Effects of buffer layer thickness on properties of ZnO thin films grown on porous silicon by plasma-assisted molecular beam epitaxy

ZnO thin films with different buffer layer thicknesses were grown on Si and porous silicon (PS) by plasma-assisted molecular beam epitaxy (PA-MBE). The effects of PS and buffer layer thickness on the structural and optical properties of ZnO thin films were investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and photoluminescence (PL). The ZnO buffer layers, the intensity of the (002) diffraction peak for the ZnO thin films and its full width at half maximum (FWHM) decreased with an increase in the thickness of the ZnO buffer layers, indicating an improvement in the crystal quality of the films. On introducing PS as a substrate, the grain sizes of the ZnO thin films became larger and their residual stress could be relaxed compared with the ZnO thin films grown on Si. The intensity ratio of the ultraviolet (UV) to visible emission peak in the PL spectra of the ZnO thin films increased with an increase in buffer layer thickness. Stronger and narrower UV emission peaks were observed for ZnO thin films grown on PS. Their structural and optical properties were enhanced by increasing the buffer layer thickness. In addition, introduction of PS as a substrate enhanced the structural and optical properties of the ZnO thin films and also suppressed Fabry-Perot interference.     

Mn掺杂对ZnO薄膜结构和光学性质的影响

利用脉冲激光淀积的方法在Si衬底上生长出了c轴高度取向的ZnO和Zn0.9Mn（0.1）O薄膜.光致发光结果显示了Mn的掺杂引起了薄膜的带边发射蓝移,强度减弱,紫光发射几乎消失,但绿光发射增强.利用X射线衍射,X射线吸收精细结构和X射线光电子能谱等实验技术对Mn掺杂的ZnO薄膜的结构及其对光学性质影响进行了研究.结果表明：Mn掺入到ZnO薄膜中形成了Zn0.9Mn0.1O合金薄膜,Mn以＋2价的价态存在,这就导致了掺Mn以后的薄膜带隙变大,在发光谱中表现为带边发射的蓝移.同时由于掺入的Mn与薄膜中的填隙Zn反应,导致薄膜的结晶性变差,薄膜中的填隙Zn减少,O空位增多,引起带边发射和紫光发射减弱,绿光发射增强.     

Growth and characterization of indium phosphide nanowires on transparent conductive ZnO:Al films

The epitaxial growth of indium phosphide nanowires (InP NWs) on transparent conductive aluminum-doped zinc oxide (ZnO:Al) thin films is proposed and demonstrated. ZnO:Al thin films were prepared on quartz substrates by radio frequency magnetron sputtering, then InP NWs were grown on them by plasma enhanced metal organic chemical vapor deposition with gold catalyst. Microstructure and optical properties of InP nanowires on ZnO:Al thin films were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectric spectroscopy (XPS), photoluminescence and Raman spectroscopy at room temperature. SEM shows that randomly oriented and intersecting InP nanowires were grown to form a network on ZnO:Al thin films. Both wurtzite (WZ) and zincblende (ZB) structures coexist in the random orientation InP NWs on ZnO:Al thin film had been proved by XRD analysis. XPS result indicates Zn diffusion exists in the InP NWs on ZnO:Al. The photoluminescence spectra of InP nanowires with Zn diffusion present an emission at 915 nm. Zn diffusion also bring effect on Raman spectra of InP NWs, leading to more Raman-shift and larger relative intensity ratio of TO/LO.     

Superior Functionality by Design: Selective Ozone Sensing Realized by Rationally Constructed High‐Index ZnO Surfaces

A new technique is reported for the transformation of smooth nonpolar ZnO nanowire surfaces to zigzagged high‐index polar surfaces using polycrystalline ZnO thin films deposited by atomic layer deposition (ALD). The c‐axis‐oriented ZnO nanowires with smooth nonpolar surfaces are fabricated using vapor deposition method and subsequently coated by ALD with a ZnO particulate thin film. The synthesized ZnO–ZnO core–shell nanostructures are annealed at 800 °C to transform the smooth ZnO nanowires to zigzagged nanowires with high‐index polar surfaces. Ozone sensing response is compared for all three types of fabricated nanowire morphologies, namely nanowires with smooth surfaces, ZnO–ZnO core–shell nanowires, and zigzagged ZnO nanowires to determine the role of crystallographic surface planes on gas response. While the smooth and core–shell nanowires are largely non‐responsive to varying O₃ concentrations in the experiments, zigzagged nanowires show a significantly higher sensitivity (ppb level) owing to inherent defect‐rich high‐index polar surfaces.     

