Spray pyrolysis deposition of ZnO thin films on FTO coated substrates from zinc acetate and zinc chloride precursor solution at different growth temperatures

ZnO thin films were fabricated using zinc chloride and zinc acetate precursors by the spray pyrolysis technique on FTO coated glass substrates. The ZnO films were grown in different deposition temperature ranges varying from 400 to 550 °C. Influences of substrate temperature and zinc precursors on crystal structure, morphology and optical property of the ZnO thin films were investigated. XRD patterns of the films deposited using chloride precursor indicate that (1 0 1) is dominant at low temperatures, while those deposited using acetate precursor show that (1 0 1) is dominant at high temperatures. SEM images show that deposition temperature and type of precursor have a strong effect on the surface morphology. Optical measurements show that ZnO films are obviously influenced by the substrate temperatures and different types of precursor solutions. It is observed that as temperature increases, transmittance decreases for ZnO films obtained using zinc chloride precursor, but the optical transmittance of ZnO films obtained using zinc acetate precursor increases as temperature increases.     

A simple growth route towards ZnO thin films and nanorods

Highly orientated ZnO thin films and the self-organized ZnO nanorods can be easily prepared by a simple chemical vapor deposition method using zinc acetate as a source material at the growth temperature of 180 and 320 °C, respectively. The ZnO thin films deposited on Si (100) substrate have good crystallite quality with the thickness of 490 nm after annealing in oxygen at 800 °C. The ZnO nanorods grown along the [0001] direction have average diameter of 40 nm with length up to 700 nm. The growth mechanism for ZnO nanorods can be explained by a vapor-solid (VS) mechanism. Photoluminescence (PL) properties of ZnO thin films and self-organized nanorods were investigated. The luminescence mechanism for green band emission was attributed to oxygen vacancies and the surface states related to oxygen vacancy played a significant role in PL spectra of ZnO nanorods.     

Photosensitivity of nanocrystalline ZnO films grown by PLD

We have studied the properties of ZnO thin films grown by laser ablation of ZnO targets on (0 0 0 1) sapphire (Al₂O₃), under substrate temperatures around 400 °C. The films were characterized by different methods including X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and atomic force microscopy (AFM). XPS analysis revealed that the films are oxygen deficient, and XRD analysis with θ-2θ scans and rocking curves indicate that the ZnO thin films are highly c-axis oriented. All the films are ultraviolet (UV) sensitive. Sensitivity is maximum for the films deposited at lower temperature. The films deposited at higher temperatures show crystallite sizes of typically 500 nm, a high dark current and minimum photoresponse. In all films we observe persistent photoconductivity decay. More densely packed crystallites and a faster decay in photocurrent is observed for films deposited at lower temperature.     

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.     

Nitrogen doping in pulsed laser deposited ZnO thin films using dense plasma focus

Pulsed laser deposition synthesized ZnO thin films, grown at 400 °C substrate temperature in different oxygen gas pressures, were irradiated with 6 shots of pulsed nitrogen ions obtained from 2.94 kJ dense plasma focus to achieve the nitrogen doping in ZnO. Structural, compositional and optical properties of as-deposited and nitrogen ion irradiated ZnO thin films were investigated to confirm the successful doping of nitrogen in irradiated samples. Spectral changes have been seen in the nitrogen irradiated ZnO thin film samples from the low temperature PL measurements. Free electron to acceptor emissions can be observed from the irradiated samples, which hints towards the successful nitrogen doping in films. Compositional analysis by X-ray photoelectron spectroscopy and corresponding shifts in binding energy core peaks of oxygen and nitrogen confirmed the successful use of plasma focus device as a novel source for nitrogen ion doping in ZnO thin films.     

