Inclined ZnO thin films produced by pulsed-laser deposition

ZnO thin films with a uniformly inclined structure are grown by pulsed-laser deposition on SrTiO₃. The c-axis of ZnO films is inclined by an angle =20±0.5° and =42±0.5° against the surface normal of 25° miscut (100) SrTiO₃ and (110) SrTiO₃ single crystal substrates, respectively. The inclined structure is due to epitaxial growth of hexagonal ZnO on cubic SrTiO₃ as evidenced by X-ray diffraction and high-resolution transmission electron microscopy investigations. The range of deposition parameters (substrate temperature, oxygen background pressure) to achieve epitaxial growth is determined. The inclined films are smooth with an rms surface roughness of 1.5 nm for layer thicknesses up to 700 nm. PACS 61.10.-i; 68.37.-d; 81.15.Fg     

ZnO films grown by successive chemical solution deposition

ZnO films were grown from 0.1-M zincate solutions on stainless-steel and aluminosilicate glass substrates by the successive chemical solution deposition method. The structure, morphology, composition, and optical emission properties of the films were studied by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and photoluminescence techniques. Results revealed that the as-grown film contains a substantial amount of amorphous zinc hydroxide (15–25%), at least on its surface. This can be reduced to 7% by annealing the film in argon (350 °C, 1 h). Despite the presence of the hydroxide phase, the films hexagonal lattice constants match the standard values. The films surface texture and the grains shape and preferential orientation depend on the type of the substrate and its surface conditioning. The UV photoluminescence emission from as-grown films at 3.22±0.04 eV (380–390 nm) and its suppression due to the effect of chlorine are addressed. PACS 81.16.Be; 81.05.Dz; 78.55.Et; 79.60.-i; 68.55.Jk     

Temperature effect on the electrical, structural and optical properties of N-doped ZnO films by plasma-free metal organic chemical vapor deposition

N-doped p-type ZnO films were grown by plasma-free metal-organic chemical vapor deposition (MOCVD). The effect of substrate temperature on the electrical, optical, and structural properties of the N-doped ZnO films was investigated by Hall-effect, photoluminescence, X-ray diffraction measurements. The electrical properties of the films were extremely sensitive to the substrate temperature and the conduction type could be reversed in a narrow range from 380 °C to 420 °C. Based on X-ray photoelectron spectroscopy, a high compensation effect in the N-doped ZnO films grown by plasma-free MOCVD was suggested to explain the temperature-dependent phenomenon.     

Band-edge photoluminescence in nanocrystalline ZnO:In films prepared by electrostatic spray deposition

ZnO:In films are successfully prepared by using the electrostatic spray deposition technique. X-ray diffraction indicates that the ZnO:In films have a polycrystalline hexagonal wurtzite structure with lattice parameters a=3.267 Å and c=5.209 Å. Photoluminescence properties of the films are investigated in the temperature range of 11.6-300 K, showing strong luminescence in the whole range of temperature. The temperature dependence of the photoluminescence are carried out with full profile fitting of spectra, which clearly shows that the ultraviolet (UV) emission in In-doped ZnO films at low temperature are attributed to emission of a neutral donor-bound exciton (D^°X) and recombination of donor-acceptor pairs (DAP), while the UV emission at room temperature originates from radiative transition of an electron bound on a donor to the valence band.     

Successive chemical solution deposition of ZnO films on flexible steel substrate: structure, photoluminescence and optical transitions

Zinc oxide is an attractive optoelectronic material with wide applications. Thin ZnO films were prepared on steel foil by successive chemical solution deposition (SCSD). The film structure, room-temperature photoluminescence (PL) and optical absorption characteristics were investigated. This study revealed that films of high structural and optical quality can be prepared by the SCSD method. PL of as-grown films shows a weak green peak at 560 nm and a strong UV peak at 380 nm. Annealing in either air or argon suppresses the green peak and red shifts the UV emission towards 390 nm. The presence of chlorine in the deposition solution destroys the PL of as-grown films. A strong UV emission, however, develops after annealing the films in air. Several optical transitions measured from the film PL and optical absorption coefficients are shown to be related to transitions through the known defect levels in ZnO, such as E₁, L₁, E₃ and V_O ²⁺ levels. PACS 81.16.Be; 81.05.Dz; 78.55.Et; 78.66.Hf; 68.55.Jk     

Low-temperature growth of ZnO epitaxial films by metal organic chemical vapor deposition

