Preparation and characterization of Al doped ZnO thin films by PLD

This paper describes the effect of doping on the composition, surface morphology and optical, structural and electrical properties of Al doped ZnO thin films by pulsed laser deposition. SEM analysis shows that the crystalline nature of the deposited films decreases with an increase of Al doping concentration from 1% to 6%. In the AFM analysis, the surface roughness of the deposited films increases by increasing the doping concentration of Al. Al doping strongly influences the optical properties of the ZnO thin films. Optical transmittance spectra show a very good transmittance in the visible region (450–700 nm). The calculated optical band gap was found to be in the range from 3.405 to 3.464 eV. Structural analysis confirms that the increases of Al concentration decrease the crystallinity of the ZnO films and the particle size decreases from 45.7±0.09 to 28.0±0.02 nm. In the Raman analysis, the active mode of Al(=1%) doped ZnO films were observed at 434.81 cm⁻¹. The shifts of the active mode (_E2)$\left(E_2\right)$ show the presence of tensile stress in the deposited films. The electrical properties of the deposited films showed that the values of the Hall mobility was in the range between 2.51 and 10.64 cm²/V s and the carrier concentration between 15.7 and 0.78×10¹⁷ and the resistivity values between 1.59 and 10.97 Ωcm, depending on the doping concentration.     

Characteristics of ZnO:In thin films prepared by RF magnetron sputtering

In-doped ZnO (ZnO:In) transparent conductive thin films were deposited on glass substrates by RF magnetron sputtering. The effect of substrate temperature on the structural, electrical and optical properties of the ZnO:In thin films was investigated. It was found that higher temperature improves the crystallinity of the films and promotes In substitution easily. ZnO:In thin films with the best crystal quality were fabricated at 300 °C, which exhibit a larger grain size of 29 nm and small tensile strain of 0.9%. The transmittance of all the films was revealed to be over 85% in the visible range independence of the substrate temperatures and the lowest resistivity of ZnO:In thin films is 2.4×10⁻³ Ω cm.     

Characteristics of ZnO:In thin films prepared by RF magnetron sputtering

In-doped ZnO (ZnO:In) transparent conductive thin films were deposited on glass substrates by RF magnetron sputtering. The effect of substrate temperature on the structural, electrical and optical properties of the ZnO:In thin films was investigated. It was found that higher temperature improves the crystallinity of the films and promotes In substitution easily. ZnO:In thin films with the best crystal quality were fabricated at 300 °C, which exhibit a larger grain size of 29 nm and small tensile strain of 0.9%. The transmittance of all the films was revealed to be over 85% in the visible range independence of the substrate temperatures and the lowest resistivity of ZnO:In thin films is 2.4×10⁻³ Ω cm.     

Properties of reactively sputtered W–B–N thin film as a diffusion barrier for Cu metallization on Si

Thin films of W–B–N (10 nm) have been evaluated as diffusion barriers for Cu interconnects. The amorphous W–B–N thin films were prepared at room temperature via reactive magnetron sputtering using a W₂B target at various N₂/(Ar + N₂) flow ratios. Cu diffusion tests were performed after in-situ deposition of 200 nm Cu. Thermal annealing of the barrier stacks was carried out in vacuum at elevated temperatures for one hour. X-ray diffraction patterns, sheet resistance measurement, cross-section transmission electron microscopy images, and energy-dispersive spectrometer scans on the samples annealed at 500°C revealed no Cu diffusion through the barrier. The results indicate that amorphous W–B–N is a promising low resistivity diffusion barrier material for copper interconnects.     

The growth of ZnO:Ga:Cu as new TCO film of advanced electrical,optical and structural quality

Because of having similarities in many physical as well as chemical properties to those of Zn, Cu has been strategically used as an effective dopant e.g., Al, Ga, F, etc., to change the optical, electrical and the micro-structural properties of ZnO thin films for obtaining its favorable opto-electronic performance as a transparent conducting oxide suitable for devices. Present study demonstrates the growth of transparent conducting ZnO:Ga:Cu thin films, by low power RF magnetron sputtering at a low substrate temperature (100 °C). Highly crystalline ZnO:Ga:Cu film with preferred c-axis orientation has been obtained demonstrating a high magnitude of transmission ~85% in the visible range and a high electrical conductivity ~40 S cm^–1, facilitated by large crystallite size (~29 nm), introducing reduced grain boundary scattering. XPS O 1S spectrum reveals the presence of a significant fraction of oxygen atoms effectively increasing the optical transparency. Incorporation of Ga and Cu ions into the ZnO matrix promotes violation of the local translational symmetry as suggested by the relaxation of Raman selection rules for the network, evident by the presence of strong (B₁^high–B₁^low) modes which are typically Raman inactive. The consequences of Cu doping has been compared with identically prepared ZnO and ZnO:Ga films.     