Microstructures and optical properties of Cu-doped ZnO films prepared by radio frequency reactive magnetron sputtering

Pure and Cu-doped ZnO (ZnO:Cu) thin films were deposited on glass substrates using radio frequency (RF) reactive magnetron sputtering. The effect of substrate temperature on the crystallization behavior and optical properties of the ZnO:Cu films have been studied. The crystal structures, surface morphology and optical properties of the films were systematically investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and a fluorescence spectrophotometer, respectively. The results indicated that ZnO films showed a stronger preferred orientation toward the c-axis and a more uniform grain size after Cu-doping. As for ZnO:Cu films, the full width at half maxima (FWHM) of (0 0 2) diffraction peaks decreased first and then increased, reaching a minimum of about 0.42° at 350 °C and the compressive stress of ZnO:Cu decreased gradually with the increase of substrate temperature. The photoluminescence (PL) spectra measured at room temperature revealed two blue and two green emissions. Intense blue-green luminescence was obtained from the sample deposited at higher substrate temperature. Finally, we discussed the influence of annealing temperature on the structural and optical properties of ZnO:Cu films. The quality of ZnO:Cu film was markedly improved and the intensity of blue peak (∼485 nm) and green peak (∼527 nm) increased noticeably after annealing. The origin of these emissions was discussed.     

Formation of Al-N co-doped p-ZnO/n-Si (1 0 0) heterojunction structure by RF co-sputtering technique

Al-N co-doped ZnO (ZnO:Al-N) thin films were grown on n-Si (1 0 0) substrate by RF co-sputtering technique. As-grown ZnO:Al-N film exhibited n-type conductivity whereas on annealing in Ar ambient the conduction of ZnO:Al-N film changes to p-type, typically at 600 °C the high hole concentration of ZnO:Al-N co-doped film was found to be 2.86 × 10¹⁹ cm⁻³ and a low resistivity of 1.85 × 10⁻² Ω-cm. The current-voltage characteristics of the obtained p-ZnO:Al-N/n-Si heterojunction showed good diode like rectifying behavior. Room temperature photoluminescence spectra of annealed co-doped films revealed a dominant peak at 3.24 eV.     

Epitaxial Properties of Co-Doped ZnO Thin Films Grown by Plasma Assisted Molecular Beam Epitaxy

High quality Co-doped ZnO thin films are grown on single crystalline Al2O3（0001） and ZnO（0001） substrates by oxygen plasma assisted molecular beam epitaxy at a relatively lower substrate temperature of 450℃. The epitaxial conditions are examined with in-situ reflection high energy electron diffraction （RHEED） and ex-situ high resolution x-ray diffraction （HRXRD）. The epitaxial thin films are single crystal at film thickness smaller than 500nm and nominal concentration of Co dopant up to 20%. It is indicated that the Co cation is incorporated into the ZnO matrix as Co^2＋ substituting Zn^2＋ ions. Atomic force microscopy shows smooth surfaces with rms roughness of 1.9 nm. Room-temperature magnetization measurements reveal that the Co-doped ZnO thin films are ferromagnetic with Curie temperatures Tc above room temperature.     

Electron transport in high quality undoped ZnO film grown by plasma-assisted molecular beam epitaxy

High quality ZnO films were grown on c-plane sapphire substrate using low temperature ZnO buffer layer by plasma-assisted molecular beam epitaxy. The film deposited at 720 °C showed the lowest value of full-width at half maximum for the symmetric (0002) diffraction peak of about 86 arcsec. The highest electron mobility in the films was about 103-105 cm²/V s. From temperature-dependent Hall effect measurements, the mobility strongly depends on the dislocation density at low temperature region and the polar optical phonon scattering at high temperature, respectively. Moreover, by obtaining the activation energy of the shallow donors, it was supposed that hydrogen was source of n-type conductivity in as-grown ZnO films.     

Effect of substrate temperature on properties of multilayer thin film based on ZnO and Mo-doped indium oxide

Zinc oxide/molybdenum-doped indium oxide/zinc oxide (ZnO/IMO/ZnO) multilayer thin films are grown using pulsed laser deposition technique. The effect of substrate temperature on structural, optical, and electrical properties of multilayer films is studied. It is observed that films grown at high substrate temperature are oriented along (0 0 2) and (2 2 2) direction for ZnO and IMO respectively. The crystallinity of these films increases with increase in substrate temperature. It is also seen that conductivity, carrier concentration, and mobility increase with increase in temperature. The multilayer film grown at 500 °C has low resistivity (7.67 × 10⁻⁵ Ω cm), high carrier concentration (3.90 × 10²⁰ cm⁻³), and high mobility (209 cm²/Vs).     

