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.     

ZnO nanowall networks grown on DiMPLA pre‐patterned thin gold films

ZnO nanowall networks grown by a high pressure pulsed laser deposition (PLD) technique on a pre‐patterned thin gold film are presented. The thin gold film on a c ‐plane oriented sapphire substrate was structured with diffraction mask projection laser ablation (DiMPLA). It is shown that only areas processed with the laser patterning technique reveal homogeneous growth of ZnO nanowall networks. Photoluminescence measurements prove the higher material quality of the pre‐patterned regions compared to the untreated ones. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of crystalline quality on the ultraviolet emission and electrical properties of the ZnO films deposited by magnetron sputtering

The ZnO films were deposited on c-plane sapphire, Si (0 0 1) and MgAl₂O₄ (1 1 1) substrates in pure Ar ambient at different substrate temperatures ranging from 400 to 750 °C by radio frequency magnetron sputtering. X-ray diffraction, photoluminescence and Hall measurements were used to evaluate the growth temperature and the substrate effects on the properties of ZnO films. The results show that the crystalline quality of the ZnO films improves with increasing the temperature up to 600 °C, the crystallinity of the films is degraded as the growth temperature increasing further, and the ZnO film with the best crystalline quality is obtained on sapphire at 600 °C. The intensity of the photoluminescence and the electrical properties strongly depend on the crystalline quality of the ZnO films. The ZnO films with the better crystallinity have the stronger ultraviolet emission, the higher mobility and the lower residual carrier concentration. The effects of crystallinity on light emission and electrical properties, and the possible origin of the n-type conductivity of the undoped ZnO films are also discussed.     

Room temperature electroluminescence from ZnO/Si heterojunction devices grown by metal-organic chemical vapor deposition

Heterojunction light-emitting diodes with ZnO/Si structure were fabricated on both high-resistivity (p) and low-resistivity (p⁺) Si substrates by metal-organic chemical vapor deposition technology. Fairly good rectifications were observed from the current-voltage curves of both heterojunctions. Ultraviolet (UV) and blue-white electroluminescence (EL) from ZnO layer were observed only from ZnO/p⁺-Si heterojunction under forward bias at room temperature (RT), while strong infrared (IR) EL emissions from Si substrates were detected from both ZnO/p-Si and ZnO/p⁺-Si heterojunctions. The UV and IR EL mechanisms have been explained by energy band structures. The realization of RT EL in UV-visible and IR region on Si substrate has great applicable potential for Si-based optoelectronic integrated circuits.     

Synchrotron radiation assistant MOCVD deposition of ZnO films on Si substrate

The growth of ZnO film on Si(1 0 0) substrate has been studied with synchrotron radiation (SR) assisted MOCVD method. The diethylzinc (DEZn) and CO₂ are used as source materials, while Nitrogen is employed as a carrier gas for DEZn. With the assistance of SR the ZnO film can be deposited even at room temperature. XRD, SEM and photoluminescence (PL) studies show that the crystal quality of ZnO films grown with the assistance of SR is higher than that of those without SR assistance. The growth mechanism of ZnO film with the SR assistant MOCVD system is primarily discussed.     

Properties of ZnO thin films grown on Si substrates in vacuum and oxygen ambient by pulsed laser deposition

Epitaxial ZnO thin films have been synthesized directly on Si(1 1 1) substrates by pulsed laser deposition (PLD) in vacuum. The reflection high-energy electron diffraction (RHEED) indicates that streaky patterns can be clearly observed from the ZnO epilayers prepared at 600 and 650 °C, revealing a two-dimensional (2D) growth mode. While the ZnO thin film deposited in oxygen ambient shows ring RHEED pattern. There is a compressive in-plane stress existing in the ZnO epitaxial film, but a tensile one in the polycrystalline film. Compared with the ZnO epilayer, the ZnO polycrystalline film shows more intense ultraviolet emission (UVE) with a small full width at half maximum (FWHM) of 89 meV. It is suggested that the atomically flat epilayers may be powerfully used as transitive stratums to grow high-quality ZnO films suitable for the fabrication of optoelectronic devices.     

