The effect of arsenic thermal diffusion on the morphology and photoluminescence properties of sub-micron ZnO rods

As-doped sub-micron ZnO rods were realized by a simple thermal diffusion process using a GaAs wafer as an arsenic resource. The surface of the sub-micron ZnO rods became rough and the morphology of As-doped sub-micron ZnO rods changed markedly with increasing diffusion temperature. From the results of energy-dispersive X-ray spectroscopy, X-ray diffraction and photoluminescence, arsenic elements were confirmed to be introduced into the sub-micron ZnO rods. The acceptor ionization energy was deduced to be about 110 meV based on the temperature-dependent PL spectra.     

Sputter deposition of ZnO thin films at high substrate temperatures

ZnO thin films have been deposited on GaN and ZnO substrates at substrate temperatures up to 750 °C by radio-frequency sputtering using ZnO ceramic targets in pure argon or in a mixture of argon and oxygen. By optimizing the sputter parameters, such as sputtering power, Ar/O₂ sputtering gas ratio and temperature of the substrates high quality films were obtained as judged from the X-ray rocking curve half width and luminescence line width. The crystallinity of the ZnO films increases with increasing substrate temperature. Yet there are distinct differences between films grown on GaN templates and on O- and Zn-polar ZnO substrates.     

Growth and characteristics of ZnO films on growth side of freestanding diamond substrate dependent on buffer layer thickness

We report the growth and properties of highly c-axis oriented ZnO films, by radio-frequency magnetron sputtering, on the growth side of freestanding chemical vapor deposited diamond film-substrate. Low-temperature ZnO buffer layer is required for the formation of continuous ZnO films. The morphology, structure, and optical properties of the ZnO films deposited are strongly dependent on the thickness of the buffer layer. The optimized thickness of ZnO buffer layer is about 10 nm to realize high-quality ZnO films having small compressive stress and high intensity ultraviolet emission. The ZnO/diamond (growth side) system is available for the applications in numerous fields, especially for high performance surface acoustic wave devices.     

Investigations on structural, optical and electrical properties of p-type ZnO nanorods using hydrothermal method

Undoped and doped ZnO nanorods were grown from an aqueous solution at low temperature (90 °C) on sapphire (100) substrates coated with ZnO thin film annealed in air at 550 °C for 1 h. X-ray diffraction results show that these nanorods have wurtzite type structure, and they are oriented in the c-axis direction. The optical properties are examined by room temperature micro photoluminescence and Raman scattering analysis which confirm that the nanorods exhibit good optical and electrical properties. A strong enhancement of multiple-phonon Raman scattering process with longitudinal optical phonon overtone up to fifth order was observed. It is found that the thin film coating of ZnO plays an important role in the c-axis oriented growth of undoped and doped ZnO nanorods due to good lattice match between the thin film and nanorods.     

Effect of annealing temperature and pH on morphology and optical property of highly dispersible ZnO nanoparticles

Highly dispersible zinc oxide nanoparticles were produced in large quantity via a simple solution method. The effect of temperature and pH impact on as-prepared ZnO nanoparticles with respect to the morphological and optical characteristics has been investigated. The average particle size of ZnO nanoparticles increased with increasing annealing temperature. A sharp UV band-edge emission was observed in as-prepared ZnO nanoparticles with negligibly less intense deep level emission. However, upon annealing at high temperature in air, UV band-edge emission disappears with an evolution of a broad deep level emission in photoluminescence spectra. Similarly, by adjusting the pH of reaction medium from 4 to pH = 8 using ammonium hydroxide solution, particle size gets bigger and bigger leads to red-shift in UV band-edge emission and an appearance of deep level emission peak. At pH = 8, well resolved sharp X-ray diffraction peaks were observed with lower FWHM values due to higher crystallite sizes.     

