ZnO Films Synthesized by Solid-Source Chemical Vapor Deposition with c-Axis Parallel to Substrate

ZnO films with c -axis parallel to the substrate are reported.ZnO films are synthesized by solid-source chemical vapor deposition,a novel CVD technique,using zinc acetate dihydrate (solid) as the source material.The properties are characterized by X-ray diffraction,atomic force microscopy and transmission spectra.The parallel oriented ZnO films with mixed orientation for (100) and (110) planes are achieved on glass at the substrate temperature of 200℃ and the source temperature of 280℃,and a qualitative explanation is given for the forming of the mixed orientation.AFM images show that the surface is somewhat rough for the parallel oriented ZnO films.The transmission spectrum exhibits a high transmittance of about 85% in the visible region and shows an optical band gap about 3.25eV at room temperature.

A Novel Approach to Synthesizing Porous ZnO Films: Inorganic Chelating Sol-Gel Method

Porous ZnO films are synthesized by inorganic chelating sol-gel method,which is a novel sol-gel technique using zinc nitrate as starting materials and citric acid as the chelating reagent.The crystal structure,surface morphology,porous and optical properties of the deposited films are investigated.X-ray diffraction pattern analysis shows that crystal structure of the ZnO films is hexagonal wurtzite.Scanning electron microscopy (SEM) shows that the ZnO film is porous.The curve of pore size distribution has two peak values at about 2.02nm and 4.97nm and BET surface area of the ZnO film is 27.57m2/g.In addition,the transmittance spectrum gives a high transmittance of 85% in the visible region and optical bandgap of the ZnO film (fired at 500℃) is 3.25eV.

Spontaneous Cracking of Graphite Oxide Sheet on Oxygen Deficient ZnO Film

Graphite oxide （GO） is an important material of wide applications. Owing to its good mechanical property, the GO sheet is always expected to be stable and remains flat on various substrates. Here we demonstrate for the first time an unexpected behavior of the GO sheet on oxygen deficient ZnO film, namely the spontaneous cracking of the entire GO sheet into many small pieces. This unusual behavior has been carefully investigated by a series of control experiments and SEM, XPS and PL measurements. It is anticipated that the oxygen vacancies in the oxygen deficient ZnO film can annihilate epoxy groups of the GO sheet, resulting in the unzipping of the aligned epoxy groups on GO sheet. A prototype of the white light detector made from the cracked GO sheet is fabricated and the device demonstrates high stability and good reproducibility.

Low-Temperature Growth of ZnO Films on GaAs by Metal Organic Chemical Vapor Deposition

ZnO thin films were grown on GaAs （001） substrates by metal-organic chemical vapor deposition （MOCVD） at low temperatures ranging from 100 to 400℃. DEZn and 1-12 O were used as the zinc precursor and oxygen precursor, respectively. The effects of the growth temperatures on the growth characteristics and optical properties of ZnO films were investigated. The X-ray diffraction measurement （XRD） results indicated that all the thin films were grown with highly c- axis orientation. The surface morphologies and crystal properties of the films were critically dependent on the growth temperatures. Although there was no evidence of epitaxial growth, the scanning electron microscopy （SEM） image of ZnO film grown at 400℃ revealed the presence of ZnO microcrystallines with closed packed hexagon structure. The photoluminescence spectrum at room temperature showed only bright band-edge （3. 33eV） emissions with little or no deep-level e- mission related to defects.

Fabrication of ZnO films by radio frequency magnetron sputtering and annealing

ZnO thin films were deposited on Si（111） substrates through a radio frequency （rf） magnetron sputtering system. Then the samples were annealed at different temperatures in air ambience and ammonia ambience respectively. The structure and composition of the ZnO films were studied by X-ray diffraction （XRD） and X-ray photoelectron spectroscopy （XPS）. The morphology of the samples was studied by scanning electron microscopy （SEM）. Measured results show that ZnO films with hexagonal wurtzite structure were grown on Si（111） substrates when annealed in the two ambiences. The volatilization process of ZnO in the ammonia ambience at high temperature was discussed and the mechanism of the reaction was analyzed.