ZnO thin films on Si(1 1 1) grown by pulsed laser deposition from metallic Zn target

ZnO thin films with highly c-axis orientation have been fabricated on p-type Si(1 1 1) substrates at 400 °C by pulsed laser deposition (PLD) from a metallic Zn target with oxygen pressures between 0.1 and 0.7 mbar. Experimental results indicate that the films deposited at 0.3 and 0.5 mbar have better crystalline and optical quality and flatter surfaces than the films prepared at other pressures. The full width at half maximum (FWHM) of (0 0 0 2) diffraction peak decreases remarkably from 0.46 to 0.19° with increasing annealing temperature for the film prepared at 0.3 mbar. In photoluminescence (PL) spectra at room temperature, the annealed film at 700 °C exhibits a smaller ultraviolet (UV) peak FWHM of 108 meV than the as-grown film (119 meV). However, an enhanced deep-level emission is observed. Possible origins to above results are discussed.     

Alumina capped ZnO quantum dots multilayer grown by pulsed laser deposition

To extend the applicability of ZnO, with the bulk band gap of about 3.3 eV, into deep UV region, we have grown a multilayer of alumina capped ZnO quantum dots of mean in-plane sizes in the range of ∼1.8-3.6 nm at room temperature using alternate Pulsed Laser Deposition. Size dependent blue shift of the band gap of these dots up to ∼4.5 eV is observed in the optical absorbance spectra. The observed blue shift can be understood using the effective mass approximation in weak and strong confinement regimes.     

Properties of ZnO thin films grown on Si substrates by photo-assisted MOCVD

ZnO thin films were grown on (1 0 0) p-Si substrates by Photo-assisted Metal Organic Chemical Vapor Deposition (PA-MOCVD) using diethylzinc (DEZn) and O₂ as source materials and tungsten-halogen lamp as a light source. The effects of tungsten-halogen lamp irradiation on the surface morphology, structural and optical properties of the deposited ZnO films have been investigated by means of atomic force microscope (AFM), X-ray diffraction and photoluminescence (PL) spectra measurements. Compared with the samples without irradiation, the several characteristics of ZnO films with irradiation are improved, including an improvement in the crystallinity of c-axis orientation, an increase in the grain size and an improvement in optical quality of ZnO films. These results indicated that light irradiation played an important role in the growth of ZnO films by PA-MOCVD.     

Laser–MBE growth of high-quality ZnO thin films on Al2O3(0001) and SiO2/Si(100) using the third harmonics of a Nd:YAG laser

High-quality ZnO thin films were grown on single-crystalline Al₂O₃(0001) and amorphous SiO₂/Si(100) substrates at 400–640 °C using laser molecular beam epitaxy. For film growth, the third harmonics of a pulsed Nd:YAG laser were illuminated on a ZnO target. The ZnO films were epitaxially grown on Al₂O₃(0001) with the narrow X-ray diffraction full width at half maximum (FWHM) of 0.04° and the films on SiO₂/Si(100) exhibited a preferred c-axis orientation. Furthermore, the films exhibited excellent optical properties in photoluminescence (PL) measurements with very sharp excitonic and weak deep-level emission peaks. At 15 K, PL FWHM values of the films grown on Al₂O₃(0001) and SiO₂/Si(100) were 3 and 18 meV, respectively. Received: 8 May 2001 / Accepted: 18 September 2001 / Published online: 20 December 2001     

Influence of annealing atmosphere on ZnO thin films grown by MOCVD

ZnO films were deposited on c-plane sapphire substrates by metal-organic chemical vapor deposition (MOCVD). Annealing treatments for as-deposited samples were performed in different atmosphere under various pressures in the same chamber just after growth. The effect of annealing atmosphere on the electrical, structural, and optical properties of the deposited films has been investigated by means of X-ray diffraction (XRD), atomic force microscope (AFM), Hall effect, and optical absorption measurements. The results indicated that the electrical and structural properties of the films were highly influenced by annealing atmosphere, which was more pronounced for the films annealed in oxygen ambient. The most significant improvements for structural and electrical properties were obtained for the film annealed in oxygen under the pressure of 60 Pa. Under the optimum annealing condition, the lowest resistivity of 0.28 Ω cm and the highest mobility of 19.6 cm² v⁻¹ s⁻¹ were obtained. Meanwhile, the absorbance spectra turned steeper and the optical band gap red shifted back to the single-crystal value.     