Growth ambient dependent electrical properties of lithium and nitrogen dual-doped ZnO films prepared by radio-frequency magnetron sputtering

Lithium (Li) and nitrogen (N) dual-doped ZnO films with wurtzite structure were prepared by radio-frequency magnetron sputtering ZnO target with Li₃N in growth ambient of pure Ar and the mixture of Ar and O₂, respectively, and then post annealing techniques. The film showed week p-type conductivity as the ambient was pure Ar, but stable p-type conductivity with a hole concentration of 3.46 × 10¹⁷ cm^− 3, Hall mobility of 5.27 cm²/Vs and resistivity of 3.43 Ω cm when the ambient is the mixture of Ar and O₂ with the molar ratio of 60:1. The stable p-type conductivity is due to substitution of Li for Zn (Li_Zn) and formation of complex of interstitial Li (Li_i) and substitutional N at O site, the former forms a Li_Zn acceptor, and the latter depresses compensation of Li_i donor for Li_Zn acceptor. The level of the Li_Zn acceptor is estimated to be 131.6 meV by using temperature-dependent photoluminescence spectrum measurement and Haynes rule. Mechanism about the effect of the ambient on the conductivity is discussed in the present work.     

Enhanced ferromagnetism in ZnO nanoribbons and clusters passivated with sulfur

Inspired by recent experimental results, the electronic and magnetic properties of sulfur-passivated ZnO clusters and zigzag nanoribbons have been studied using first principles calculations in the framework of the local spin density approximation. In the case of the ZnO nanoribbons, the sulfur atoms or thiol groups were attached in different ways to the zinc or oxygen atoms located at the edges, whereas in clusters, the sulfur atoms were set on the surface, mainly interacting with atoms with low-coordinate number. After an exhaustive atomic relaxation, we found that a magnetic moment emerges in zigzag nanoribbons both with and without sulfur-passivation on the edges. However, the magnitude of the magnetic moment is very sensitive to sulfur passivation. In particular, we found that when sulfur is attached to the zinc atoms in an alternating fashion along the ribbon edges, the magnetic moment is a maximum (1.4 μ_B/unit cell). In the case of clusters, we found that the Zn₁₅O₁₅ cluster exhibits a high spin moment of 5.5 μ_B when capped with sulfur atoms. Our calculations indicate that sulfur-passivating of ZnO nanosystems could be responsible for recently observed ferromagnetic responses. This article is published with open access at Springerlink.com     

Structural and luminescence properties of pure and Al-doped ZnO nanopowders

Pure and Al doped zinc oxide nanopowders have been synthesized by sol-gel route. This is a simple and inexpensive method permitting to obtain a very small grain size powders. Zinc acetate dehydrate was first dissolved in a mixture of 2-methoxyethanol and mono-ethanolamine (MEA) solution, were used as a solvent and stabilizer respectively and doped with a quantity of aluminum nitrate, varying from 0 to 10 mol%. The obtained gel is then calcinated in air at 500 °C. The samples are characterized by XRD, SEM and photoluminescence (PL) studies. The XRD results indicate that pure and Al-doped ZnO powders are solid solutions crystallizing in pure würtzite structure, and consisted of a mixture of nanoparticles with grain size between 23 and 36 nm. The grain size decreases strongly with increasing Al concentration and reaches its lowest value at 5 mol% Al. The PL spectra show that the most important establishment is that the powders show luminescence peaks from green to ultraviolet light, and thus can be used to manufacture transmitters using these emissions. The peaks connected to the blue luminescence are the most intense, and they are generated by transitions involving (Zn_i). The SEM images show a formation of pebbles with sizes decreasing with Al concentration and a morphology evaluating, qualitatively, from pebbles without cavities to highly porous ones.     

Fabrication of ZnO Nanoneedle/nanocolumn Composite Films and Annealing Induced Improvement in Their Microstructural and Photoluminescence Characteristics

ZnO nanoneedle/nanocolumn （NN/NC） composite films were grown via reactive electron beam evaporation （REBE） in the NH3/H2 gaseous mixture by using polycrystalline ZnO ceramic targets as source materials. The growth was performed at low substrate temperatures （450～500℃） without employing any metallic catalysts. As-prepared samples were then rapidly annealed in 02 ambient at a higher temperature （600℃）. Electron microscopic observations revealed the typical composite-structured morphologies of NN/NC/substrate of ZnO nanomaterials grown at 500℃. Such unique morphologies should render potential applications, for instance, as an efficient microwave absorption material utilized in the fabrication of concealed aerostat. In addition, X-ray diffraction and photoluminescence measurements showed remarkable improvement in crystal and optical qualities of ZnO NN/NC composite films after annealing.     