Determination of the optimal parameters for the fabrication of ZnO thin films prepared by spray pyrolysis method

In this work, ZnO thin films have been prepared by spray pyrolysis deposition method on the glass substrates. The effect of deposition parameters, such as deposition rate, substrate temperature and solution volume has been studied by X-ray diffraction (XRD) method, UV–Vis–NIR spectroscopy, scanning electron microscopy (SEM), and electrical measurements. The XRD patterns indicate polycrystalline wurtzite structure with preferred direction along (0 0 2) planes. Thin films have transparency around 90% in the visible range. The optical band gap was determined at 3.27 eV which did not change significantly. Evolution of electrical results containing the carriers’ density, sheet resistance and resistivity are in agreement with structural results. All the results suggest the best deposition parameters are: deposition rate, R = 3 ml/min, substrate temperature, T _s = 450°C and thickness of the thin films t = 110–130 nm.     

Microstructure and optical properties of nanocrystalline ZnO and ZnO:(Li or Al) thin films

Zinc oxide thin films (ZnO, ZnO:Li, ZnO:Al) were deposited on glass substrates by a sol-gel technique. Zinc acetate, lithium acetate, and aluminum chloride were used as metal ion sources in the precursor solutions. XRD analysis revealed that Li doped and undoped ZnO films formed single phase zincite structure in contrast to Al:ZnO films which did not fully crystallize at the annealing temperature of 550 °C. Crystallized films had a grain size under 50 nm and showed c-axis grain orientation. All films had a very smooth surface with RMS surface roughness values between 0.23 and 0.35 nm. Surface roughness and optical band tail values increased by Al doping. Compared to undoped ZnO films, Li doping slightly increased the optical band gap of the films.     

Synthesis and characterization of Mg-doped ZnO hollow spheres

Mg-doped ZnO nanoparticles were synthesized by a simple chemical method at low temperature with Mg:Zn atomic ratio from 0 to 7%. The synthesis process is based on the hydrolysis of zinc acetate dihydrate and magnesium acetate tetrahydrate were heated under refluxing at 65 °C using methanol as a solvent. X-ray diffraction analysis reveals that the Mg-doped ZnO crystallizes in a wurtzite structure with crystal size of 5–12 nm. These nanocrystals self-aggregated themselves into hollow spheres of size of 800–1100 nm. High resolution transmission electron microscopy images show that each sphere is made up of numerous nanoparticles of average diameter 5–11 nm. The XRD patterns, SEM and TEM micrographs of doping of Mg in ZnO confirmed the formation of hollow spheres indicating that the Mg²⁺ is successfully substituted into the ZnO host structure of the Zn²⁺ site. Furthermore, the UV–Vis spectra and photoluminescence (PL) spectra of the ZnO nanoparticles were also investigated. The band gap of the nanoparticles can be tuned in the range of 3.36–3.55 eV by the use of the dopants.     

Photoluminescence properties of thin nitrogen- and phosphorus-doped ZnO films fabricated using pulsed laser deposition

The production of n- and p-type high-quality film structures is a foreground task in tackling the problem of growing the light-emitting p-n junctions based on zinc oxide. The ZnO:N and ZnO:P thin-film samples are produced from ceramic targets using the pulsed laser deposition. Zn₃N₂, MgO, and Zn₃P₂ are introduced in the ZnO ceramic targets for the fabrication of the p-type ZnO films. Gases O₂ and N₂O are used as buffer gases. The thermal annealing of the ZnO films is employed. The resistance and photoluminescence (PL) spectra of the ZnO films are measured prior to and after annealing. The dependence of the ZnO PL peak amplitude and position prior to and after annealing on the level of doping with nitrogen and phosphorus is established. The PL characteristics of the films are studied at cw optical excitation using a He-Cd laser with a radiation wavelength of 325 nm. The PL spectra in the interval 300–700 nm are recorded by an HR4000 Ocean Optics spectrometer in the temperature range 10–400 K. The effect of the conditions for the film deposition on the PL spectra is analyzed. The effect of the N- and P-doping level of the ZnO films on the PL intensity of the films and the position of the PL bands in the UV region is investigated. The short-wavelength (250–400 nm) transmission spectra of the ZnO:P films are measured. The effect of the P-doping level on the band gap of the ZnO films is studied.     

