Characterization of ZnO-SnO2 thin film composites prepared by pulsed laser deposition

Thin films of ZnO-SnO₂ composites have been deposited on Si(1 0 0) and glass substrates at 500 °C by pulsed laser ablation using different composite targets with ZnO amount varying between 1 and 50 wt%. The effect of increasing ZnO-content on electrical, optical and structural properties of the ZnO-SnO₂ films has been investigated. X-ray diffraction analysis indicates that the as-deposited ZnO-SnO₂ films can be both crystalline (for ZnO <1 wt%) and amorphous (for ZnO ≥ 10 wt%) in nature. Atomic force microscopy studies of the as-prepared composite films indicate that the surfaces are fairly smooth with rms roughness varying between 3.07 and 2.04 nm. The average optical transmittance of the as-deposited films in the visible range (400-800 nm), decreases from 90% to 72% for increasing ZnO concentration in the film. The band gap energy (E_g) seems to depend on the amount of ZnO addition, with the maximum obtained at 1 wt% ZnO. Assuming that the interband electron transition is direct, the optical band gap has been found to be in the range 3.24-3.69 eV for as-deposited composite films. The lowest electrical resistivity of 7.6 × 10⁻³ Ω cm has been achieved with the 25 wt% ZnO composite film deposited at 500 °C. The photoluminescence spectrum of the composite films shows a decrease in PL intensity with increasing ZnO concentration.     

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.     

The influence of titanium on the properties of zinc oxide films deposited by radio frequency magnetron sputtering

TiO₂-doped zinc oxide thin films were deposited on glass substrates by radio frequency (RF) magnetron sputtering with TiO₂-doped ZnO targets in an argon atmosphere. The structural properties of TiO₂-doped ZnO films doped with different TiO₂ contents were investigated. The experimental results show that polycrystalline TiO₂-doped ZnO films had the (0 0 2) preferred orientation. The deposition parameters such as the working pressure and substrate temperature of TiO₂-doped ZnO films were also investigated. The crystalline structure of the TiO₂-doped ZnO films gradually improved as the working pressure was lowered and the substrate temperature was raised. The lowest electrical resistivity for the TiO₂-doped ZnO films was obtained when the Ti addition was 1.34 wt%; its value was 2.50 × 10⁻³ Ω cm, smaller than that found in previous studies. The transmittance of the TiO₂-doped ZnO films in the visible wavelength range was more than 80%. The optical energy gap was related to the carrier concentration, and was in the range of 3.30-3.48 eV.     

Characteristics of ZnO:Al thin films co-doped with hydrogen and fluorine

Fluorine and hydrogen co-doped ZnO:Al (AZO) films were prepared by radio frequency (rf) magnetron sputtering of ZnO targets containing 1 wt.% Al₂O₃ on Corning glass at substrate temperature of 150 °C with Ar/CF₄/H₂ gas mixtures, and the structural, electrical and optical properties of the as-deposited and the vacuum-annealed films were investigated. In as-deposited state, films with fairly low resistivity of 3.9-4 × 10⁻⁴ Ω cm and very low absorption coefficient below 900 cm⁻¹ when averaged in 400-800 nm could be fabricated. After vacuum-heating at 300 °C, the minimum resistivity of 2.9 × 10⁻⁴ Ω cm combined with low absorption loss in visible region, which enabled the figure of merit to uplift as high as 4 Ω⁻¹, could be obtained for vacuum-annealed film. It was shown that, unlike hydrogenated ZnO films which resulted in degradation upon heating in vacuum at moderately high temperature, films with fluorine addition could yield improved electrical properties mostly due to enhanced Hall mobility while preserving carrier concentration level. Furthermore, stability in oxidizing environment could be improved by fluorine addition, which was ascribed to the filling effect of dangling bonds at the grain boundaries. These results showed that co-doping of hydrogen and fluorine into AZO films with low Al concentration could be remarkably compatible with thin film solar cell applications.     

Optical and electrical properties of In-doped CdO thin films fabricated by pulse laser deposition

Transparent indium-doped cadmium oxide (In-CdO) thin films were deposited on quartz glass substrates by pulse laser deposition (PLD) from ablating Cd-In metallic target at a fixed pressure 10 Pa and a fixed substrate temperature 300 °C. The influences of indium concentrations in target on the microstructure, optical and electrical performances were studied. When the indium concentration reaches to 3.9 wt%, the as-deposited In-CdO film shows high optical transmission in visible light region, obviously enhanced direct band gap energy (2.97 eV), higher carrier concentration and lower electric resistivity compared with the undoped CdO film, while a further increase of indium concentration to 5.6 wt% induces the formation of In₂O₃, which reverse the variation of these parameters and performance.     