Nitrogen-doped p-type ZnO thin films and ZnO/ZnSe p-n heterojunctions grown on ZnSe substrate by radical beam gettering epitaxy

We investigate the p-type doping in ZnO prepared by the method of radical beam gettering epitaxy using NO gas as the oxygen source and nitrogen dopant. Secondary ion mass spectroscopy measurements demonstrate that N is incorporated into ZnO film in concentration of about 8 × 10¹⁸ cm^− 3. The hole concentration of the N-doped p-type ZnO films was between 1.4 × 10¹⁷ and 7.2 × 10¹⁷ cm^− 3, and the hole mobility was 0.9-1.2 cm²/Vs as demonstrated by Hall effect measurements. The emission peak of 3.312 eV is observed in the photoluminescence spectra at 4.2  of N-doped p-type ZnO films, probably neutral acceptor bound. The activation energy of the nitrogen acceptor was obtained by temperature-dependent Hall-effect measurement and equals about 145 meV. The p-n heterojunctions ZnO/ZnSe were grown on n-type ZnSe substrate and have a turn-on voltage of about 3.5 V.     

Comparative study of hydrothermal treatment and thermal annealing effects on the properties of electrodeposited micro-columnar ZnO thin films

We report a comparison of the role played by different sample treatments, namely, a low-temperature hydrothermal treatment by hot H₂O vapor in an autoclave versus thermal annealing in air on the properties of ZnO films grown by electrochemical deposition (ECD). Scanning electron microscopy studies reveal a homogeneous micro-columnar morphology and changes in the film surface for the two different treatments. It is found that post-growth hydrothermal treatments of ECD ZnO films at 150 °C under an aqueous environment enhance their structural and optical properties (photoluminescence, transmission, Raman spectra, etc.) similar to thermal annealing in air at higher temperatures (> 200 °C). The modifications of the structural and optical properties of ZnO samples after thermal annealing in air in the temperature range of 150-600 °C are discussed. The removal of chlorine from the films by the hydrothermal treatment was evidenced which could be the main reason for the improvement of the film quality. The observation of the enhanced photoluminescence peak at 380 nm demonstrates the superior properties of the hydrothermally treated ZnO films as compared to the films annealed in air ambient at the same or higher temperature. This post-growth hydrothermal treatment would be useful for the realization of high performance optoelectronic devices on flexible supports which might not withstand at high temperature annealing treatments.     

Influence of VI/II ratios on the growth of ZnO thin films on sapphire substrates by low temperature MOCVD

We investigated the structural, electrical, and optical properties of ZnO thin films grown at different VI/II ratios on sapphire substrates by metalorganic chemical vapor deposition. Transmission electron microscopy and X-ray diffraction revealed the epitaxial nature with a reduced dislocation density of the ZnO films grown at increased VI/II ratios. The carrier concentration of the films increased to 4.9 × 10¹⁸ cm^− 3 and their resistivity decreased to 1.4 × 10^− 1 Ω cm at a VI/II ratio of 513.4 μmol/min. The ZnO films also showed good optical transmittance (> 80%) in the visible and near-infrared wavelength regions. The room temperature PL revealed a strong band-edge emission with a weak deep level emission, suggesting the good crystalline quality of the ZnO films on the sapphire substrates. Furthermore, the intensity ratio of the band-edge emission to the deep-level emission (I_UV/I_Vis) increased with increasing VI/II ratio.     