Particulate assisted growth of ZnO nanorods and microrods by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on the gallium nitride (GaN) and sapphire (Al₂O₃) substrates by pulsed laser deposition (PLD) without using any metal catalyst. The experiment was carried out at three different laser wavelengths of Nd:YAG laser (λ = 1064 nm, λ = 532 nm) and KrF excimer laser (λ = 248 nm). The ZnO films grown at λ = 532 nm revealed the presence of ZnO nanorods and microrods. The diameter of the rods varies from 250 nm to 2 μm and the length varies between 9 and 22 μm. The scanning electron microscopy (SEM) images of the rods revealed the absence of frozen balls at the tip of the ZnO rods. The growth of ZnO rods has been explained by vapor-solid (V-S) mechanism. The origin of growth of ZnO rods has been attributed to the ejection of micrometric and sub-micrometric sized particulates from the ZnO target. The ZnO films grown at λ = 1064 nm and λ = 248 nm do not show the rod like morphology. X-ray photoelectron spectroscopy (XPS) has not shown the presence of any impurity except zinc and oxygen.     

Porous ZnO nanobelts evolved from layered basic zinc acetate nanobelts

Novel porous ZnO nanobelts were successfully synthesized by heating layered basic zinc acetate (LBZA) nanobelts in the air. The precursor of LBZA nanobelts consisted of a lamellar structure with two interlayer distances of 1.325 and 0.99 nm were prepared using a low-temperature, solution-based method. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and infrared spectroscopy are used to characterize the as-products. PL measurements show that the porous ZnO nanobelts have strong ultraviolet emission properties at 380 nm, while no defect-related visible emission is detected. The good performance for photoluminescence emission makes the porous ZnO nanobelts promising candidates for photonic and electronic device applications.     

Synthesis and optical properties of Co-doped ZnO nanofibers prepared by electrospinning

In this work, Co-doped ZnO nanofibers have been fabricated successfully by an electrospinning technique. The as-prepared nanofibers are characterized by themogravimetric analysis (TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), Raman spectra and photoluminescence spectroscopy (PL). Results have showed that a wurtzite ZnO nanofibers were obtained and the PL spectrum showed a red-shift by 10 nm due to narrowing of the ZnO band gap (∼3.29 eV) as a result of Co doping. Meanwhile, Raman scattering spectra exhibited an unusual peak at 540 cm⁻¹.     

Well-aligned ZnO nanocolumns grown by reactive electron beam evaporation

We report on the reactive electron beam evaporative growth of well-aligned ZnO nanocolumns on Si (001) wafers in the environment of NH₃/H₂ gas mixture by using polycrystalline ZnO ceramic target as source material. The growth was carried out at low temperatures (400-450 °C) without employing any metal catalysts. Field emission scanning electron microscopy (FESEM) revealed that nanocolumns with uniform distributions in their diameters, lengths, and densities were grown vertically from the substrates and terminated by smooth hexagonal (0001) facets with no terrace-like steps emerged, which should render potential applications such as inherent resonance cavities in fabricating ultraviolet-laser arrays. X-ray diffraction measurements revealed that ZnO nanocolumns were highly c-axis oriented, which is well consistent with the FESEM observations. More importantly, photoluminescence investigations of the nanocolumns demonstrated the strong excitonic emission and extremely weak deep level emission, indicating the high crystalloid and optical quality of the nanocolumns.     

Formation of Al-N co-doped p-ZnO/n-Si (1 0 0) heterojunction structure by RF co-sputtering technique

Al-N co-doped ZnO (ZnO:Al-N) thin films were grown on n-Si (1 0 0) substrate by RF co-sputtering technique. As-grown ZnO:Al-N film exhibited n-type conductivity whereas on annealing in Ar ambient the conduction of ZnO:Al-N film changes to p-type, typically at 600 °C the high hole concentration of ZnO:Al-N co-doped film was found to be 2.86 × 10¹⁹ cm⁻³ and a low resistivity of 1.85 × 10⁻² Ω-cm. The current-voltage characteristics of the obtained p-ZnO:Al-N/n-Si heterojunction showed good diode like rectifying behavior. Room temperature photoluminescence spectra of annealed co-doped films revealed a dominant peak at 3.24 eV.     