Microstructure and magnetic properties of Co(Cr)/Ti(Cr)/ZnO films prepared by laser ablation on Si substrates

High-quality Co(Cr)(50–66 nm)/Ti(Cr)(25–30 nm)/ZnO(165–225 nm) films were grown on Si substrates by the pulsed-laser deposition technique at 450–500°C. The microstructure of the films and their magnetic properties were investigated by X-ray diffraction, transmission electron microscopy and a vibrating sample magnetometer. It was found that the Co(Cr)/Ti(Cr)/ZnO thin films had a highly preferential c-axis direction normal to the surface of the substrate, and the ZnO sublayer had columnar structures in the growth direction. The interface of the multi-layer films is smooth without interface reaction. The as-produced films had in-plane easy magnetization. It indicates that the enhancements of the magnetic properties of the films are mainly ascribed to the grain structure and multi-domain state of the Co-alloy layer, which can be controlled by the ZnO sublayer.     

Effect of thickness on the stability of transparent conducting impurity‐doped ZnO thin films in a high humidity environment

The resistivity of transparent conducting Al‐ and Ga‐doped ZnO (AZO and GZO) thin films prepared with a thickness in the range from 20 to 200 nm on glass substrates at a temperature below 200 °C was found to increase with exposure time when tested in a high humidity environment (air at 90% relative humidity and 60 °C). The resistivity stability (resistivity increase) was considerably affected by the thin film thickness. In particular, thin films with a thickness below about 50 nm were very unstable. The increase in resistivity is interpreted as carrier transport being dominated by grain boundary scattering resulting from the trapping of free electrons due to oxygen adsorption on the grain boundary surface. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Transparence and electrical properties of ZnO-based multilayer electrode

Three-layered ZnO/Ag–Ti/ZnO structures were prepared using both the sol-gel technique and DC magnetron sputtering. This study focuses on the electrical and optical properties of the ZnO/Ag–Ti/ZnO multilayers with various thicknesses of the Ag–Ti layer. The ZnO thin film prepared by the sol–gel method was dried at 300°C for 3 minutes, and a fixed thickness of 20 nm was obtained. The thickness of the Ag–Ti thin film was controlled by varying the sputtering time. The Ag–Ti layer substantially reduced the electrical resistivity of the sol–gel-sprayed ZnO thin films. The sheet resistance of the Ag–Ti layer decreased dramatically and then became steady beyond a sputtering time of 60 s. The sputtering time of Ag–Ti thin film deposition was determined to be 60 s, taking into account the optical transmittance. Consequently, the transmittance of the ZnO/Ag–Ti/ZnO multilayer films was 71% at 550 nm and 60% at 350 nm. The sheet resistance was 4.2 Ω/sq.     

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.     

氢气引入对宽光谱Mg和Ga共掺杂ZnO透明导电薄膜的特性影响

为适应宽光谱高效率硅基薄膜太阳电池的应用需求,本文尝试采用直流磁控溅射技术在553 K衬底温度下生长氢化Mg和Ga共掺杂ZnO(HMGZO)透明导电氧化物(TCO)薄膜.通过对薄膜微观结构、表面形貌、电学以及光学性能的测试和分析,详细地研究了氢气(H2)流量(0—16.0 sccm)对HMGZO薄膜结晶特性及光电性能的影响.实验结果表明:生长获得的HMGZO薄膜均为六角纤锌矿结构的多晶薄膜,择优取向为(002)晶面生长方向.薄膜的生长速率随着氢气流量的增加呈现逐渐减小趋势,主要归因于溅射产额的减小.适当的氢气引入会引起晶粒尺寸的增加.随着氢气流量由0增加至4.0 sccm,ZnO薄膜电阻率从177?·cm急剧减小至7.2×10-3?·cm,主要是由于H施主的引入显著地增加了载流子浓度;然而进一步增加氢气流量(4.0—16.0 sccm)造成电阻率的轻微增加,主要归因于载流子浓度的减小以及过多氢杂质引入造成杂质散射的增加.所有生长获得的HMGZO薄膜平均光学透过率在波长λ～320—1100 nm范围内可达87%以上.由于Mg的作用及Burstein-Moss效应的影响造成了带隙展宽,带隙变化范围～3.49—3.70 eV,其中最大光学带隙Eg可达～3.70 eV.     