Propagations of Rayleigh and Love waves in ZnO films/glass substrates analyzed by three-dimensional finite element method

Propagation characteristics of surface acoustic waves（SAWs） in ZnO films/glass substrates are theoretically investigated by the three-dimensional（3D） finite element method. At first, for（11ˉ20） ZnO films/glass substrates, the simulation results confirm that the Rayleigh waves along the [0001] direction and Love waves along the [1ˉ100] direction are successfully excited in the multilayered structures. Next, the crystal orientations of the ZnO films are rotated, and the influences of ZnO films with different crystal orientations on SAW characterizations, including the phase velocity, electromechanical coupling coefficient, and temperature coefficient of frequency, are investigated. The results show that at appropriate h/λ, Rayleigh wave has a maximum k^2 of 2.4% in（90°, 56.5°, 0°） ZnO film/glass substrate structure; Love wave has a maximum k^2 of 3.81% in（56°, 90°, 0°） ZnO film/glass substrate structure. Meantime, for Rayleigh wave and Love wave devices, zero temperature coefficient of frequency（TCF） can be achieved at appropriate ratio of film thickness to SAW wavelength. These results show that SAW devices with higher k^2 or lower TCF can be fabricated by flexibly selecting the crystal orientations of ZnO films on glass substrates.

The low temperature growth of stable p-type ZnO films in HiPIMS

In this study,the influence of substrate temperature on properties of Al-N co-doped p-type ZnO films is explored.Benefitting from the high ionization rate in high-power impulsed magnetron sputtering,the concentration of ionized nitrogen N+and ionized zinc Zn+were increased,which promoted the formation of ZnO films and lowered the necessary substrate temperature.After optimization,a co-doped p-type ZnO thin film with a resistivity lower than 0.35Ωcm and a hole concentration higher than 5.34×10^(18)cm^(-3)is grown at 280°C.X-ray diffraction results confirm that Al-N co-doping does not destruct the ZnO wurtzite structure.X-ray photoelectron spectroscopy demonstrates that the presence of Al promotes the formation of acceptor(No)defects in ZnO films,and ensures the role of Al in stabilizing p-type ZnO.

Effects of Homo-buffer Layer on Properties of Sputter-deposited ZnO Films

Two-step growth regimes were applied to realize a homoepitaxial growth of ZnO films on freestanding diamond substrates by radio-frequency （RF） reactive magnetron sputtering method. ZnO buffer layers were deposited on freestanding diamond substrates at a low sputtering power of 50 W, and then ZnO main layers were prepared on this buffer layer at a high sputtering power of 150 W. For comparison, a sample was also deposited directly on freestanding diamond substrate at a power of 150 W. The effects of ZnO buffer layers on the structural, optical, electrical and morphological properties of the ZnO main layer were studied by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, Raman spectroscopy, semiconductor characterization system and atomic force microscopy （AFM） respectively. The experimental results suggested that homo-buffer layer was helpful to improve the crystalline quality of ZnO/diamond heteroepitaxial films.

Studies on Crystal Orientation of ZnO Film on Sapphire Using High-throughout X-ray Diffraction

The orientation of the nano-columnar ZnO films grown on sapphire using the technique of metal-organic chemical vapor deposition （MOCVD） exhibits deviation because of the mismatch between the crystal lattices of the films and the sapphire substrate. A high-throughout X-ray diffraction method was employed to determine the crystal orientation of the ZnO films at a time scale of the order of minutes based on the general area detection diffraction system （GADDS）. This rapid, effective, and ready method, adapted for characterizing the orientation of the nano-columnar crystals is used to directly explain the results of observation of the X-ray diffraction images, by the measurements of the orientations of the crystal columns of the ZnO films along c-axis and in parallel to ab plane.

Preparation and Characterization of Highly Oriented ZnO Film by Ultrasonic Assisted SILAR Method

Ultrasonic Assisted SILAR method （UA-SILAR） was developed and highly oriented ZnO films were deposited on the glass substrate by this novel technique. The crystallinity and microstructure of as-deposited ZnO films were analyzed by means of XRD and SEM. Moreover, the underling deposition mechanism of ZnO films was discussed. Results show that obtained ZnO films exhibit an excellent crystallinity with the preferentioal orientation of （002） plane. The crystalline grain of films is about 40nm in size,which is supported by both the Sherrer equation and the SEM result. However, the ZnO film is composed of numerous clustered purticulates in the size of 200 to 300nm, and each particulate is the compact aggregation of smaller ZnO crystalline grains. It is .speculated that the excellent crystallinity of ZnO films may chiefly originate from the cavatition effect of the ultrasonic rinsing process.