Activation of phosphorous doping in high quality ZnO thin film grown on Yttria-stabilized zirconia (1 1 1) by thermal treatment

Phosphorous doped (P-doped) ZnO thin films are grown on c-sapphire and Yttria-stabilized zirconia (YSZ) (111) substrates by pulsed laser deposition. Post growth annealing is carried out to activate phosphorous to act as acceptor. The rocking curve of annealed P-doped ZnO films grown on YSZ (111) has full width at half maximum of 0.08°, more than two times narrower than that of the as-grown one. Neutral acceptor bound exciton (A⁰X) is observed from low temperature photoluminescence with estimated activation energy of 11.3 meV. Low carrier concentration of as-grown P-doped ZnO films indicated phosphorous doping creates acceptor states and/or reduced the oxygen vacancies. The carrier concentration of annealed samples is reduced by five order magnitudes from 3.21 × 10¹⁸ cm^− 3 to 1.21-8.19 × 10¹³ cm^− 3. At annealing temperature of 850 °C, the sample has the lowest carrier concentration and highest resistivity. This is an indication that the phosphorous in P-doped ZnO has been activated.     

Effect of precursor concentration on structural and optical properties of ZnO microrods by spray pyrolysis

ZnO films have been prepared by spray pyrolysis technique on glass substrate at 500 °C. Zinc Chloride has been used as a precursor. Effect of precursor concentration on structural and optical properties has been investigated. Homogenous films are obtained with precursor concentration rating between 0.1 M and 0.4 M. X-ray diffraction patterns show that ZnO films are polycrystalline with (002) plane as preferential orientation. Field emission scanning electron microscopy images show that ZnO films consist of microrods that their length increases with increasing precursor concentration and tallest microrods obtain by spraying precursor with 0.3 M concentration. The optical transmittance spectrum shows that transmittance increases with decreasing of the concentration and transmittance reaches to a maximum value of about 80% for the visible region ZnO films prepared with 0.1 M. Photoluminescence spectra at room temperature show an ultraviolet emission at 3.21 eV that can be related to band gap and two visible emissions at 2.88 eV and 2.38 eV.     

Influence of process variables on growth of ZnO nanowires by cathodic electrodeposition on zinc substrate

Influence of the deposition duration and electrolyte concentration on the structural and morphological features of the ZnO thin films, grown by cathodic electrodeposition on zinc substrate followed by annealing in air at 400 °C, have been investigated. The surface morphology of the as-synthesized films shows two distinct features, presence of ‘2-dimensional nanosheets’ on the area near the electrolyte-air interface and ‘granular’ nanostructures, below the interface region. However, upon annealing, the formation of ZnO nanowires, possessing length of several microns and diameter less than 20 nm, on the entire substrate is observed. The X-ray and selected area electron diffraction patterns clearly confirm the polycrystalline nature of the ZnO nanowires.     

Epitaxial growth of ZnO layers on (111) GaAs substrates by laser molecular beam epitaxy

ZnO layers were grown on (111) GaAs substrates by laser molecular epitaxy at substrate temperatures between 200 and 550 °C. X-ray diffraction analysis revealed that c-axis of ZnO epilayer with a wurtzite structure is perpendicular to the substrate surface. X-ray rocking curves and Raman spectroscopy showed that the crystal quality of ZnO epilayers depends on the substrate temperature during the growth. Strong near-band-edge emission in the UV region without any deep-level emissions was observed from the ZnO epilayers at room temperature. The results indicate that laser molecular beam epitaxy is a promising growth method for obtaining high-quality ZnO layers on (111) GaAs substrates.     

ZnO nanorods arrays with Ag nanoparticles on the (002) plane derived by liquid epitaxy growth and electrodeposition process

Well-aligned ZnO nanorods (NRs) arrays with Ag nanoparticles (NPs) on the (002) plane are obtained by combining a liquid epitaxy technique with an electrodeposition process. Cyclic voltammetry study is employed to understand the electrochemical behaviors of the electrodeposition system, and potentiostatic method is employed to deposit silver NPs on the ZnO NRs in the electrolyte with an Ag⁺ concentration of 1 mM. X-ray diffraction analysis is used to study the crystalline properties of the as-prepared samples, and energy dispersive X-ray is adopted to confirm the composition at the surface of the deposited samples. Results indicate only a small quantity of silver can be deposited on the surface of the samples. Effect of the deposition potential and time on the morphological properties of the resultant Ag NPs/ZnO NRs are investigated in detail. Scanning electron microscopy images and transmission electron microscopy images indicate that the Ag NPs deposited on the (002) plane of the ZnO NRs with a large dispersion in diameter can be obtained by a single potentiostatic deposition process, while dense Ag NPs with a much smaller diameter dispersion on the top of the ZnO NRs, most of which locate on the conical tip of the ZnO NRs, can be obtained by a two-potentiostatic deposition process, The mechanism of this deposition process is also suggested.     

