Effects of substrate temperature on the efficiency of hydrogen incorporation on the properties of Al-doped ZnO films

Al-doped ZnO (AZO) transparent conducting films were successfully prepared on glass substrates by RF magnetron sputtering at different substrate temperatures in Ar and H₂ + Ar sputtering ambient. The effects of substrate temperature on the effectiveness of hydrogen incorporation in Al-doped ZnO films were investigated. The microstructural, electrical and optical properties of AZO films were systematically analyzed by surface profiler, X-ray diffractometry, scanning electron microscope, four-point probe measurement and UV/vis spectrophotometer. The XRD patterns and SEM pictures indicate that the crystallinity of AZO thin films was markedly improved with hydrogen incorporation at low substrate temperature, while the improvement of crystallinity was not an obvious change at high substrate temperature. The results also indicate that hydrogen incorporation has the stronger effectiveness on the transparent conductive properties of AZO films with the substrate temperature decreasing. The resistivity of the films decreases, especially for lower substrate temperatures, due to the incorporation of hydrogen atoms. These results suggest that substrate temperature should be controlled to the lower level to effectively reduce resistivity without detriment to transmittance of AZO thin films when hydrogen is incorporated.     

Optical properties of Al-doped ZnO thin films by ellipsometry

Al-doped ZnO thin films (AZO) were prepared on Si (1 0 0) substrates by using sub-molecule doping technique. The Al content was controlled by varying Al sputtering time. The as-prepared samples were annealed in vacuum chamber at 800 °C for 30 min. From the XRD observations, it is found that all films exhibit only the (0 0 2) peak, suggesting that they have c-axis preferred orientation. The average transmittance of the visible light is above 80%. Spectroscopic ellipsometry was used to extract the optical constants of the films. The absorption coefficient and the energy gap were then calculated. The results show that the absorption edge initially blue-shifts and then red-shifts with increase of Al content.     

Effects of deposition temperatures and annealing conditions on the microstructural, electrical and optical properties of polycrystalline Al-doped ZnO thin films

Al-doped ZnO (AZO, ZnO:Al₂O₃ = 98:2 wt%) films are deposited on different substrates by an RF magnetron sputtering and subsequently annealed at three different conditions to investigate the microstructural, electrical, and optical properties. X-ray diffraction and scanning electron microscope results show that all the samples are polycrystalline and the samples rapid-thermal-annealed at 900 °C in an N₂ ambient contain larger grains compared to the furnace-annealed samples. It is shown that the sample deposited at room temperature on the sapphire gives a resistivity of 5.57 × 10⁻⁴ Ω cm when furnace-annealed at 500 °C in a mixture of N₂:H₂ (9:1). It is also shown that the Hall mobility vs. carrier concentration (μ-n) relation is divided into two groups, depending on the annealing conditions, namely, either rapid-thermal annealing or furnace annealing. The relations are described in terms of either grain boundary scattering or ionized impurity scattering mechanism. In addition, the samples produce fairly high transmittance of 91-96.99% across the wavelength region of 400-1100 nm. The optical bandgaps of the samples increase with increasing carrier concentration.     

Effects of deposition temperature on the structural and morphological properties of thin ZnO films fabricated by pulsed laser deposition

ZnO thin films were grown on Si(1 0 0) substrates using pulsed laser deposition in O₂ gas ambient (10 Pa) and at different substrate temperatures (25, 150, 300 and 400 °C). The influence of the substrate temperature on the structural and morphological properties of the films was investigated using XRD, AFM and SEM. At substrate temperature of T=150 °C, a good quality ZnO film was fabricated that exhibits an average grain size of 15.1 nm with an average RMS roughness of 3.4 nm. The refractive index and the thickness of the thin films determined by the ellipsometry data are also presented and discussed.     

