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.     

The influence of using different substrates on the structural and optical characteristics of ZnO thin films

ZnO thin films with thikness d = 100 nm were deposited onto different substrates such as glass, kapton, and silicon by radio frequency magnetron sputtering. The structural analyses of the films indicate they are polycrystalline and have a wurtzite (hexagonal) structure.The ZnO layer deposited on kapton substrate shows a stronger orientation of the crystallites with (0 0 2) plane parallel to the substrate surface, as compared with the other two samples of ZnO deposited on glass and silicon, respectively.All three layers have nanometer-scale values for roughness, namely 1.7 nm for ZnO/glass, 2.4 nm for ZnO/silicon, and 6.8 nm for ZnO/kapton. The higher value for the ZnO layer deposited on kapton substrate makes this sample suitable for solar cells applications. Transmission spectra of these thin films are strongly influenced by deposition conditions. With our deposition conditions the transparent conducting ZnO layer has a good transmission (78-88%) in VIS and NIR domains. The values of the energy gap calculated from the absorption spectra are 3.23 eV for ZnO sample deposited onto glass substrate and 3.30 eV for the ZnO sample deposited onto kapton polymer foil substrate. The influence of deposition arrangement and oxidation conditions on the structural, morphological, and optical properties of the ZnO films is discussed in the present paper.     

Reversible wettability of nanostructured ZnO thin films by sol-gel method

Nanostructured ZnO thin films were deposited on Si(1 1 1) and quartz substrate by sol-gel method. The thin films were annealed at 673 K, 873 K, and 1073 K for 60 min. Microstructure, surface topography, and water contact angle of the thin films have been measured by X-ray diffractometer, atomic force microscopy, and water contact angle apparatus. XRD results showed that the ZnO thin films are polycrystalline with hexagonal wurtzite structure. AFM studies revealed that rms roughness changes from 2.3 nm to 7.4 nm and the grain size grow up continuously with increasing annealing temperature. Wettability results indicated that hydrophobicity of the un-irradiated ZnO thin films enhances with annealing temperature increase. The hydrophobic ZnO surfaces could be reversibly switched to hydrophilic by alternation of UV illumination and dark storage (thermal treatment). By studying the magnitude and the contact angle reduction rate of the light-induced process, the contribution of surface roughness is discussed.     

Preparation and characterization of Mg-doped ZnO thin films by sol-gel method

Undoped and Mg-doped ZnO thin films were deposited on Si(1 0 0) and quartz substrates by the sol-gel method. The thin films were annealed at 873 K for 60 min. Microstructure, surface topography and optical properties of the thin films have been measured by X-ray diffraction (XRD), atomic force microscope (AFM), UV-vis spectrophotometer, and fluorophotometer (FL), respectively. The XRD results show that the polycrystalline with hexagonal wurtzite structure are observed for the ZnO thin film with Mg:Zn = 0.0, 0.02, and 0.04, while a secondary phase of MgO is evolved for the thin film with Mg:Zn = 0.08. The ZnO:Mg-2% thin film exhibits high c-axis preferred orientation. AFM studies reveal that rms roughness of the thin films changes from 7.89 nm to 16.9 nm with increasing Mg concentrations. PL spectra show that the UV-violet emission band around 386-402 nm and the blue emission peak about 460 nm are observed. The optical band gap calculated from absorption spectra and the resistivity of the ZnO thin films increase with increasing Mg concentration. In addition, the effects of Mg concentrations on microstructure, surface topography, PL spectra and electrical properties are discussed.     

Structural and optical properties of sputtered ZnO thin films

Zinc oxide (ZnO) and aluminium-doped zinc oxide (ZnO:Al) thin films were prepared by RF diode sputtering at varying deposition conditions. The effects of negative bias voltage and RF power on structural and optical properties were investigated. X-ray diffraction measurements (XRD) confirmed that both un-doped and Al-doped ZnO films are polycrystalline and have hexagonal wurtzite structure. The preferential 〈0 0 1〉 orientation and surface roughness evaluated by AFM measurements showed dependence on applied bias voltage and RF power. The sputtered ZnO and ZnO:Al films had high optical transmittance (>90%) in the wavelength range of 400-800 nm, which was not influenced by bias voltage and RF power. ZnO:Al were conductive and highly transparent. Optical band gap of un-doped and Al-doped ZnO thin films depended on negative bias and RF power and in both cases showed tendency to narrowing.     