Preferential growth of ZnO thin films by the atomic layer deposition technique

Preferred orientation of ZnO thin films deposited by the atomic layer deposition (ALD) technique could be manipulated by deposition temperature. In this work, diethyl zinc (DEZn) and deionized water (H(2)O) were used as a zinc source and oxygen source, respectively. The results demonstrated that (10.0) dominant ZnO thin films were grown in the temperature range of 155-220?°C. The c-axis crystal growth of these films was greatly suppressed. Adhesion of anions (such as fragments of an ethyl group) on the (00.2) polar surface of the ZnO thin film was believed to be responsible for this suppression. In contrast, (00.2) dominant ZnO thin films were obtained between 220 and 300?°C. The preferred orientations of (10.0) and (00.2) of the ZnO thin films were examined by XRD texture analysis. The texture analysis results agreed well with the alignments of ZnO nanowires (NWs) which were grown from these ZnO thin films. In this case, the nanosized crystals of ZnO thin films acted as seeds for the growth of ZnO nanowires (NWs) by chemical vapor deposition (CVD) process. The highly (00.2) textured ZnO thin films deposited at high temperatures, such as 280?°C, contained polycrystals with the c?axis perpendicular to the substrate surface and provided a good template for the growth of vertically aligned ZnO NWs.     

A comparative study on the NO2 gas sensing properties of ZnO thin films, nanowires and nanorods

ZnO thin films were fabricated using the spin coating method, ZnO nanowires by cathodically induced sol-gel deposition by the means of an anodic aluminum oxide (AAO) template, and ZnO nanorods with the hydrothermal technique. For thin film preparation, a clear, homogeneous and stable ZnO solution was prepared by the sol-gel method using zinc acetate (ZnAc) precursor which was then coated on a glass substrate with a spin coater. Vertically aligned ZnO nanowires which were approximately 65 nm in diameter and 10 μm in length were grown in an AAO template by applying a cathodic voltage in aqueous zinc nitrate solution at room temperature. For fabrication of the ZnO nanorods, the sol-gel ZnO solution was coated on glass substrate by spin coating as a seed layer. Then ZnO nanorods were grown in zinc nitrate and hexamthylenetetramine aqueous solution. The ZnO nanorods are approximately 30 nm in diameter and 500 nm in length. The ZnO thin film, ZnO nanowires and nanorods were characterized by X-ray diffraction (XRD) analysis and scanning electron microscope (SEM). The NO₂ gas sensing properties of ZnO thin films, nanowires and nanorods were investigated in a dark chamber at 200 °C in the concentration range of 100 ppb-10 ppm. It was found that the response times of both ZnO thin films and ZnO nanorods were approximately 30 s, and the sensor response was depended on shape and size of ZnO nanostructures and electrode configurations.     

Effect of Al concentrations on the electrodeposition and properties of transparent Al-doped ZnO thin films

Al-doped zinc oxide (AZO) thin films are prepared on polycrystalline fluorine-doped tin oxide-coated conducting glass substrates from nitrates baths by the electrodeposition process at 70 °C. The electrochemical, morphological, structural and optical properties of the AZO thin films were investigated in terms of different Al concentration in the starting solution. It was found that the carrier density of AZO thin films varied between ?3.11 and ?5.56 × 10²⁰ cm^?3 when the Al concentration was between 0 and 5 at.%. Atomic force microscopy images reveal that the concentration of Al has a very significant influence on the surface morphology and roughness of thin AZO. X-ray diffraction spectra demonstrate preferential (002) crystallographic orientation having c-axis perpendicular to the surface of the substrate and average crystallites size of the films was about 33–54 nm. With increasing Al doping, AZO films have a strong improved crystalline quality. As compared to pure ZnO, Al-doped ZnO exhibited lower crystallinity and there is a shift in the (002) diffraction peak to higher angles. Due to the doping of Al of any concentration, the films were found to be showing >80 % transparency. As Al concentration increased the optical band gap was also found to be increase from 3.22 to 3.47 eV. The room-temperature photoluminescence spectra indicated that the introduction of Al can improve the intensity of ultraviolet (UV) emission, thus suggesting its greater prospects in UV optoelectronic devices. A detailed comparison and apprehension of electrochemical, optical and structural properties of ZnO and ZnO:Al thin films is done for the determination of optimum concentration of Al doping.     