Structural, optical and electrical properties of Al-N codoped ZnO films by RF-assisted MOCVD method

N-doped ZnO films were produced using N₂ as N source by metal-organic chemical vapor deposition (MOCVD) system which has been improved with radio-frequency (RF)-assisted equipments. The data of secondary ion mass spectroscopy (SIMS) indicate that the concentration of N in N-doped ZnO films is around 5 × 10²⁰ cm⁻³, implying that sufficient incorporation of N into ZnO can be obtained by RF-assisted equipment. On this basis, the structural, optical and electrical properties of Al-N codoped ZnO films were studied. Then, the effect of RF power on crystal quality, surface morphologies, optical properties was analyzed using X-ray diffraction, atomic force microscopy and photo-luminescence methods. The results illustrate that the RF plasma is the key factor for the improvement of crystal quality. Then the observation of A⁰X recombination associated with N_O acceptor in low-temperature PL spectrum proved that some N atoms have occupied the positions of O atoms in ZnO films. Hall measurements shown that p-type ZnO film deposited on quartz glasses was obtained when RF power was 150 W for the Al-N codoped ZnO films, while the resistivity of N-doped ZnO films was rather high. Compared with the Al-doped ZnO film, the obviously increased resistivity of codoped films indicates that the formation of N_O acceptors compensate some donors in ZnO films effectively.     

Effects of hydrogen flux on the properties of Al-doped ZnO films sputtered in Ar + H2 ambient at low temperature

Al-doped ZnO (AZO) transparent conductive thin films were grown by magnetron sputtering with AZO (98 wt.% ZnO, 2 wt.% Al₂O₃) ceramic target in Ar + H₂ ambient at a relatively low temperature of 100 °C. To investigate the dependence of crystalline and properties of as-grown AZO films on the H₂-flux, X-ray diffraction (XRD), X-ray photoemission spectrometer (XPS), Hall and transmittance spectra measurements were employed to analyze the AZO samples deposited with different H₂-flux. The results indicate that H₂-flux has a considerable influence on the transparent conductive properties of AZO films. The resistivity of 4.15 × 10⁻⁴ Ω cm and the average transmittance of more than 94% in the visible range were obtained with the optimal H₂-flux of 1.0 sccm. Such a low temperature growing method present here may be especially useful for some low-melting point photoelectric devices and substrates.     

Characterisation of porous doped ZnO thin films deposited by spray pyrolysis technique

Al or Sn doped ZnO films were deposited by spray pyrolysis using aqueous solutions. The films were deposited on either indium tin oxide coated or bare glass substrates. ZnCl₂, AlCl₃ and SnCl₂ were used as precursors. The effect of ZnCl₂ molar concentration (0.1-0.3 M) and doping percentage (2-4% AlCl₃ or SnCl₂) have been investigated. The main goal of this work being to grow porous ZnO thin films, small temperature substrates (200-300 °C) have been used during the spray pyrolysis deposition. It is shown that, if the X-ray diffraction patterns correspond to ZnO, the films deposited onto bare glass substrate are only partly crystallized while those deposited onto ITO coated glass substrate exhibit better crystallization. The homogeneity of the films decreases when the molar concentration of the precursor increases, while the grain size and the porosity decrease when the Al doping increases. The optical study shows that band tails are present in the absorption spectrum of the films deposited onto bare glass substrate, which is typical of disordered materials. Even after annealing 4 h at 400 °C, the longitudinal resistivity of the films is quite high. This result is attributed to the grain boundary effect and the porosity of the films. Effectively, the presence of an important reflection in the IR region in samples annealed testifies of a high free-carriers density in the ZnO crystallites. Finally it is shown that when deposited in the same electrochemical conditions, the transmission of a polymer film onto the rough sprayed ZnO is smaller than that onto smooth sputtered ZnO.     

Fabrication of Sb-doped p-type ZnO thin films by pulsed laser deposition

p-Type ZnO thin films have been realized via monodoping antimony (Sb) acceptor by using pulsed laser deposition. The obtained films with the best electrical properties show a hole concentration in the order of 10¹⁸ cm⁻³ and resistivity in the range of 2-4 Ω cm. X-ray diffraction measurements revealed that all the films possessed a good crystallinity with (0 0 2)-preferred orientation. Guided by X-ray photoemission spectroscopy analysis and a model for large-sized-mismatched group-V dopant in ZnO, an Sb_Zn-2V_Zn complex is believed to be the most possible acceptor in the Sb-doped p-type ZnO thin films.     

Boron doped ZnO thin films fabricated by RF-magnetron sputtering

By using the radio frequency-magnetron sputtering (RF-MS) method, both pure ZnO and boron doped ZnO (ZnO:B) thin films were deposited on glass substrates at ambient temperature and then annealed at 450 °C for 2 h in air. It is found that both ZnO and ZnO:B thin films have wurtzite structure of ZnO with (0 0 2) preferred orientation and high average optical transmission (≥80%). Compared with the resistivity of 6.3 × 10² Ω cm for ZnO film, both as-deposited and annealed ZnO:B films exhibit much lower resistivity of 9.2 × 10⁻³ Ω cm and 7.5 × 10⁻³ Ω cm, respectively, due to increase in the carrier concentration. Furthermore, the optical band gaps of 3.38 eV and 3.42 eV for as-deposited and annealed ZnO:B films are broader than that of 3.35 eV for ZnO film. The first-principles calculations show that in ZnO:B thin films not only the band gap becomes narrower but also the Fermi level shifts up into the conduction band with respect to the pure ZnO film. These are consistent with their lower resistivities and suggest that in the process of annealing some substituted B in the lattice change into interstitial B because of its smaller ion radius and this transformation widens the optical band gap of ZnO:B thin film.