Cathodoluminescent and nonlinear optical properties of undoped and erbium doped nanostructured ZnO films deposited by spray pyrolysis

We have deposited zinc oxide (ZnO) and erbium doped zinc oxide (ZnO:Er) thin films on heated glass substrates using spray pyrolysis technique. The effect of erbium dopant on structural, morphological, luminescent and nonlinear optical properties was studied. The deposited films have been analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), ex situ compositional analysis (ESCA), profilometry, cathodoluminescence (CL) and third harmonic generation (THG) measurements. All films were polycrystalline, having a preferential growth orientation along the ZnO (0 0 2) plane, with a corresponding average crystallite size of less than 41 nm. Addition of erbium can effectively control the film surface morphology and its cathodoluminescent properties. The films containing low erbium concentration show a uniform surface covered with hexagonal shaped grains and a strong UV light emission intensity as well as TH response. In contrast, when the erbium doping ratio exceeds 3%, a porous surface with columnar textural growth becomes more pronounced, and a substantial reduction of the cathodoluminescent and TH response. A strong TH signal was obtained for the film with good crystalline quality at the concentration of 2%. Third order nonlinear optical susceptibility (χ^〈3〉) values of the studied materials were in the remarkable range of 10⁻¹² esu.     

High-quality oriented ZnO films grown by sol-gel process assisted with ZnO seed layer

High-quality oriented ZnO films were prepared on silicon and quartz glass by sol-gel, assisted with a ZnO seed layer. The effects of the seed layer on the orientation, morphology and optical properties of ZnO films were investigated. Results show that the seed layer can effectively induce the growth of high-quality oriented ZnO films on two substrates, and the effectiveness of the seed layer strongly depends on preparation conditions, i.e., the spin-coating layer number and the preheating temperature. ZnO films with five layers on the seed layer preheated at 500 °C exhibit the single (0 0 2) orientation, which is much stronger than that on the flat substrate. Additionally, ZnO films on the seed layer show a denser internal structure and higher optical quality than that on the flat substrate. At ten layers, however, ZnO films on the seed layer show the multiple-orientation, which is similar to that on the flat substrate. Finally, the physical mechanism underlying the growth behavior of ZnO films assisted with the seed layer was discussed.     

Synthesis, characterization and optical properties of multipod ZnO whiskers

Multipod ZnO whiskers were synthesized successfully by two steps: pulsed laser deposition (PLD) and thermal evaporation process. First, a thin layer of Zn films were deposited on Si(1 1 1) substrates by PLD. Then the whiskers grew on Zn-coated Si(1 1 1) substrate by the simple thermal evaporation oxidation of the metallic zinc powder at 900 °C in the air without any catalysts or additives. The pre-deposited Zn films by PLD on the substrate can promote the growth of ZnO multipod whiskers effectively. The as-synthesized ZnO whiskers were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The results revealed that the whiskers are highly crystalline with the wurtzite hexagonal structure. Room temperature photoluminescence (PL) spectrum of the whiskers shows a UV emission peak at ∼393 nm and a broad green emission peak at ∼517 nm, which was assigned to the near band-edge emission and the deep-level emission, respectively.     

Effect of temperature on pulsed laser deposition of ZnO films

ZnO thin films have been deposited on Si(1 1 1) substrates at different substrate temperature by pulsed laser deposition (PLD) of ZnO target in oxygen atmosphere. An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the deposition temperature on the thickness, crystallinity, surface morphology and optical properties of ZnO films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), photoluminescence (PL) spectrum and infrared spectrum. The results show that in our experimental conditions, the ZnO thin films deposited at 400 °C have the best surface morphology and crystalline quality. And the PL spectrum with the strongest ultraviolet (UV) peak and blue peak is observed in this condition.     

Effect of sputtered films on morphology of vertical aligned ZnO nanowires

Vertical aligned ZnO nanowires were grown by MOCVD technique on silicon substrate using ZnO and AlN thin films as seed layers. The shape of nanostructures was greatly influenced by the under laying surface. Vertical nanopencils were observed on ZnO/Si, whereas the nanowires on both sapphire and AlN/Si substrate have the similar aspect ratio. XRD patterns suggest that the nanostructures have good crystallinity. High-resolution transmission electron microscopy (HRTEM) confirmed the single crystalline growth of the ZnO nanowires along [0 0 1] direction. Room-temperature photoluminescence (PL) spectra of ZnO nanowires on AlN/Si clearly show a band-edge luminescence accompanied with a visible emission. More interestingly, no visible emission for the nanopencils on ZnO/Si substrates, were observed.     