反应磁控溅射ZnO薄膜的高温退火研究

ZnO薄膜是一种新型的II VI族直接能带化合物半导体材料 ,有可能实现短波长的探测器 ,LED和LD等光电子器件。用磁控溅射法在硅衬底上生长ZnO薄膜 ,由于薄膜与衬底之间较大的应力失配 ,以及由于较快的生长速率 ,薄膜中存在较多的Zn间隙原子和O空位 ,在薄膜中存在应力。通过高温退火 ,可以使应力得到弛豫 ,降低O空位和Zn间隙原子的浓度 ,提高薄膜的化学计量比和改善薄膜的结晶质量。本实验用XRD和AFM研究了高温退火对ZnO薄膜的晶体性能和表面的影响。对ZnO薄膜在退火处理后c轴方向的应力性质的转变作了机理上的探讨。     

Chemical deposition of ZnO films for gas sensors

Zinc oxide (ZnO) thin films were prepared following a chemical, deposition technique using a sodium zincate bath. Structural characterizations by scanning electron microscopy (SEM) and X-ray diffraction (XRD) indicate the formation of ZnO film with a preferred c-axis orientation. The electrical conductance of the ZnO films became stable and reproducible in the 300–500 K temperature range with two activation energy barrier values of 0.3 eV and 0.8 eV in the low temperature (300–420 K) and high temperature (430–500 K) ranges, respectively. The ZnO films prepared by this method are highly resistive, indicating the presence of a large density of oxygen adsorbed acceptor-like trap states (O ₂ ^- , O_-, etc.). Palladium sensitized ZnO films were exposed to hydrogen (H₂) with air as a carrier gas at different operating temperatures ranging between 150–375°C and the response is evaluated.     

Local vapor transport synthesis of zinc oxide nanowires for ultraviolet-enhanced gas sensing

A novel local vapor transport technique via induction heating is presented to enable selective, localized synthesis and self-assembly of nanowires, providing a simple and fast method for the direct integration of nanowires into functional devices. The single-crystalline zinc oxide (ZnO) nanowires are grown locally across the silicon-on-insulator microelectrodes within minutes, and the enhancement of gas sensing of ZnO nanowires is demonstrated under ultraviolet (UV) illumination at room temperature. Experiments indicate that when suspended nanowires are exposed to UV light, a twelve-fold increase in conductance and a near five-fold improvement in oxygen response are measured. Furthermore, the UV-enhanced transient responses exhibit a two-level photocurrent decay attributed to carrier recombination and oxygen readsorption. As such, the local vapor transport synthesis and UV-enhanced sensing scheme could provide a promising approach for the construction of miniaturized and highly responsive nanowire-based gas sensors.     

Effect of ethylene glycol monomethyl ether ratio in mixed solvent on surface morphology,wettability and photocatalytic properties of ZnO thin films

Zinc oxide (ZnO) thin films with different ethylene glycol monomethyl ether (EGME) ratio were prepared on Si substrates using a two-step process. The results show that they possess a polycrystalline hexagonal wurtzite crystal structure. The topography of the ZnO thin films evolves from nanoparticles to hexagonal nanorods with the decrease of EGME content. The photoluminescence spectra consist of a near-band-edge emission and two visible emissions. The optical band gap energy decreases first and then increases with the increase of EGME ratio in mixed solvent, the broadening of the optical band gap can be explained by Moss–Burstein effect. The wetting behavior of all the samples can switch from hydrophobicity to hydrophilicity through UV illumination. The degradation efficiency of the thin films increases with decreasing EGME content, photocatalytic reaction mechanism of the ZnO thin films is discussed in detail.     

Low temperature growth and optical properties of ZnO nanowires using an aqueous solution method

ZnO nanowires were grown on indium tin oxide (ITO) coated glass substrates at a low temperature of 90 degrees C using an aqueous solution method. The ZnO seeds were coated on the ITO thin films by using a spin coater. ZnO nanowires were formed in an aqueous solution containing zinc nitrate hexahydrate (Zn(NO3)2 x 6H2O) and hexamethylenetetramine (C6H12N4). The pH value and concentration of the solution play an important role in the growth and morphologies of ZnO nanowires. The size of ZnO naonowires increased as the concentration of the solution increased. It was formed with a top surface of hexagonal and tapered shape at low and high pH values respectively. Additionally, the single crystalline structure and optical property of the ZnO nanowires were investigated using high-resolution transmission electron microscopy and photoluminescence spectroscopy.     

