Characterization of bulk ZnO single crystal grown by a CVT method - art. no. 68410F

Hall effect, photoluminescence spectroscopy (PL), mass spectroscopy and X-ray diffraction have been used to study bulk ZnO single crystal grown by a closed seeded chemical vapor transport method. Enhancement of n-type electrical conduction and increase of nitrogen concentration are observed of the ZnO samples after high temperature annealing. The results suggest that vacancy is dominant native defect in the ZnO material. These phenomena are explained by a generation of shallow donor defect and suppression of deep level defects in ZnO after the annealing.

Native deep level defects in ZnO single crystal grown by CVT method - art. no. 68410I

Hall effect, photoluminescence (PL), infrared absorption, deep level transient spectroscopy (DLTS), and Raman scattering have been used to study property and defects of ZnO single crystal grown by a chemical vapor transport method (CVT). As-grown ZnO is N type with free electron density Of 10(16)-10(17)cm(-3). It has a slight increase after 900 degrees C annealing in oxygen ambient. The DLTS measurement revealed four deep level defects with energy at 0.30eV, 0.50eV, 0.68eV and 0.90eV in the as-grown ZnO sample, respectively. After the high temperature annealing, only the 0.5eV defect survive and has a concentration increase. PL results of the as-grown and annealed ZnO indicate that the well-known green emission disappear after the annealing. The result suggests a correlation between the 0.68eV defect and the green PL peak. Results of P-doped ZnO were also compared with the undoped ZnO sample. The nature of the defects and their influence on the material property have been discussed.

Growth of ZnO single crystal by chemical vapor transport method

ZnO crystals were grown by CVT method in closed quartz tube under seeded condition. Carbon was used as a transport agent to enhance the chemical transport of ZnO in the growth process. ZnO single crystals were grown by using GaN/sapphire and GaN/Si wafer as seeds. The property and crystal quality of the ZnO single crystals was studied by photoluminescence spectroscopy and X-ray diffraction technique.

Donor defect in P-diffused bulk ZnO single crystal

A high concentration of shallow donor defect is formed in P-diffused ZnO single crystals. X-ray photoelectron spectroscopy analysis indicates that P atom occupy different lattice site at different diffusion temperature. Nature of the donor defect has been discussed.

Synthetic strategy of porous ZnO and CdS nanostructures doped ferroelectric liquid crystal and its optical behavior

A simple and scalable chemical approach has been proposed for the generation of 1-dimensional nanostructures of two most important inorganic materials such as zinc oxide and cadmium sulfide. By controlling the growth habit of the nanostructures with manipulated reaction conditions, the diameter and uniformity of the nanowires/nanorods were tailored. We studied extensively optical behavior and structural growth of CdS NWs and ZnO NRs doped ferroelectric liquid crystal Felix-017/100. Due to doping band gap has been changed and several blue shifts occurred in photoluminescence spectra because of nanoconfinement effect and mobility of charges.

Tailoring the visible photoluminescence of mass-produced ZnO nanowires

We have grown defect-rich ZnO nanowires on a large scale by the vapour phase reaction method without using any metal catalyst and vacuum system. The defects, including zinc vacancies, oxygen interstitials and oxygen antisites, are related to the excess of oxygen in ZnO nanowires and are controllable. The nanowires having high excess of oxygen exhibit a brown-colour photoluminescence, due to the dominant emission band composed by violet, blue and green emissions. Those having more balanced Zn and O show a dominant green emission, giving rise to a green colour under UV light illumination. By O2-annealing treatment the violet luminescence after the band-edge emission UV peak can be enhanced for as-grown nanowires. However, the green emission shows different changing trends under O2-annealing treatment, associated with the excess of oxygen in the nanowires.

Facet-controlled Self-assembly of ZnO Nanocrystals by Non-Hydrolytic Aminolysis and their Photodegradation Activities

We report a method for controlling the exposed facets and hence the dimensionality and shape of ZnO nanocrystals using a non-hydrolytic aminolysis synthesis route. The effects of changes to reaction conditions on ZnO formation were investigated and possible self-assembly mechanisms proposed. The crystal facet growth and hence morphologies of the ZnO nanocrystals were controlled by varying reaction temperature and the reactant ratio. Four distinct ZnO nanocrystal types were produced (nanocones, nanobullets, nanorods and nanoplates). The relative photocatalytic activities of the exposed facets of these ZnO nanostructures were also examined, which showed the activities obviously depended on the reactivity of exposed crystal facets in the order: {1011}>>{0001}, {1010}.