The effect of heat treatment on the physical properties of sol-gel derived ZnO thin films

Zinc oxide (ZnO) thin films were deposited on microscope glass substrates by sol-gel spin coating method. Zinc acetate (ZnAc) dehydrate was used as the starting salt material source. A homogeneous and stable solution was prepared by dissolving ZnAc in the solution of monoethanolamine (MEA). ZnO thin films were obtained after preheating the spin coated thin films at 250 °C for 5 min after each coating. The films, after the deposition of the eighth layer, were annealed in air at temperatures of 300 °C, 400 °C and 500 °C for 1 h. The effect of thermal annealing in air on the physical properties of the sol-gel derived ZnO thin films are studied. The powder and its thin film were characterized by X-ray diffractometer (XRD) method. XRD analysis revealed that the annealed ZnO thin films consist of single phase ZnO with wurtzite structure (JCPDS 36-1451) and show the c-axis grain orientation. Increasing annealing temperature increased the c-axis orientation and the crystallite size of the film. The annealed films are highly transparent with average transmission exceeding 80% in the visible range (400-700 nm). The measured optical band gap values of the ZnO thin films were between 3.26 eV and 3.28 eV, which were in the range of band gap values of intrinsic ZnO (3.2-3.3 eV). SEM analysis of annealed thin films has shown a completely different surface morphology behavior.     

A comparative study on structural and optical properties of ZnO and Al-doped ZnO thin films obtained by ultrasonic spray method using different solvents

Transparent conducting ZnO and Al doped ZnO thin films were deposited on glass substrate by ultrasonic spray method. The thin films with concentration of 0.1 M were deposited at 350 °C with 2 min of deposition time. The effects of ethanol and methanol solution before and after doping on the structural, optical and electrical properties were examined. The DRX analyses indicated that ZnO films have nanocrystalline nature and hexagonal wurtzite structure with (1 0 0) and (0 0 2) preferential orientation corresponding to ZnO films resulting from methanol and ethanol solution, respectively. The crystallinity of the thin films improved with methanol solution after doping to (0 0 2) oriented. All films exhibit an average optical transparency about 90%, in the visible range. The band gaps values of ZnO thin films are increased after doping from 3.10 to 3.26 eV and 3.27 to 3.30 eV upon Al doping obtained by ethanol and methanol solution, respectively. The electrical conductivity increase from 7.5 to 15.2 (Ω cm)⁻¹ of undoped to Al doped ZnO thin films prepared by using ethanol solution. However, for the methanol solution; the electrical conductivity of the film is stabilized after doping.     

Low temperature synthesis wide optical band gap Al and (Al, Na) co-doped ZnO thin films

Al-doped ZnO (AZO) and (Al, Na) co-doped ZnO (ANZO) thin films were prepared via sol-gel technique with an annealing process at temperatures between 450 and 550 °C for 60 min in air ambient, and their structural and optical properties have been investigated. The deposited films exhibited hexagonal zinc oxide structure except annealing at 450 °C. For the 500 °C-annealed samples, the surface morphology was analyzed via scanning electron microscopy, Photoluminescence (PL) of different Na content ANZO thin films showed that there were very obvious violet and blue emission bands between 400 and 500 nm, and intensity of which were enhanced with Na content increasing. Transparency of the films was improved along with increasing Na content. The result of UV indicated the absorb bands appeared obviously red shift with Na doping into ZnO, the optical gaps of all films far beyond 3.37 eV of pure ZnO, and gradually decreased with Na content increasing, this is very virtual for improving photoelectricity performance of transparent conduct oxide (TCO) film. The possible origins responsible for structure and optical properties also had been discussed.     

Structural and optical characteristics of spin-coated ZnO thin films

Zinc oxide (ZnO) thin films were deposited onto glass substrates by spin-coating method, from a precursor solution containing zinc acetate, ethanol and ammonium hydroxide. After deposition, the films were heated at a temperature of 100 °C in order to remove unwanted materials. Finally, the films were annealed at 500 °C for complete oxidation. X-ray diffraction showed that ZnO films were polycrystalline and have a hexagonal (wurtzite) structure. The crystallites are preferentially oriented with (0 0 2) planes parallel to the substrate surface. The films have a high transparency (more than 75%) in the spectral range from 450 nm to 1300 nm. The analysis of absorption spectra shows the direct nature of band-to-band transitions. The optical bandgap energy ranges between 3.15 eV and 3.25 eV.Some correlations between the processing parameters (spinning speed, temperature of post deposition heat treatment) and structure and optical characteristics of the respective thin films were established.     

The crystalline structure,conductivity and optical properties of Co-doped ZnO thin films

Transparent conductive Co-doped ZnO thin films were deposited by ultrasonic spray technique. Conditions of preparation have been optimized to get good quality. A set of cobalt (Co)-doped ZnO (between 0 and 3 wt%) thin films were grown on glass substrate at 350 °C. The thin films were annealed at 500 °C for improvement of the physical properties. Nanocrystalline films with hexagonal wurtzite structure and a strong (0 0 2) preferred orientation were obtained. The maximum value of grain size G = 63.99 nm is attained with undoped ZnO film. The optical transmissions spectra showed that both the undoped and doped ZnO films have transparency within the visible wavelength region. The band gap energy decreased after doping from 3.367 to 3.319 eV when Co concentration increased from 0 to 2 wt% with slight increase of electrical conductivity of the films from 7.71 to 8.33 (Ω cm)⁻¹. The best estimated structure, optical and electrical results are achieved in Co-doped ZnO film with 2 wt%.     