Investigation of p-type behavior in Ag-doped ZnO thin films by E-beam evaporation

Ag-doped ZnO (ZnO:Ag) thin films were grown on glass substrates by E-beam evaporation technique. The structural, electrical and optical properties of the films were investigated as a function of annealing temperature. The films were subjected to post annealing at different temperatures in the range of 350-650 °C in an air ambient. All the as grown and annealed films at temperature of 350 °C showed p-type conduction. The films lost p-type conduction after post annealing treatment temperature of above 350 °C, suggesting a narrow post annealing temperature window for the fabrication of p-type ZnO:Ag films. ZnO:Ag film annealed at 350 °C revealed lowest resistivity of 7.25 × 10⁻² Ω cm with hole concentration and mobility of 5.09 × 10¹⁹ cm⁻³ and 1.69 cm²/V s, respectively. Observation of a free-to-neutral-acceptor (e,A^o) and donor-acceptor-pair (DAP) emissions in the low temperature photoluminescence measurement confirms p-type conduction in the ZnO:Ag films.     

Effect of growth time on the structure, Raman shift and photoluminescence of Al and Sb codoped ZnO nanorod ordered array thin films

Al and Sb codoped ZnO nanorod ordered array thin films have been deposited on glass substrate with a ZnO seed layer by hydrothermal method at different growth time. The effect of growth time on structure, Raman shift, and photoluminescence (PL) was studied. The thin films at growth time of 5 h consist of nanorods growth vertically oriented with ZnO seed layer, and the nanorods with an average diameter of 27.8 nm and a length of 1.02 μm consist of single crystalline wurtzite ZnO crystal and grow along [0 0 1] direction. Raman scattering analysis demonstrates that the thin films at the growth time of 5 h have great Raman shift of 15 cm⁻¹ to lower wavenumber and have low asymmetrical factor Г_a/Г_b of 1.17. Room temperature photoluminescence reveals that there is more donor-related PL in films with growth time of 5 h.     

Realization of p-ZnO thin films by GaP codoping

An attempt has been made to realize p-ZnO by directly doping (codoping) GaP into ZnO thin films. GaP codoped ZnO thin films of different concentrations (1, 2 and 4 mol%) have been grown by RF magnetron sputtering. The grown films on sapphire substrate have been characterized by X-ray diffraction (XRD), Hall measurement, Photoluminescence (PL) and Energy dispersive spectroscopy (EDS) to validate the p-type conduction. XRD result shows that all the films have been preferentially oriented along (0 0 2) orientation. The decrease of full-width at half maximum (FWHM) with increase in GaP doping depicts the decrease in native donor defects. Hall measurement shows that among the three films, 2 and 4 mol% GaP doped ZnO shows p-conductivity due to the sufficient amount of phosphorous incorporation. It has been found that low resistivity (2.17 Ωcm) and high hole concentration (1.8×10¹⁸ cm⁻³) for 2% GaP codoped ZnO films due to best codoping. The red shift in near-band-edge (NBE) emission and donar-acceptor-pair (DAP) and neutral acceptor bound recombination (A°X) observed by room temperature and low temperature (10 K) PL, respectively, well acknowledged the formation of p-ZnO. The incorporated phosphorous in the film has been also confirmed by EDS analysis.     

Nitrogen incorporation in homoepitaxial ZnO CVD epilayers

ZnO:N thin films have been deposited on oxygen and zinc terminated polar surfaces of ZnO. The nitrogen incorporation in the epilayers, using NH₃ as doping source, was investigated as a function of the growth temperature in the range between 380 °C and 580 °C. We used Raman spectroscopy and low temperature photoluminescence to investigate the doping properties. It turned out that the nitrogen incorporation strongly depends on both, the surface polarity of the epitaxial films and the applied growth temperatures. In our CVD process low growth temperatures and Zn‐terminated substrate surfaces clearly favour the nitrogen incorporation in the ZnO thin films. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