The Third-Order Nonlinear Optical Properties in Cobalt-Doped ZnO Films

We quantitatively investigate the third-order optical nonlinear response of Co-doped ZnO thin films prepared by magnetron sputtering using the Z-scan method. The two-photon absorption and optical Kerr effect are revealed to contribute to the third-order nonlinear response of the Co-doped ZnO films. The nonlinear absorption coefficient β is determined to be approximately 8.8 × 10-5 cm/W and the third-order nonlinear susceptibility X（3） is 2.93 × 10-6 esu. The defect-associated energy levels within the band gap are suggested to be responsible for the enhanced nonlinear response observed in Co-doped ZnO films.

ZnO Films Deposited on Glass by Means of DC Sputtering

ZnO films were deposited on glass substrates by means of a direct current (DC) sputtering technique. The physical properties of the films were investigated on the basis of X-ray diffraction measurements. It was found that as-deposited films show c-axis oriented crystal normal to the surface with the extension of c axis by 1.27% that is estimated from the shift of the peak in the X-ray diffraction pattern. Post-deposition annealing in air at higher than 400℃ eliminates the shift and sharpens the diffraction peak structure at the same time. The electrical resistivity continues to decrease from 500 Ω•cm down to 0.6 Ω•cm by annealing as high as 600℃.

Nanoscaled ZnO films used as enhanced substrates for fluorescence detection of dyes

The ability of nanoscaled ZnO films to enhance fluorescence was studied. We found that the fluorescence intensities of Cy5, rhodamine 6G, and fiuorescein can be enhanced about 10-fold on nanoscaled ZnO films as compared to that on glass substrates. The lifetimes of all samples were measured, and no obvious change in lifetime was observed for dyes on different substrates. The mechanism for the nanoscaled ZnO film enhanced fluorescence appears to be different from that for the metal-fluorophore systems.

Structural and Optical Properties of ZnO Films with Different Thicknesses Grown on Sapphire by MOCVD

ZnO（002） films with different thicknesses, grown on Al2O3 （006） substrates by metal-organic chemical vapor deposition（ MOCVD）, were etched by Ar ion beams. The samples were examined by D8 X-ray diffraction, scanning electron microscopy（SEM）, and photoluminescence（PL） spectrometry. The structural properties vary with the increasing thickness of the films. When the film thickness is thin, the phi（Φ） scanning curves for ZnO（103） and sapphire（116） substrate show the existence of two kinds of orientation relationships between ZnO films and sapphire, which are ZnO（002）//Al2O3 （006）, ZnO（ 100）//Al2O3 （110） and ZnO（002）//Al2O3 （006）, ZnO（ 110）//Al2O3 （110）. When the thickness increases to 500 nm there is only one orientation relationship, which is ZnO（002）// Al2O3 （006）, ZnO [ 100]//Al2O3 [ 110]. Their photoluminescence（PL） spectra at room temperature show that the optical properties of ZnO films have been greatly improved when increasing the thickness of films is increased.

Photoluminescence Properties of Two-dimensional Planar Layer and Three-dimensional Island Layer for ZnO Films Grown Using MOCVD

ZnO（002） films with different thicknesses ranging from 7 to 300 nm were grown on sapphire（006） substrates via metal-organic chemical vapor deposition （MOCVD）. The two-dimensional（2D） planar layer and the three-dimensional（3D） island layer were studied by using of X-ray diffraction（XRD） rocking curves and atomic force microscopy （AFM）. The room temperature photoluminescence （PL） spectra show a blue shift of the peak positions of the uhraviolet（UV） emission with increasing film thickness. The blue shift is remarkably high（393-380 nm） when an increase in film thickness（7-15 nm） is accompanied by the change of structure from a 2D planar layer to a 3D island layer. The PL spectra at 77 K also indicate that there are different transition mechanisms in the film thickness from a 2D planar layer to a 3D island layer near the 2D layer region.