Effects of annealing on structural,optical and electrical properties of Al-doped ZnO thin films

Transparent conducting oxide (TCO) thin films such as SnO2, In2O3, and Cd2SnO4, have been used extensively as sensor devices, surface acoustic wave devices, coating to heat glass windows and transparent electrodes for solid state display devices, solar cells[1,2] because of their high optical transparency in the visible range, infrared reflec-tance and low d.c. resistivity. Although SnO2 film was developed early, nowadays Sn-doped In2O3 (ITO) films are the predominant TCO thin film in …     

Effects of hydrogen flow on properties of hydrogen doped ZnO thin films prepared by RF magnetron sputtering

The hydrogen doped ZnO (ZnO:H) thin films were deposited on quartz glass substrates by radio frequency magnetron sputtering. The doping characteristics of ZnO:H thin films with varied hydrogen flow ratio were investigated. At low hydrogen flow ratio (H₂/(H₂+Ar)≤0.02), the ZnO:H thin films exhibited dominant (002) peaks from X-ray diffraction and the lattice constants became smaller. The particles were mainly a columnar structure. The particles’ size became smaller, and the island-like structure appeared on the thin films surface. In addition, the low resistivity properties of ZnO:H thin films was ascribed to the increase of the carriers concentration and carriers mobility; When the hydrogen flow ratio was more than 0.02 (M≥0.02), two absorption bands at 1400–1800 cm^?1 and 3200–3900 cm^?1 were observed from the FT-IR spectra, which indicated that the ZnO:H thin films had typical Zn–H bonding, O–H bonding (hydroxyl), and Zn–H–O bonding (like-hydroxyl). The scanning electron microscope (SEM) results show that a large number of hydroxyl agglomeration formed an island-like structure on the thin films surface. The absorption peak at about 575 cm^?1 in the Raman spectra indicated that oxygen vacancies (V_O) defects were produced in the process of high hydrogen doping. In this condition, the low resistivity properties of ZnO:H thin films were mainly due to the increasing electron concentration resulted from V_O. Meanwhile, the Raman absorption peaks at approximately 98 cm^?1 and 436 cm^?1 became weaker, and the (002) XRD diffraction peak quenched and the lattice constants increased, which shows that the ZnO:H thin films no longer presented a typical ZnO hexagonal wurtzite structure. With the increasing of hydrogen flow ratio, the optical transmittance of ZnO:H thin films in the ultraviolet band show a clear Burstein–Moss shift effect, which further explained that electron concentration was increased due to the increasing V_O with high hydrogen doping concentration. Moreover, the optical reflectance of the thin films decreased, indicating the higher roughness of the films surface. It was noteworthy that etching effect of H plasma was obvious in the process of heavy hydrogen doping.     

Effects of post-annealing on structural, optical and electrical properties of Al-doped ZnO thin films

Aluminum-doped zinc oxide (AZO) films were deposited at 400 °C by radio-frequency magnetron sputtering using a compound AZO target. The effects of annealing atmospheres as well as hydrogen annealing temperatures on the structural, optical and electrical properties of the AZO films were investigated. It was found that the electrical resistivity varied depending on the atmospheres while annealing in air, nitrogen and hydrogen at 300 °C, respectively. Comparing with that for the un-annealed films, the resistivity of the films annealed in hydrogen decreased from 9.8 × 10⁻⁴ Ω cm to 3.5 × 10⁻⁴ Ω cm, while that of the films annealed in air and nitrogen increased. The variations in electrical properties are ascribed to both the changes in the concentration of oxygen vacancies and adsorbed oxygen at the grain boundaries. These results were clarified by the comparatively XPS analyzing about the states of oxygen on the surface of the AZO films. There was great increase in electrical resistivity due to the damage of the surfaces, when AZO films were annealed in hydrogen with a temperature higher than 500 °C, but high average optical transmittance of 80-90% in the range of 390-1100 nm were still obtained.     

Properties of amorphous silicon films: Dependence on deposition rate

We have measured the d.c. conductivity at 300 K, the spin density and the optical absorption in amorphous silicon films deposited at rates between 0.4 and 10 Å/sec. It is found that all these quantities reduce sharply as the deposition rate is decreased. The data are compared to the heat treatment behavior reported recently. The possibility of oxygen contamination is discussed.     

Electrical and optical properties of Al-doped ZnO thin films by sol-gel process

Al-doped ZnO (AZO) thin films oriented along the (0 0 2) plane have been prepared by the sol-gel process and their electrical and optical properties with post-deposition heating temperature were investigated. The preferred c-axis orientation along the (0 0 2) plane was enhanced with increasing post-deposition heating temperature and the surface of the films showed a uniform and nano-sized microstructure. The electrical resistivity of the films decreased from 73 to 22 Ω cm as the post-deposition heating temperature increased from 500 to 650 °C; however, the film postheated at 700 °C increased greatly to 580 Ω cm. The optical transmittance of the films postheated below 650 °C was over 86%, but it decreased at 700 °C. The electrical and optical properties of the AZO films with post-deposition heating temperature are discussed.     