ZnO films were grown on Al₂O₃ (0001) substrates by metal organic chemical vapor deposition at temperatures of T_g=150300 °C. Epitaxial growth was obtained for T_g200 °C. The in-plane orientation of the ZnO unit cells was found to change from a no-twist one with respect to that of the substrate at T_g=200 °C to a 30°-twist one at T_g=300 °C. Absorption and photoluminescence were observed from the film grown at 150 °C, although there was no evidence of epitaxial growth. Films grown at T_g200 °C exhibited smoother surfaces. Moreover, all the films grown at T_g=150300 °C revealed acceptor-related emission peaks, indicating the incorporation of acceptors into the films. PACS 81.15.Gh; 78.55.Et; 78.66.Hf     

Controllable growth of well-aligned ZnO nanorod arrays by low-temperature wet chemical bath deposition method

Well-aligned ZnO nanorod arrays were synthesized by low-temperature wet chemical bath deposition (CBD) method on Si substrate under different conditions. Results illustrated that dense ZnO nanorods with hexagonal wurtzite structure were vertically well-aligned and uniformly distributed on the substrate. The effects of precursor concentration, growth temperature and time on nanorods morphology were investigated systematically. The mechanism for the effect of preparation parameters was elucidated based on the chemical process of CBD and basic nucleation theory. It is demonstrated that the controllable growth of well-aligned ZnO nanorods can be realized by readily adjusting the preparation parameters. Strong near-band edge ultraviolet (UV) emission were observed in room temperature photoluminescence (PL) spectra for the samples prepared under optimized parameters, yet the usually observed defect related deep level emissions were nearly undetectable, indicating high optical quality ZnO nanorod arrays could be achieved via this easy process chemical approach at low temperature.     

Temperature dependent photoluminescence processes in ZnO thin films grown on sapphire by pulsed laser deposition

Temperature dependence of the photoluminescence (PL) transitions in the range of 10–300 K was studied for ZnO thin films grown on sapphire by pulsed laser deposition. The low temperature PL spectra were dominated by recombination of donor bound excitons (B_X) and their phonon replicas. With increasing temperature, free exciton (F_X) PL and the associated LO phonon replicas increased in intensity at the expense of their bound counterparts. The B_X peak with line width of ∼6 meV at 10 K exhibited thermal activation energy of ∼17 meV, consistent with the exciton-defect binding energy. The separation between the F_X and B_X peak positions was found to reduce with increasing temperature, which was attributed to the transformation of B_X into the shallower donor bound exciton complexes at consecutive lower energy states with increasing temperature, which are possible in ZnO. The energy separation between F_X peak and its corresponding 1-LO phonon replica showed stronger dependence on temperature than that of 2-LO phonon replica. However, their bound counterparts did not exhibit this behavior. The observed temperature dependence of the energy separation between the free exciton and it is LO phonon replicas are explained by considering the kinetic energy of free exciton. The observed PL transitions and their temperature dependence are consistent with observations made with bulk ZnO crystals implying high crystalline and optical quality of the grown films.     

高质量纳米ZnO薄膜的光致发光特性研究

报道了利用低压-金属有机物化学气相沉积技术生长纳米ZnS薄膜，然后，将ZnS薄膜在氧气中于800℃温度下进行热氧化制备高质量纳米ZnO薄膜.x射线衍射结果表明，纳米ZnO薄膜具有六角纤锌矿多晶结构.室温下观察到一束强的紫外(3.26 eV) 光致发光和很弱的深能级发射.根据激子峰的半高宽度与温度的关系确定了激子-纵向光学声子（LO）的耦合强度（ГLO）.由于量子限域效应使ГLO减少较多. 关键词： 光致发光 热氧化 激子 纳米ZnO薄膜     

Photoluminescence properties of Eu-doped ZnO films grown by sputtering-assisted metalorganic chemical vapor deposition

Photoluminescence (PL) properties of Eu-doped ZnO (ZnO:Eu) grown by a sputtering-assisted metalorganic chemical vapor deposition technique were investigated. In PL measurements at 300 K, the samples annealed at 600 °C for 30 min showed clear red-emission lines due to the intra-4f shell transition of ⁵D₀→⁷F_J (J=0–4) in Eu³⁺. In photoluminescence excitation (PLE) spectra, the PL was observed under the high-energy excitation above the band-gap energy of ZnO (indirect excitation) and the low-energy excitation resonant to the energy levels of ⁷F₀–⁵D₃ and ⁷F₀–⁵D₂ transitions in Eu³⁺ (direct excitation). The PL lifetime under the indirect excitation was shorter than that under the direct excitations. These PL properties revealed that the energy transfer from ZnO host to Eu³⁺ was accompanied under indirect excitation.     