Synthesis and characterization of ZnO nano/microfibers thin films by catalyst free solution route

Zinc oxide (ZnO) nano/microfibrous thin films were successfully synthesized by a catalyst free solution route on glass and Si substrates. X-ray diffraction study revealed the formation of ZnO nanofibers of hexagonal crystalline structure. The texture coefficient of different planes varied with annealing temperature and that of the (0 0 2) plane was the highest for films annealed at temperature 873 K. Scanning electron micrograph showed the well formation of ZnO nano/microfibers with an average diameter 500 nm and having an average aspect ratio 150. UV–Vis–NIR spectroscopic study for the films deposited on glass substrates showed the high transmittance in the visible and near-infrared region. It was also observed that the band gap energy decreased as the films were annealed at higher temperature. The band gap energies of nanostructured ZnO thin films were determined to be in the range 3.03–3.61 eV. The photoluminescence study showed an UV emission peak at 397 nm, a visible blue–green emission peak at 468 nm and a green emission peak at 495 nm. Field emission properties of nanofiber ZnO thin film showed considerably low turn-on field around 1.4 V/μm. The emission current was as high as 70 μA at the field of 3.6 V/μm.     

Effect of crystallinity of ZnO buffer layer on the properties of epitaxial (ZnO:Al)/(ZnO:Ga) bi-layer films deposited on c-sapphire substrate

Bi-layer ZnO films with 2 wt.% Al (AZO; ZnO:Al) and 4 wt.% Ga-doped (GZO; ZnO:Ga) were deposited on the ZnO buffered and annealed ZnO buffered c(0 0 0 1)-sapphire(Al₂O₃) substrates respectively by Pulsed Laser Deposition (PLD). The effect of crystallinity of ZnO buffer layer on the crystallinity and electrical properties of the AZO/GZO bi-layer thin films was investigated. It was seen that the crystallinity of ZnO buffer layer had a great influence on the orientation and defect density of AZO/GZO bi-layer thin films from X-ray Diffraction (XRD) peaks and High Resolution Transmission Electron Microscopy (HRTEM) images. In a word, it was found in the films that more preferred c-axis orientation texture and reduction of the defects such as stacking faults and dislocations, with increasing of the crystallinity of ZnO buffer layer.     

Fabrication of high hole-carrier density p-type ZnO thin films by N-Al co-doping

In order to obtain p-type ZnO thin films, effect of atomic ratio of Zn:N:Al on the electronic and structural characteristic of ZnO thin films was investigated. Hall measurement indicated that with the increase of Al doping, conductive type of as-grown ZnO thin films changed from n-type to p-type and then to n-type again, reasons are discussed in details. Results of X-ray diffraction revealed that co-doped ZnO thin films have similar crystallization characteristic (0 0 2 preferential orientation) like that of un-doping. However, SEM measurement indicated that co-doped ZnO thin films have different surface morphology compared with un-doped ZnO thin films. p-type ZnO thin films with high hole concentration were obtained on glass (4.6 × 10¹⁸ cm⁻³) and n-type silicon (7.51 × 10¹⁹ cm⁻³), respectively.     

Highly oriented (1 0 0) ZnO thin films by spray pyrolysis

Undoped ZnO thin films have been deposited onto glass substrates by spray pyrolysis. The structural, electrical and optical properties were studied on thin films, prepared from precursor solutions with varying the ethanol concentrations. X-ray diffraction studies have shown polycrystalline nature of the films with a hexagonal wurtzite-type structure. The preferential orientation plane (1 0 0) of the ZnO thin film is found to be sensitive to ethanol concentration. The texture coefficient (TC) and grain size value have been calculated. Also ethanol concentration was found to have significant effect on sheet resistivity of the films.     

Temperature dependence of excitonic luminescence from nanocrystalline ZnO films

The properties of the excitonic luminescence for nanocrystalline ZnO thin films are investigated by using the dependence of excitonic photoluminescence (PL) spectra on temperature. The ZnO thin films are prepared by thermal oxidation of ZnS films prepared by low-pressure metalorganic chemical vapor deposition (LP-MOCVD) technique. The X-ray diffraction (XRD) indicates that ZnO thin films have a polycrystalline hexagonal wurtzite structure with a preferred (0 0 2) orientation. A strong ultraviolet (UV) emission peak at 3.26 eV is observed, while the deep-level emission band is barely observable at room temperature. The strength of the exciton-longitudinal-optical (LO) phonon coupling is deduced from the temperature dependence of the full-width at half-maximum (FWHM) of the fundamental excitonic peak, decrease in exciton-longitudinal-optical (LO) phonon coupling strength is due to the quantum confinement effect.