X-ray photoelectron spectroscopy study and thermoelectric properties of Al-doped ZnO thin films

In this paper, high quality Al-doped ZnO (AZO) thin films were prepared by direct current (DC) reactive magnetron sputtering using a Zn target (99.99%) containing Al of 1.5 wt.%. The films obtained were characterized by X-ray photoelectron spectroscopy (XPS) and thermoelectric measurements. The XPS results reveal that Zn and Al exist only in oxidized state, while there are dominant crystal lattice and rare adsorbed oxygen for O in the annealed AZO thin films. The studies of thermoelectric property show a striking thermoelectric effect in the AZO thin films. On the one hand, the thermoelectromotive and magnetothermoelectromotive forces increase linearly with increasing temperature difference (ΔT). On the other hand, the thermoelectric power (TEP) decreases with the electrical resistance of the sample. But the TEP increases with the increase of temperature below 300 K, and it nearly does not change around room temperature. The experimental results also demonstrate that the annealing treatment increases TEP, while the external magnetic field degrades TEP.     

Effect of substrate temperature on the structural and optical properties of ZnO and Al-doped ZnO thin films prepared by dc magnetron sputtering

ZnO and Al-doped ZnO(ZAO) thin films have been prepared on glass substrates by direct current (dc) magnetron sputtering from 99.99% pure Zn metallic and ZnO:3 wt%Al₂O₃ ceramic targets, the effects of substrate temperature on the crystallization behavior and optical properties of the films have been studied. It shows that the surface morphologies of ZAO films exhibit difference from that of ZnO films, while their preferential crystalline growth orientation revealed by X-ray diffraction remains always the (0 0 2). The optical transmittance and photoluminescence (PL) spectra of both ZnO and ZAO films are obviously influenced by the substrate temperature. All films exhibit a transmittance higher than 86% in the visible region, while the optical transmittance of ZAO films is slightly smaller than that of ZnO films. More significantly, Al-doping leads to a larger optical band gap (E_g) of the films. It is found from the PL measurement that near-band-edge (NBE) emission and deep-level (DL) emission are observed in pure ZnO thin films. However, when Al was doped into thin films, the DL emission of the thin films is depressed. As the substrate temperature increases, the peak of NBE emission has a blueshift to region of higher photon energy, which shows a trend similar to the E_g in optical transmittance measurement.     

Excimer-laser-assisted RF glow-discharge deposition of amorphous and microcrystalline silicon thin films

We combine the deposition of Hydrogenated amorphous Silicon (a-Si:H) by rf glow discharge with XeCl-excimer laser irradiation of the growing surface in order to obtain different kinds of silicon films in the same deposition system. In-situ UV-visible ellipsometry allows us to measure the optical properties of the films as the laser fluence is increased from 0 up to 180 mJ/cm² in separate depositions. For fixed glow-discharge conditions and a substrate temperature of 250° C we observe dramatic changes in the film structure as the laser fluence is increased. With respect to a reference a-Si:H film (no laser irradiation) we observe at low laser fluences (15–60 mJ/cm²) that the film remains amorphous but demonstrates enchanced surface roughness and bulk porosity. At intermediate fluences (80–165 m/Jcm²), we obtain an amorphous film with an enhanced density with respect to the reference film. Finally, at high fluences (165–180 mJ/cm²), we obtain microcrystalline films. The in-situ ellipsometry measurements are complemented by ex-situ measurements of the dark conductivity, X-ray diffraction, and Elastic Recoil Detection Analysis (ERDA). Simulation of the temperature profiles for different film thicknesses and for three laser fluences indicates that crystallization occurs if the surface temperature reaches the melting point of a-Si:H ( 1420 K). The effects of laser treatment on the film properties are discussed by taking into account the photonic and thermal effects of laser irradiation.Presented at LASERION 93, Munich, June 21–23, 1993     