Comparison of ZnO Films Grown on before- and after-vapor Transport Equilibration (VTE) LiAlO_2 Substrates by Pulsed Laser Deposition (PLD)

About φ45 mm LiAlO2 single crystal was grown by Czochralski （Cz） technique. However, the full-width at half-maximum （FWHM） value was high to 116.9 arcsec. After three vapor transport equilibration （VTE） processes, we can obtain high-quality LiAlO2 slice with the FWHM value of 44.2 arcsec. ZnO films were fabricated on as-grown slices and after-VTE ones by pulsed laser deposition （PLD）. It was found that ZnO films on the two slices have similar crystallinity, optical transmittance and optical band gap at room temperature. These results not only show that LAO substrate is suitable for ZnO growth, but also prove that the crystal quality of LAO substrate slightly affects the structural and optical properties of ZnO film.

Zn/O ratio and oxygen chemical state ofnanocrystalline ZnO films grown atdifferent temperatures

ZnO nanocrystalline films are prepared on Si substrates at different temperatures by using metal-organic chemical vapour deposition （MOCVD）. It is observed that when the growth temperature is low, the stoichiometric ratio between Zn and 0 atoms has a large deviation from the ideal ratio of 1：1. The ZnO grains in the film have small sizes and are not well crystallized, resulting in a poor photoluminescence （PL） property. When the temperature is increased to an appropriate value, the Zn/O ratio becomes optimized, and most of Zn and 0 atoms are combined into Zn-O bonds. Then the film has good crystal quality and good PL property. If the temperature is fairly high, the interracial mutual diffusion of atoms between the substrate and the epitaxial film appears, and the desorption process of the oxygen atoms is enhanced. However, it has no effect on the film property. The film still has the best crystal quality and PL property.

Cubic ZnO films obtained at low pressure by molecular beam epitaxy

A zinc oxide thin film in cubic crystalline phase, which is usually prepared under high pressure, has been grown on the Mg O（001） substrate by a three-step growth using plasma-assisted molecular beam epitaxy. The cubic structure is confirmed by in-situ reflection high energy electron diffraction measurements and simulations. The x-ray photoelectron spectroscopy reveals that the outer-layer surface of the film（less than 5 nm thick） is of ZnO phase while the buffer layer above the substrate is of ZnMgO phase, which is further confirmed by the band edge transmissions at the wavelengths of about 390 nm and 280 nm, respectively. The x-ray diffraction exhibits no peaks related to wurtzite ZnO phase in the film. The cubic ZnO film is presumably considered to be of the rock-salt phase. This work suggests that the metastable cubic ZnO films, which are of applicational interest for p-type doping, can be epitaxially grown on the rock-salt substrates without the usually needed high pressure conditions.

PEDOT:PSS Schottky contacts on annealed ZnO films

Polycrystalline ZnO and ITO films on SiO2 substrates are prepared by radio frequency （RF） reactive magnetron sputtering. Schottky contacts are fabricated on ZnO films by spin coating with a high conducting polymer, poly（3, 4-ethylenedioxythiophene）： poly（styrenesulfonate） （PEDOT：PSS） as the metal electrodes. The current-voltage mea- surements for samples on unannealed ZnO films exhibit rectifying behaviours with a barrier height of 0.72 eV （n ---- 1.93）. The current for the sample is improved by two orders of magnitude at 1 V after annealing ZnO film at 850 ~C, whose barrier height is 0.75 eV with an ideality factor of 1.12. X-ray diffraction, atomic force microscopy and scanning electron microscopy are used to study the properties of the PEDOT：PSS/ZnO/ITO/SiO2. The results are useful for applications such as metal-semiconductor field-effect transistors and UV photodetectors.

Microstructure and optical properties of nitrogen-doped ZnO film

The nitrogen doping of ZnO film deposited by the magnetron sputtering method is subsequently realized by the hydrothermal synthesis method.The nitrogen-doped ZnO film is preferably（002） oriented.With the increase of hexamethylenetetramine（HMT） solution concentration,the average grain size of the film along the 002 direction almost immediately decreases and then monotonously increases,conversely,the lattice strain first increases and then decreases.The structural evolution of the film surface from compact and even to sparse and rough is attributed to the enhanced nitrogen doping content in the hydrothermal process.The transmission and photoluminescence properties of the film are closely related to grain size,lattice strain,and nitrogen-related defect arising from the enhanced nitrogen doping content with HMT concentration increasing.