MBE生长ZnO薄膜的结构和光学特性的研究

用等离子体源辅助分子束外延(P-MBE)方法在蓝宝石(0001)面上生长出了高质量的ZnO薄膜,并对其结构和发光特性进行了研究。在XRD中只观察到ZnO薄膜的(0002)衍射峰,其半高宽(FWHM)值为0.18°;而在共振Raman散射光谱中观测到1LO(579 cm-1 )和2LO(1 152 cm-1 )两个峰位,这些结果表明ZnO薄膜具有单一c轴取向和高质量的纤维锌矿晶体结构。在吸收光谱中观测到自由激子吸收和激子-LO声子吸收峰,这表明在ZnO薄膜中激子稳定的存在于室温,并且两峰之间能量间隔为71.2 meV,与文献上报道的ZnO纵向光学声子能量(71 meV)相符。室温下在光致发光光谱(PL)中仅观测到位于376 nm处的自由激子发光峰,而没有观测到与缺陷相关的深能级发射峰,表明ZnO薄膜具有较高的质量和低的缺陷密度。     

基片温度对PLD制备ZnO薄膜光学常数的影响

光谱椭偏仪被用来研究用脉冲激光沉积方法在Si(100)基片上,温度分别为400,500,600,700 ℃制备的ZnO薄膜的特性。利用三层Cauchy散射模型拟合椭偏参数,计算了每个温度下制备的ZnO薄膜在400~800 nm波长范围内的折射率(n)和消光系数(k)。发现基片温度对光学常数有很大的影响。通过分析XRD表征的晶体结构和 AFM表征的薄膜表面形貌,发现折射率的变化归因于薄膜堆积密度的变化。为了获得具有较好的光学和薄膜质量的ZnO薄膜,相比与其他沉积温度600 ℃或许是最佳的沉积温度。     

Structure and properties of ZnO films grown on Si substrates with low temperature buffer layers

Zinc oxide (ZnO) thin films were grown on Si (1 0 0) substrates by pulsed laser deposition (PLD) using two-step epitaxial growth method. Low temperature buffer layer (LTBL) was initially deposited in order to obtain high quality ZnO thin film; the as-deposited films were then annealed in air at 700 °C. The effects of LTBL and annealing treatment on the structural and luminescent properties of ZnO thin film were investigated. It was found that tensile strain was remarkably relaxed by employing LTBL and the band-gap redshifted, correspondingly. The shift value was larger than that calculated from band-gap theories. After annealing treatment, it was found that the annealing temperature with 700 °C has little influence on strains of ZnO films with LTBLs other than directly deposited film in our experiments. Interestingly, the different behaviors in terms of the shift of ultraviolet (UV) emission after annealing between films with and without buffer were observed, and a tentative explanation was given in this paper.     

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.     

Low-temperature growth of epitaxial ZnO films on (001) sapphire by ultraviolet- assisted pulsed laser deposition

ZnO thin films have been grown on thin Si₃N₄ membranes and (001) sapphire substrates by an ultraviolet-assisted pulsed laser deposition (UVPLD) technique. The microstructure of the films grown on Si₃N₄ membranes, investigated by transmission electron microscopy, showed that crystalline and textured films can be grown by UVPLD at a substrate temperature of only 100 °C. For deposition temperatures higher than 400 °C, ZnO films grown on sapphire substrates were found to be epitaxial by Rutherford backscattering (RBS) and X-ray diffraction measurements. The minimum yield of channeling RBS spectra recorded from films deposited at 550 °C was around 2% and the FWHM of the rocking curve for the (002) diffraction peak was 0.17°; these values are similar to those recorded from ZnO layers grown by conventional PLD at 750 °C.     

Effects of temperature-induced stress on the structural,electrical, and optical properties of ZnO:Ga thin films grown on Si substrates

Crystalline ZnO:Ga thin films with highly preferential c-axis oriented crystals were prepared on Si(001) substrates at different temperatures using the reactive magnetron sputtering technique. Effects of temperature-induced stress in ZnO:Ga films were investigated using X-ray diffraction (XRD), atomic force microscopy (AFM), electrical transport, and spectroscopic ellipsometry measurements. XRD results showed that the films were highly c-axis (out-of-plane) oriented and crystallinity improved with growth temperature. The residual compressive stress in films grown at low temperature relaxes with substrate temperature and becomes tensile stress with further increases in growth temperature. Resistivity of the films decreases with increasing stress, while the carrier concentration and mobility increase as the stress increases. The mechanism of the stress-dependent bandgap of ZnO:Ga films grown at different temperatures is suggested in the present work.