Optical and electrical characteristics of Al-doped ZnO thin films prepared by aqueous phase deposition

Transparent conducting Al-doped ZnO (AZO) thin films have been deposited by sol-gel route. Starting from an aqueous solution of zinc acetate by adding aluminum chloride as dopant, a c-axis oriented polycrystalline ZnO thin film 100 nm in thickness could be spin-coated on glass substrates via a two-step annealing process under reducing atmosphere. The effects of thermal annealing and dopant concentration on the structural, electrical and optical properties of AZO thin films were investigated. The post-treated AZO films exhibited a homogenous dense microstructure with grain sizes less than 10 nm as characterized by SEM photographs. The annealing atmosphere has prominent impact on the crystallinity of the films which will in turn influence the electrical conductivity. By varying the doping concentrations, the optical and electrical properties could be further adjusted. An optimal doping concentration of Al/Zn = 2.25 at.% was obtained with minimum resistivity of 9.90 × 10⁻³ Ω-cm whereas the carrier concentration and mobility was 1.25 × 10²⁰ cm⁻³ and 5.04 cm² V⁻¹ s⁻¹, respectively. In this case, the optical transmittance in the visible region is over 90%.     

Influence of deposition temperature on the crystallinity of Al-doped ZnO thin films at glass substrates prepared by RF magnetron sputtering method

Al-doped ZnO (AZO) transparent conducting films were successfully prepared on glass substrates by RF magnetron sputtering method under different substrate temperatures. The microstructural, electrical and optical properties of AZO films were investigated in a wide temperature range from room temperature up to 350 °C by X-ray Diffraction (XRD), Field-Emission Scanning Electron Microscopy (FESEM), High-Resolution Transmission Electron Microscopy (HRTEM), Hall measurement, and UV–visible meter. The nature of AZO films is polycrystalline thin films with hexagonal wurtzite structure and a preferred orientation along c-axis. The crystallinity and surface morphologies of the films are strongly dependent on the growth temperature, which in turn exerts a great effect on microstructural, electrical and optical properties of the AZO films. The atomic arrangement of AZO film having an wurtzite structure was indeed identified by the HRTEM as well as the Selected Area Electron Diffraction (SAED). The defect density of AZO film was investigated by HRTEM. The film deposited at 100 °C exhibited the relatively well crystallinity and the lowest resistivity of 3.6 × 10⁻⁴ Ω cm. The average transmission of AZO films in the visible range is all over 85%. More importantly, the low-resistance and high-transmittance AZO film was also prepared at a low temperature of 100 °C.     

Influence of the total gas flow rate on high rate growth microcrystalline silicon films and solar cells

This paper reports that high-rate-deposition of microcrystalline silicon solar cells was performed by very-high-frequency plasma-enhanced chemical vapor deposition. These solar cells, whose intrinsic μ c-Si:H layers were prepared by using a different total gas flow rate (F_total), behave much differently in performance, although their intrinsic layers have similar crystalline volume fraction, opto-electronic properties and a deposition rate of ～ 1.0~nm/s. The influence of F_total on the micro-structural properties was analyzed by Raman and Fourier transformed infrared measurements. The results showed that the vertical uniformity and the compact degree of μ c-Si:H thin films were improved with increasing F_total. The variation of the microstructure was regarded as the main reason for the difference of the J--V parameters. Combined with optical emission spectroscopy, we found that the gas temperature plays an important role in determining the microstructure of thin films. With F_total of 300~sccm, a conversion efficiency of 8.11% has been obtained for the intrinsic layer deposited at 8.5~\AA/s (1~\AA=0.1\,nm).     

Room-temperature deposition of transparent conductive Al-doped ZnO thin films using low energy ion bombardment

Al-doped zinc oxide (AZO) films are prepared on quartz substrates by dual-ion-beam sputtering deposition at room temperature (∼25°C). An assisting argon ion beam (ion energy E _i =0–300 eV) directly bombards the substrate surface to modify the properties of AZO films. The effects of assisted-ion beam energy on the characteristics of AZO films were investigated in terms of X-ray diffraction, atomic force microscopy, Raman spectra, Hall measurement and optical transmittance. With increasing assisting-ion beam bombardment, AZO films have a strong improved crystalline quality and increased radiation damage such as oxygen vacancies and zinc interstitials. The lowest resistivity of 4.9×10⁻³Ω cm and highest transmittance of above 85% in the visible region were obtained under the assisting-ion beam energy 200 eV. It was found that the bandgap of AZO films increased from 3.37 to 3.59 eV when the assisting-ion beam energy increased from 0 to 300 eV.     