Infrared characterization of silicon dioxide films obtained by chemical vapour deposition

Summary In this work we report new FTIR absorbance measurements due to Si−O stretching bond, Si−O−Si and O−Si−O bending bonds of silicon dioxide amorphous films. We compare the optical results obtained from films grown by APCVD, LPCVD, PACVD and thermal oxidation techniques. The effect of thermal annealing on optical obsorbance structures has been studied. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Controllable synthesis and characterization of tube brush-like ZnO nanowires produced via a simple chemical vapor deposition method

Tube brush-like ZnO nanostructures were synthesized by a simple chemical vapor deposition method with Zn and ZnO as precursors. These special ZnO nanostructures were characterized by Scanning Electron Microscope, Energy Dispersive X-ray Spectroscopy, High Resolution Transmission Electron Microscope and Cathodoluminescence (CL) techniques. Empty backbones or comb ribbons backbones were found inside the tube brush-like ZnO structures and fuzzy ZnO nanowires outside. Outside ZnO nanowires grow along the c axis and show green CL emission. The growth mechanism of the hierarchical ZnO nanostructures was investigated by a series of experiments at different growth temperatures and different duration times, and a secondary growth mechanism has been proposed and discussed.     

Atomic layer deposition and characterization of Ga-doped ZnO thin films

Low-resistivity n-type ZnO thin films were grown by atomic layer deposition (ALD) using diethylzinc (DEZ) and H₂O as Zn and O precursors. ZnO thin films were grown on c-plane sapphire (c- Al₂O₃) substrates at 300 C. For undoped ZnO thin films, it was found that the intensity of ZnO () reflection peak increased and the electron concentration increased from 6.8×10¹⁸ to 1.1×10²⁰ cm⁻³ with the increase of DEZ flow rate, which indicates the increase of O vacancies () and/or Zn interstitials (Zn_i). Ga-doping was performed under Zn-rich growth conditions using triethylgallium (TEG) as Ga precursor. The resistivity of 8.0×10⁻⁴ Ω cm was achieved at the TEG flow rate of 0.24 μmol/min.     

One-step preparation of N-doped strontium titanate films by pulsed laser deposition

Perovskite-type oxynitrides exhibit promising electrical and optical properties and can possibly be used in the future as functional materials for electrical, photo-, and electrochemical applications. Continuous heterovalent substitution of oxygen ions by nitrogen ions allows tuning of the desired optical and/or electronic properties to the application specifications. In the present work deposition of SrTiO₃:N films by pulsed reactive crossed beam laser ablation was studied in order to examine the influence of different deposition parameters on the film crystallinity and composition. The deposited films exhibit a perovskite-type crystal structure and reveals epitaxial growth on MgO(100) substrates. The unit cell parameters of the deposited SrTiO₃:N films range within , which is slightly larger than for polycrystalline SrTiO₃ (a=3.905). The studied films reveal an oxygen content in the range of (2.70-2.98)±0.15. The relative N content (vs. O) can be tuned within the range of 1.0–3.0% by adjusting the deposition parameters. The N:O concentration ratio increases with increasing laser fluence and target-to-substrate distances, while the substrate temperature has a more complex influence on the nitrogen concentration. In the range of 580–650 °C the [N]/[O] ratio increases while further heating results in a gradual decrease of the N content. PACS  81.15.Fg; 68.55.-a; 81.05.Zx     

A wet chemical preparation of transparent conducting thin films of Al-doped ZnO nanoparticles

A wet chemical deposition method for preparing transparent conductive thin films on the base of Al-doped ZnO (AZO) nanoparticles has been demonstrated. AZO nanoparticles with a size of 7 nm have been synthesised by a simple precipitation method in refluxed conditions in ethanol using zinc acetate and Al-isopropylate. The presence of Al in ZnO was revealed by the EDX elemental analysis (1.8 at.%) and UV–Vis spectroscopy (a blue shift due to Burstein–Moss effect). The obtained colloid solution with the AZO nanoparticles was used for preparing by spin-coating thin films on glass substrates. The film demonstrated excellent homogeneity and transparency (T > 90%) in the visible spectrum after heating at 400 °C. Its resistivity turned to be excessively high (ρ = 2.6 Ω cm) that we ascribe to a poor charge percolation due to a high film porosity revealed by SEM observations. To improve the percolation via reducing the porosity, a sol–gel solution was deposited “layer-by-layer” in alternation with layers derived from the AZO colloid followed by heating. As it was shown by optical spectroscopy measurements, the density of thus prepared film was increased more than twice leading to a significant decrease in resistivity to 1.3 × 10⁻² Ω cm.     