Controlling the size and alignment of ZnO microrods using ZnO thin film templates deposited by pulsed laser ablation

The production of dense arrays of well aligned ZnO nano- and microrods with a controllable distribution of diameters is demonstrated. The rods were grown using a hydrothermal method, on pre-deposited ZnO thin films exhibiting a range of different grain sizes. These template ZnO thin films were deposited by pulsed laser ablation, at 193 nm, in a low background pressure of O₂; average grain sizes ranged from 10 nm (room temperature deposition) to 50 nm when deposited at a substrate temperature (T_sub) of 500 °C. The morphology of the ZnO microrod arrays grown onto these ZnO thin films was found to depend on the T_sub used during film deposition. Increasing T_sub resulted in a lower density of larger nanorods, with a more pronounced [0001] alignment. The diameters of the rods produced are typically an order of magnitude greater than the grain size of the template ZnO film. Thus the rods cannot be a direct continuation of the grain structure of the template films. Rather, we suggest that the rod diameter is controlled by the density of sites at which the initial nucleation occurs, which is expected to be higher on the smaller grain size films deposited at lower temperatures. The factor controlling the final size of the rods is thus the available free space into which they can grow, which is smaller at the higher nucleation densities. The increased extent of [0001] texturing of the thin film templates deposited at higher T_sub is proposed as the reason for the improved [0001] alignment of rods grown on these templates. PACS 81.07.De; 81.10.Dn; 52.38.Mf     

Effect of energetic electron beam treatment on Ga-doped ZnO thin films

Transparent conductive zinc oxide (ZnO) thin films were synthesized by a sol–gel spin coating method with the addition of Ga(NO₃)₃ in a Zn(CH₃COO)₂ solution and exposed to electron beam treatment. The UV–Vis spectra demonstrated that all of the films had transmittances of over 85% in the visible region. When Ga(NO₃)₃ was added to the ZnO precursor solution, the resistivity of the ZnO thin film decreased and the carrier concentration increased significantly. After electron beam treatment was performed on the 0.4 at.% Ga-doped ZnO film, the optical band gap increased and the resistivity significantly decreased resulting from the increases of the carrier concentration and mobility. By combining Ga doping and electron beam treatment, the resistivity of the ZnO thin film was reduced by a factor of nine hundred.     

Pulsed laser deposition of Zr–N codoped <Emphasis Type="Italic">p</Emphasis>-type ZnO thin films

Present p-type ZnO films tend to exhibit high resistivity and low carrier concentration, and they revert to their natural n-type state within days after deposition. One approach to grow higher quality p-type ZnO is by codoping the ZnO during growth. This article describes recent results from the growth and characterization of Zr–N codoped p-type ZnO thin films by pulsed laser deposition (PLD) on (0001) sapphire substrates. For this work, both N-doped and Zr–N codoped p-type ZnO films were grown for comparison purposes at substrate temperatures ranging between 400 to 700 °C and N₂O background pressures between 10⁻⁵ to 10⁻² Torr. The carrier type and conduction were found to be very sensitive to substrate temperature and N₂O deposition pressure. P-type conduction was observed for films grown at pressures between 10⁻³ to 10⁻² Torr. The Zr–N codoped ZnO films grown at 550 °C in 1×10⁻³ Torr of N₂O show p-type conduction behavior with a very low resistivity of 0.89 Ω-cm, a carrier concentration of 5.0×10¹⁸ cm⁻³, and a Hall mobility of 1.4 cm² V⁻¹ s⁻¹. The structure, morphology and optical properties were also evaluated for both N-doped and Zr–N codoped ZnO films.     

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.     

Characterization of dip-coated ITO films derived from nanoparticles synthesized by␣low-pressure spray pyrolysis

In₂O₃:Sn (Indium Tin Oxide; ITO) films were prepared from a sol solution with highly crystalline ITO nanoparticles (less than 20 nm in size with 10 at.% Sn) which had been prepared by low-pressure spray pyrolysis (LPSP) in a single step. The ITO sol solution was prepared by dispersing LPSP-prepared ITO nanoparticles into ultra pure water. The nanoparticle ITO film was deposited on a glass substrate using a dip-coating method and then annealed in air at various temperatures. The optical transmittances of the ITO films were measured by UV–Vis spectrometry, and the films were found to have a high transparency to visible light (in the case of a film thickness of 250 nm annealed at 400°C, the transparency was in excess of 95% over the range λ=450–800 nm, with a maximum value near 100% at wavelengths above λ=700 nm). The optical transmittances of the films were influenced by the size of the ITO particle used, the film thickness and the annealing temperature. The ITO films showed a minimum resistivity of 9.5×10⁻² Ω cm, and their resistivity was affected by both the ITO particle size and the annealing temperature used.