Effects of substrate temperature and Zn addition on the properties of Al-doped ZnO films prepared by magnetron sputtering

Al-doped ZnO (AZO) films prepared at different substrate temperature and AZO films with intentional Zn addition (ZAZO) during deposition at elevated substrate temperature were fabricated by radio frequency magnetron sputtering on glass substrate, and the resulting structural, electrical, optical properties together with the etching characteristics and annealing behavior were comparatively examined. AZO films deposited at 150 °C showed the optimum electrical properties and the largest grain size. XPS analysis revealed that AZO films deposited at elevated temperature of 450 °C contained large amount of Al content due to Zn deficiency, and that intentional Zn addition during deposition could compensate the deficiency of Zn to some extent. It was shown that the electrical, optical and structural properties of ZAZO films were almost comparable to those of AZO film deposited at 150 °C, and that ZAZO films had much smaller etching rate together with better stability in severe annealing conditions than AZO films due possibly to formation of dense structure.     

Studies on the properties of sputter-deposited Al-doped ZnO films

ZnO is a well known material; however, the research interest in this material is still high enough because ZnO is one of the materials with the most potential for optoelectronics due to its promising properties of high conductivity as well as good transparency. In this work, aluminum doped zinc oxide films (ZnO:Al) were deposited by RF magnetron sputtering on glass and silicon substrates with different deposition times of 2, 3 and 4 h. The aim of this work is the study of the deposition time effect on the properties of ZnO:Al films. It is shown that films grow with the hexagonal c$c$-axis perpendicular to the substrate surface. The morphological characteristics show a granular and homogenous surface and the cristallinity of the films is enhanced with increased deposition time. The deposited films show good optical transmittance (80%–90%) in the visible and near infrared spectrum. The calculated band gap is about 3.3 eV. The electrical ZnO:Al/Si(p) junction properties were investigated using the Capacitance–Voltage (C–V$C\text{–}V$) dependence. Calculations of the built-in potential from classical 1/C²–V$1/C^2\text{–}V$ characterization give values between 0.54 and 0.71 V.     

The transparence comparison of Ga- and Al-doped ZnO thin films

The Ga-doped ZnO (GZO) and Al-doped ZnO (AZO) thin films were grown on quartz glass substrates by pulsed laser deposition under different oxygen partial pressures (PO₂). The transparent performances of films versus properties of structure and conductivity were discussed. With the increase of PO₂, the transmittance of both GZO films and AZO films increased to maximum and then decreased which were in according with the change of crystallization quality. The transmittance of GZO films was higher than that of AZO films, which were not dominated by the impurity ions induced by doping. AFM images and surface roughness mean square coefficients showed that the surfaces of GZO films were smoother than that of AZO films, which were due to the dopant Ga acting as the surfactant and smoothed the GZO films surface.     

Investigation on antireflection coatings for Al:ZnO in silicon thin-film solar cells

We numerically investigate the role of antireflection (AR) coatings, composed of SiO₂ and/or ZnO, in suppression of interfacial reflections in the presence of the transparent conducting oxide, Al-doped ZnO (AZO). Three structures are simulated: (a) AR coatings in organic light-emitting diodes (OLEDs) and flat panel displays, (b) AR coating located between the glass and the AZO, and (c) same as the case b except the involvement of another AR coating between the AZO and the amorphous silicon layers. The weighted average transmittance according to the AM1.5 solar spectrum, the photovoltaic transmittance (T_pv), suggests that there is no evident difference between the structures a and b, especially when the layer number of AR coatings is less than three. An effective way to improve T_pv is presented in the structure c, where T_pv is increased from 73.54% to 76.32% with a three-layered AR coating located between AZO and a-Si. It implies that the suppression of interfacial reflections, resulting from the considerable mismatch of refractive indices at the interface of AZO and a-Si, would benefit the efficiency improvement of silicon thin-film solar cells.