a suitable technique for growing transparent conducting ZnO films.     

Influence of oxygen pressure on the structural, electrical and optical properties of VO2 thin films deposited on ZnO/glass substrates by pulsed laser deposition

The influence of oxygen pressure on the structural and electrical properties of vanadium oxide thin films deposited on glass substrates by pulsed laser deposition, via a 5-nm thick ZnO buffer, was investigated. For the purposes of comparison, VO₂ thin films were also deposited on c-cut sapphire and glass substrates. During laser ablation of the V metal target, the oxygen pressure was varied between 1.33 and 6.67 Pa at 500 °C, and the interaction and reaction of the VO₂ and the ZnO buffer were studied. X-ray diffraction studies showed that the VO₂ thin film deposited on a c-axis oriented ZnO buffer layer under 1.33 Pa oxygen had (020) preferential orientation. However, VO₂ thin films deposited under 5.33 and 6.67 Pa were randomly oriented and showed (011) peaks. Crystalline orientation controlled VO₂ thin films were prepared without such expensive single crystal substrates as c-cut sapphire. The metal-insulator transition properties of the VO₂/ZnO/glass samples were investigated in terms of electrical conductivity and infrared reflectance with varying temperatures, and the surface composition was investigated by X-ray photoelectron spectroscopy.     

A comparative study on the NO2 gas sensing properties of ZnO thin films, nanowires and nanorods

ZnO thin films were fabricated using the spin coating method, ZnO nanowires by cathodically induced sol-gel deposition by the means of an anodic aluminum oxide (AAO) template, and ZnO nanorods with the hydrothermal technique. For thin film preparation, a clear, homogeneous and stable ZnO solution was prepared by the sol-gel method using zinc acetate (ZnAc) precursor which was then coated on a glass substrate with a spin coater. Vertically aligned ZnO nanowires which were approximately 65 nm in diameter and 10 μm in length were grown in an AAO template by applying a cathodic voltage in aqueous zinc nitrate solution at room temperature. For fabrication of the ZnO nanorods, the sol-gel ZnO solution was coated on glass substrate by spin coating as a seed layer. Then ZnO nanorods were grown in zinc nitrate and hexamthylenetetramine aqueous solution. The ZnO nanorods are approximately 30 nm in diameter and 500 nm in length. The ZnO thin film, ZnO nanowires and nanorods were characterized by X-ray diffraction (XRD) analysis and scanning electron microscope (SEM). The NO₂ gas sensing properties of ZnO thin films, nanowires and nanorods were investigated in a dark chamber at 200 °C in the concentration range of 100 ppb-10 ppm. It was found that the response times of both ZnO thin films and ZnO nanorods were approximately 30 s, and the sensor response was depended on shape and size of ZnO nanostructures and electrode configurations.     

High mobility, transparent, conducting Gd-doped In2O3 thin films by pulsed laser deposition

Highly transparent and conducting thin films of gadolinium doped indium oxide, which have high electron mobility, were deposited on quartz substrate to study the effect of growth temperature and oxygen pressure on their structural, optical, and electrical properties. X-ray diffraction study reveals that these films are randomly oriented on the quartz surface. The average particle size of the films grown at 600 °C was calculated to be ∼ 23 nm. The optical transparency of the films increases with an increase in the growth temperature. The film transparency is also found to increase with increased oxygen pressure during deposition. The electrical properties of these films strongly depend on both the growth temperature and the oxygen pressure. Analysis of the electrical data shows that the mobility of the films increases with increase in the growth temperature.     

Nano-polycrystalline vanadium oxide thin films prepared by pulsed laser deposition

Nano-polycrystalline vanadium oxide thin films have been successfully produced by pulsed laser deposition on Si(100) substrates using a pure vanadium target in an oxygen atmosphere. The vanadium oxide thin film is amorphous when deposited at relatively low substrate temperature (500 degrees C) and enhancing substrate temperature (600-800 degrees C) appears to be efficient in crystallizing VOx thin films. Nano-polycrystalline V3O7 thin film has been achieved when deposited at oxygen pressure of 8 Pa and substrate temperature of 600 degrees C. Nano-polycrystalline VO2 thin films with a preferred (011) orientation have been obtained when deposited at oxygen pressure of 0.8 Pa and substrate temperatures of 600-800 degrees C. The vanadium oxide thin films deposited at high oxygen pressure (8 Pa) reveal a mix-valence of V5+ and V4+, while the VOx thin films deposited at low oxygen pressure (0.8 Pa) display a valence of V4+. The nano-polycrystalline vanadium oxide thin films prepared by pulsed laser deposition have smooth surface with high qualities of mean crystallite size ranging from 30 to 230 nm and Ra ranging from 1.5 to 22.2 nm. Relative low substrate temperature and oxygen pressure are benifit to aquire nano-polycrystalline VOx thin films with small grain size and low surface roughness.     

Effect of aluminum and indium co-doping on zinc oxide films prepared by dc magnetron sputtering

Aluminum and indium co-doped zinc oxide (AIZO) thin films were prepared by direct current (dc) magnetron sputtering on glass substrate in pure argon atmosphere. Three inches of zinc oxide ceramic with 0.5 wt.% of aluminum and indium doping was used as a target in static mode. The influence of sputtering conditions i.e. substrate-target distance, pressure and power on AIZO films was studied. The electrical resistivity and microstructure of thin films were investigated by the four point probe technique and the scanning electron microscope, respectively. The optical transmittance of AIZO films was measured by UV visible spectrophotometer in the wavelength of 300-1100 nm. Depending on the deposited conditions, highly transparent films up to 80% with low resistivities in the range of 2.6-7.9 × 10^− 4 Ω cm were achieved at room temperature. Possible mechanism in the processing which, ultimately, determines the physical properties of AIZO films will be discussed.     

Fabrication of high quality zinc-oxide layers through electrohydrodynamic atomization

Zinc oxide (ZnO) is a useful material in the fabrication of many electronic devices because of its wide band-gap, excellent transparency and high electron mobility. Thin films of ZnO have been fabricated where an alcosol solution containing 7 wt.% ZnO nano-particles was synthesized and subjected to controlled flow through a metal capillary exposed to an electric field at the ambient temperature to generate an electrohydrodynamic jet, which subsequently disintegrated into droplets thereby depositing a uniform thin film of zinc oxide on the glass substrates with an average thickness of 115 nm at a constant substrate speed of 0.25 mm/s. Pure and perfectly uniform transparent films with an average transmittance of 88% have been deposited with wurtzite crystal structure and an electrical resistivity of approximately 64 Ω.cm.