Enhanced H2 sensing properties of a-plane ZnO prepared on c-cut sapphire substrate by sputtering

Zinc oxide (ZnO) thin films have been prepared on c-plane sapphire substrate by magnetron sputtering technique. The influence of deposition time on the structural, optical and photoluminescence properties of the films have been investigated. XRD patterns reveal the growth of preferentially oriented (101) non-polar a-plane ZnO film with hexagonal wurtzite structure. The PL peak shifts towards lower wavelength for deposition time up to 20 min, which is in consistent with the results obtained from UV absorption studies. The blue shift in the PL peak confirms the possibility for quantum confinement effect. The band gap energy of the film increases from 3.33 to 3.38 eV, indicating enhanced quantum confinement effects. FESEM micrographs showed that the films have a smooth and dense morphology with uniform grain growth. Hydrogen sensing measurements indicated that a-plane ZnO film on c-sapphire showed higher response than c-plane ZnO film reported earlier. The sensor response of 44 nm thick ZnO film exhibit highest response of 145 towards 500 ppm H₂ gas at the operating temperature of 200 °C.     

Influence of Al concentration on structural and optical properties of Al-doped ZnO thin films

Undoped ZnO and Al-doped zinc oxide (ZnO:Al) thin films with different Al concentrations were prepared onto Si (100) substrate by pulsed filtered cathodic vacuum arc deposition system at room temperature. The influence of doping on the structural and optical properties of thin films was investigated. The preferential (002) orientation was weakened by high aluminum doping in films. Raman measurement was performed for the doping effects in the ZnO. Atomic force microscopy images revealed that the surface of undoped ZnO film grown at RT was smoother than that of the Al-doped ZnO (ZnO:Al) films. The reflectance of all films was studied as a function of wavelength using UV–Vis–NIR spectrophotometer. Average total reflectance values of about 35 % in the wavelength range of 400–800 nm were obtained. Optical band gap of the films was determined using the reflectance spectra by means of Kubelka–Munk formula. From optical properties, the band gap energy was estimated for all films.     

Nonlinear optical investigations on Al doping ratio in ZnO thin film under pulsed Nd:YAG laser irradiation

In the present study, it has been reported on the effect of Al doping on linear and nonlinear optical properties of ZnO thin films synthesized by spray pyrolysis method. The structural properties of ZnO thin films with different Al doping levels (0–4 wt%) were analyzed using X-ray diffraction (XRD). The results obtained from XRD analysis indicated that the grain size decreased as the Al doping value increased. The UV–Vis diffused refraction spectroscopy was used for calculation of band gap. The optical band gap of Al-doped ZnO (AZO) thin films is increased from 3.26 to 3.31 eV with increasing the Al content from 0 to 4 wt%. The measurements of nonlinear optical properties of AZO thin films have been performed using a nanosecond Nd:YAG pulse laser at 532 nm by the Z-scan technique. The undoped ZnO thin film exhibits reverse saturation absorption (RSA) whereas the AZO thin films exhibit saturation absorption (SA) that shows RSA to SA process with adding Al to ZnO structure under laser irradiation. On the other hand, all the films showed a self-defocusing phenomenon because the photons of laser stay on below the absorption edge of the ZnO and AZO films. The third-order nonlinear optical susceptibility, χ⁽³⁾, of AZO thin films, was varied from of the order of 10^?5–10^?4 esu. The results suggest that AZO thin films may be promising candidates for nonlinear optical applications.     

Effect of solution concentration on surface morphology and photocatalytic activity of ZnO thin films synthesized by hydrothermal methods

ZnO thin films were synthesized via hydrothermal method on silicon substrate at various solution concentrations. The thin films were characterized by X-ray diffraction, field-emission scanning electron microscope and UV–Vis spectrophotometer. The results show that the thin films are polycrystalline with wurtzite hexagonal structure. The T _c values of (101) surface of the thin film increase from 0.929 to 1.840 at first, and then decrease to 0.779 with increasing solution concentration. The preferential orientation along the (101) crystal surface can be controlled by changing the solution concentration. Solution concentration has a significant effect on surface morphology of the thin films. The optical band gap of the thin films decreases, when the solution concentration of zinc nitrate hexahydrate increases from 0.01 to 0.06 mol/L and then increases when the solution concentration of zinc nitrate hexahydrate further increases to 0.08 mol/L. Photocatalytic activity of the thin films on degradation of methyl orange under UV light irradiation was studied in detail. The ZnO thin film with many cracks prepared from 0.01 mol/L shows the higher photocatalytic activity but the tower-like ZnO thin film prepared from 0.08 mol/L reveals the lower photocatalytic activity. Therefore, the photocatalytic activity of the thin films are mainly relate to surface morphology and crystallographic orientation.     