Photoluminescence properties of nitrogen-doped ZnO films deposited on ZnO single crystal substrates by the plasma-assisted reactive evaporation method

Photoluminescence (PL) spectra of nitrogen-doped ZnO films (ZnO:N films) grown epitaxially on n-type ZnO single crystal substrates by using the plasma-assisted reactive evaporation method were measured at 5 K. In PL spectra, free exciton emission at about 3.375 eV was very strong and emissions at 3.334 and 3.31 eV were observed. These two emissions are discussed in this paper. The nitrogen concentration in ZnO:N films measured by secondary ion mass spectroscopy was 10^19-20 cm⁻³. Current-voltage characteristics of the junction consisting of an n-type ZnO single crystal substrate and ZnO:N film showed good rectification. Also, ultraviolet radiation and visible light were emitted from this junction under a forward bias at room temperature. It is therefore thought that ZnO:N films have good crystallinity and that doped nitrogen atoms play a role as acceptors in ZnO:N films to form a good pn junction. From these phenomena and the excitation intensity dependency of PL spectra, emissions at 3.334 and 3.31 eV were assigned to neutral acceptor-bound exciton (A⁰X) emission and a donor-acceptor pair (DAP) emission due to doped nitrogen, respectively.     

Effect of Post-Annealing on Microstructural and Electrical Properties of N^＋Ion-Implanted into ZnO：In Films

We fabricate p-type conductive ZnO thin films on quartz glass substrates by codoping of In-N using radio frequency magnetron sputtering technique together with the direct implantation of acceptor dopants （nitrogen）. The effects of thermal annealing on the structure and electrical properties of the ZnO films are investigated by an x-ray diffractometer （XRD） and a Hall measurement system. It is found that the best p-type ZnO film subjected to annealed exhibits excellent electrical properties with a hole concentration of 1.22 × 10^18 cm^-3, a Hall mobility of 2.19 cm^2 V^-1 s^- 1, and a low resistivity of about 2.33 Ωcm, indicating that the presence of In may facilitates the incorporation of N into ZnO thin films.     

Investigation of p-type behavior in Ag-doped ZnO thin films by E-beam evaporation

Ag-doped ZnO (ZnO:Ag) thin films were grown on glass substrates by E-beam evaporation technique. The structural, electrical and optical properties of the films were investigated as a function of annealing temperature. The films were subjected to post annealing at different temperatures in the range of 350-650 °C in an air ambient. All the as grown and annealed films at temperature of 350 °C showed p-type conduction. The films lost p-type conduction after post annealing treatment temperature of above 350 °C, suggesting a narrow post annealing temperature window for the fabrication of p-type ZnO:Ag films. ZnO:Ag film annealed at 350 °C revealed lowest resistivity of 7.25 × 10⁻² Ω cm with hole concentration and mobility of 5.09 × 10¹⁹ cm⁻³ and 1.69 cm²/V s, respectively. Observation of a free-to-neutral-acceptor (e,A^o) and donor-acceptor-pair (DAP) emissions in the low temperature photoluminescence measurement confirms p-type conduction in the ZnO:Ag films.     

Photoluminescence characteristics of ZnO doped with Eu powders

In this work, we have investigated the photoluminescence spectra of europium-doped zinc oxide crystallites prepared by a vibrating milled solid-state reaction method. X-ray diffraction, scanning electron microscopy, luminescence spectra and time-resolved spectra analysis were used to characterize the synthetic ZnO:Eu³⁺ powders. XRD results of the powders showed a typical wurtzite hexagonal crystal structure. A second phase occurred at 5 mol% Eu₂O₃-doped ZnO. The ⁵D₀-⁷F₁ (590 nm) and ⁵D₀-⁷F₂ (609 nm) emission characteristics of Eu³⁺ appeared after quenching with more than 1.5 mol% Eu₂O₃ doping. The Commission Internationale d’Eclairage (CIE) chromaticity coordinates of a ZnO:Eu³⁺ host excited at λ_ex=467 nm revealed a red-shift phenomenon with increase in Eu³⁺ ion doping. The lifetime of the Eu³⁺ ion decreased as the doping concentration was increased from 1.5 to 10 mol%, and the time-resolved ⁵D₀→⁷F₂ transition presents a single-exponential decay behavior.