Thin ZnO films prepared by chemical solution deposition on glass and flexible conducting substrate

Thin films of zinc oxide (ZnO) are deposited by a simple method of successive immersion of substrate in (NH₄)₂ZnO₂(0.1 M) chemical solution and in boiling water. Films of a thickness ≈ 500 nm could be deposited on stainless steel and glass by 40 immersions. The composition, structure, optical bandgap and the charge transport mechanism were determined and the results are presented. Films are stoichiometric and have the same hexagonal lattice parameters as for powder samples. Films are formed from grains with a mean size of a few 100 nm. Grains consist of crystallites of mean size 20–30 nm. For films deposited on stainless steel, the crystallites are highly oriented along their c-axis perpendicular to the substrate. Films have a high optical transparency (above 80%) in the visible region and bandgap energy in the range 3.38–3.42 eV. Films are intrinsically n-type and the charge transport across the films is controlled by a shallow trapping level in accordance with the Poole–Frenkel mechanism. The doubly-ionized trapping level has a concentration of 4×10¹¹ cm^-3 and zero-field ionization energy of 110 meV. Adsorption of oxygen by annealing the films in air yields a singly-ionized trap. PACS 81.15.Lm; 81.05.Dz; 68.37.Hk; 73.61.Ga     

Lead films produced by laser vapor deposition

The deposition of lead film on quartz substrates by photolysing tetraethyl lead vapor with a laser is reported. The dependence of the deposition rate on the pressure of tetraethyl lead, on the light intensity and on the pressure of the buffer gas is measured. Deposition phenomena at low light intensity are discussed.     

Structural, optical and photoelectrochemical characterization of CdS nanowire synthesized by chemical bath deposition and wet chemical etching

Nanocrystalline thin films of CdS have been grown onto flexible plastic and titanium substrates by a simple and environmentally benign chemical bath deposition (CBD) method at room temperature. The films consist of clusters of CdS nanoparticles. The clusters of CdS nanoparticles in the films were successfully converted into nanowire (NW) networks using chemical etching process. The possible mechanism of the etching phenomenon is discussed. These films were examined for their structural, surface morphological and optical properties by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-vis spectrophotometry techniques, respectively. Photoelectrochemical (PEC) investigations were carried out using cell configuration as n-CdS/(1 M NaOH + 1 M Na₂S + 1 M S)/C. The film of nanowires was found to be hexagonal in structure with the preferential orientation along the (0 0 2) plane. The nanowires have widths in the range of 50-150 nm and have lengths of the order of a few micrometers. Optical studies reveal that the CdS nanowires have value of band gap 2.48 eV, whereas it is 2.58 eV for nanoparticles of CdS. Finally, we report on the ideality of junction improvement of PEC cells when CdS nanoparticles photoelectrode converted into nanowires photoelectrode.     

ZnO nanoparticles produced by novel reactive physical deposition process

This paper reports the deposition of ZnO nanoparticles with controlled sizes and different particle densities and their structural, composition and optical properties. They were deposited by means of a DC magnetron based vacuum nanoparticle source onto different substrates (GaAs, Si and Ti/SiO₂/Si). We believe that this is the first time that such nanoparticles have been produced using this unique technique. Zinc was used as sputtering target to produce zinc nanoparticles which were oxidized in-line using molecular oxygen. The structural properties and chemistry of the ZnO were studied by transmission electron microscopy. An average particle size of 6(±2) nm was produced with uniform size distribution. The particle density was controlled using a quartz crystal monitor. Surface densities of 2.3 × 10¹¹/cm², 1.1 × 10¹³/cm² and 3.9 × 10¹³/cm² were measured for three different deposition runs. The ZnO particles were found to be single crystalline having hexagonal structure. Photoluminescence measurements of all samples were performed at room temperature using a cw He-Cd laser at 325 nm excitation. The UV emission around 375 nm at room temperature is due to excitonic recombination and the broad emission centered at 520 nm may be attributed to intrinsic point defects such as oxygen interstitials.