Optical and electrical properties of ZnO films, codoped with Al and Ga deposited at room temperature by an RF sputtering method

ZnO thin films, codoped with Al and Ga, were prepared on fused quartz (FQ) and cyclo-olefin polymer (COP) substrates using a radial frequency magnetron sputtering technique at room temperature, without the introducing of oxygen. The elemental distributions of Al, Ga, Zn and O throughout the films were found and no compositional variation in working pressure was observed. A resistivity of 0.03-4.07 Ω cm in AGZ/FQ films (Fig. 2b and 0.04-5.73 Ω cm in AGZ/COP films as well as a transmittance of above 85% were obtained by appropriate control of the working pressure. Compared with the band gap energy of single crystal ZnO, the band gap energy of the AGZ/FQ thin film was somewhat higher. The band gap energy of the AGZ/FQ films showed a tendency to increase with the working pressure employed.     

Electrical charge conductivity behavior of electrodeposited Cu2O/ZnO heterojunction thin films on PET flexible substrates by impedance spectroscopy analysis

The bottom-up self-assembly Cu₂O/ZnO heterojunction thin films electrodeposited on indium tin oxide flexible substrate (polyethylene terephthalate, PET) have been investigated by impedance spectroscopy. It is used to study the electric conductivity of the Cu₂O/ZnO heterojunction thin films combined electric modulus and impedance plots. The electric modulus and impedance as a function of the frequency analysis show the distribution of the relaxation times due to the hopping of charge carriers among defects in the Cu₂O/ZnO heterojunction thin films. The values of activation energies derived from the electric modulus and impedance are found to be 0.42 and 0.40 eV, respectively, which is close to the activation energy (0.28 eV) of dc electrical conductivity and activation energy of ac conductivity (0.45–0.14 eV at the range of 100 Hz–1 MHz) in the temperature range over 303–423 K.     

Thickness dependence of structural, electrical and optical properties of sprayed ZnO:Cu films

ZnO:Cu thin films have been deposited by spray pyrolysis techniques within two different (450 °C and 500 °C) substrate temperatures. The structural properties of ZnO:Cu thin films have been investigated by X-ray diffraction techniques. The X-ray diffraction spectra showed that ZnO:Cu thin films are polycrystalline with the hexagonal structure and show a good c-axis orientation perpendicular to the substrate. The most preferential orientation is along the (002) direction for all spray deposited ZnO:Cu films together with orientations in the (100) and (101) planes also being abundant. Some parameters of the films were calculated and correlated with the film thickness for two different substrate temperatures. The optical properties of ZnO:Cu thin films have been investigated by UV/VIS spectrometer and the band gap values were found to be ranging from 3.29 eV to 3.46 eV.     

Post annealing effect on structural and optical properties of ZnO thin films derived by sol–gel route

Zinc oxide thin films have been spun coated on p-Si (100) substrates by sol–gel route. These films were annealed at different annealing temperatures from 300 to 1,000 °C in the oxygen ambient. In this way a suitable annealing temperature window for the sol–gel derived ZnO films exhibiting minimum defects (points and dislocations) and better quality (crystal and optical) was investigated. The structural and optical features of ZnO thin films have been examined by X-ray diffraction, atomic force microscopy, UV–Vis spectroscopy, and photoluminescence spectra. The results revealed that the crystallization in the films initiated at 300 °C, improved further with annealing. All the deposited films exhibited wurtzite phase with c-axis orientations. The variations in the position of characteristic (002) peak, stress, strain and lattice parameters are investigated as a function of annealing temperature. The optical band gap is not significantly affected with annealing as observed by UV–Vis transmission spectroscopy. The Photoluminescence spectra exhibited three luminescence centers. The near band edge esmission was observed in UV region which enhanced with the heat treatment, is an indication of improvement in the optical quality of films. The other two visible emissions are related to native defects in ZnO lattice were appeared only for higher annealing (≥700 °C).