Anomalous behavior in ZnMgO thin films deposited by sol-gel method

The magnesium doped zinc oxide is a promising optical material to enhance the luminescence for possible application in solid state lighting. Magnesium doped zinc oxide thin films (Zn_0.85Mg_0.15O) were deposited by sol-gel route on p-type silicon and annealed at different temperatures in oxygen environment for an hour. The doping of magnesium in zinc oxide was confirmed by X-Ray diffraction and the samples were found to have wurtzite crystal structure with (002) preferred orientation. The films were characterized by Hall-effect, atomic force microscopy, UV-VIS spectroscopy, photoluminescence (PL) and work function measurements. The different studies exhibited an anomalous behavior for the film annealed at 900 °C. The Hall effect, work function measurements and UV-VIS spectroscopy indicated that the resistivity, work function and optical band gap increased as a function of annealing temperature (from 300 °C to 700 °C) however these parameters were found to decrease for the films annealed above 700 °C. The particle size increased with the annealing but for the samples annealed at 900 °C, the shape of the grains changed and became elongated like fibers as observed by the atomic force microscopy. The PL measurements displayed the existence of oxygen vacancies defects for the samples annealed at and above 600 °C. The possible mechanism for this anomaly has been discussed in this work.     

Room temperature ferromagnetism in Fe-doped CeO2 thin films grown on LaAlO3 (001)

Ce_1 − xFe_xO_2 − δ/LaAlO₃(001) thin films (x = 0.01 and 0.03) have been prepared by pulsed laser deposition method and thoroughly characterized using X-ray diffraction (XRD), dc magnetization, near edge X-ray absorption fine structure (NEXAFS), and X-ray magnetic circular dichroism (XMCD). XRD data reveal a single-phase cubic structure with a strong crystallographic orientation along the (200) plane. Room temperature ferromagnetism is confirmed through isothermal hysteresis as well as temperature dependent magnetization measurements, which clearly show the ferromagnetic Curie temperature occurring at least above 350 K. The Fe L_3,2 edge NEXAFS spectra for both Fe-doped thin films exhibit mixed valent Fe²⁺/Fe³⁺ states, whereas Ce M_5,4 edge shows the 4+ state of Ce, throughout the doping. With the increase in Fe doping, Fe²⁺ state increases and a simultaneous decrease in magnetization value is also observed. The XMCD signal of both samples reveals the ferromagnetic ordering of substituted Fe ions in the ceria matrix. Our results indicate that ferromagnetism is intrinsic to the ceria system and is not due to any secondary magnetic impurity.     

Comparison of structural and photoluminescence properties of ZnO thin films grown by pulsed laser deposition and ultrasonic spray pyrolysis

ZnO thin films have been deposited by pulsed laser deposition (PLD) and ultrasonic spray pyrolysis (USP) method, respectively. X-ray diffraction and transmission electron microscopy characterizations indicate that ZnO film grown by PLD exhibits better crystallinity than that grown by USP. Photoluminescence spectra show that the near-band edge ultraviolet emission of film grown by PLD is narrower and shifts to higher energy, compared with that of film grown by USP. In the visible range, ZnO film grown by PLD exhibits four local level emission centered at 470 nm, 486 nm, 544 nm, and 613 nm, respectively, while the film grown by USP only presents a weak broad band emission centered at 502 nm. Hall measurement shows higher carrier density and lower hall mobility in ZnO film grown by PLD than that in film grown by USP. The higher density of intrinsic defects as well as higher crystallintiy is considered to account for the difference of photoluminescence in ZnO film grown by PLD with that in film grown by USP.