Experimental and theoretical investigation of ligand effects on the synthesis of ZnO nanoparticles

ZnO nanoparticles with highly controllable particle sizes(less than 10 nm) were synthesized using organic capping ligands in Zn(Ac)2 ethanolic solution. The molecular structure of the ligands was found to have significant influence on the particle size. The multi-functional molecule tris(hydroxymethyl)-aminomethane (THMA) favoured smaller particle distributions compared with ligands possessing long hydrocarbon chains that are more frequently employed. The adsorption of capping ligands on ZnnOn crystal nuclei (where n = 4 or 18 molecular clusters of(0001) ZnO surfaces) was modelled by ab initio methods at the density functional theory (DFT) level. For the molecules examined, chemisorption proceeded via the formation of Zn...O, Zn...N, or Zn...S chemical bonds between the ligands and active Zn2+ sites on ZnO surfaces. The DFT results indicated that THMA binds more strongly to the ZnO surface than other ligands, suggesting that this molecule is very effective at stabilizing ZnO nanoparticle surfaces. This study, therefore, provides new insight into the correlation between the molecular structure of capping ligands and the morphology of metal oxide nanostructures formed in their presence.

Hybrid light-emitting diodes based on ZnO nanowires

ZnO is a wide band-gap semiconductor that has several desirable properties for optoelectronic devices. With its large exciton binding energy of ~60 meV, ZnO is a promising candidate for high stability, room-temperature luminescent and lasing devices [1]. Ultraviolet light-emitting diodes (LEDs) based on ZnO homojunctions had been reported [2,3], while preparing stable p-type ZnO is still a challenge. An alternative way is to use other p-type semiconductors, ether inorganic or organic, to form heterojunctions with the naturally n-type ZnO. The crystal structure of wurtzite ZnO can be described as Zn and O atomic layers alternately stacked along the [0001] direction. Because of the fastest growth rate over the polar (0001) facet, ZnO crystals tend to grow into one-dimensional structures, such as nanowires and nanobelts. Since the first report of ZnO nanobelts in 2001 [4], ZnO nanostructures have been particularly studied for their potential applications in nano-sized devices. Various growth methods have been developed for growing ZnO nanostructures, such as chemical vapor deposition (CVD), Metal-organic CVD (MOCVD), aqueous growth and electrodeposition [5]. Based on the successful synthesis of ZnO nanowires/nanorods, various types of hybrid light-emitting diodes (LEDs) were made. Inorganic p-type semiconductors, such as GaN, Si and SiC, have been used as substrates to grown ZnO nanorods/nanowires for making LEDs. GaN is an ideal material that matches ZnO not only in the crystal structure but also in the energy band levels. However, to prepare Mg-doped p-GaN films via epitaxial growth is still costly. In comparison, the organic semiconductors are inexpensive and have many options to select, for a large variety of p-type polymer or small-molecule semiconductors are now commercially available. The organic semiconductor has the limitation of durability and environmental stability. Many polymer semiconductors are susceptible to damage by humidity or mere exposure to oxygen in the air. Also the carrier mobilities of polymer semiconductors are generally lower than the inorganic semiconductors. However, the combination of polymer semiconductors and ZnO nanostructures opens the way for making flexible LEDs. There are few reports on the hybrid LEDs based on ZnO/polymer heterojunctions, some of them showed the characteristic UV electroluminescence (EL) of ZnO. This chapter reports recent progress of the hybrid LEDs based on ZnO nanowires and other inorganic/organic semiconductors. We provide an overview of the ZnO-nanowire-based hybrid LEDs from the perspectives of the device configuration, growth methods of ZnO nanowires and the selection of p-type semiconductors. Also the device performances and remaining issues are presented.

Temperature-dependent growth mechanisms of low-dimensional ZnO nanostructures

One-dimensional ZnO nanostructures were successfully synthesized on single-crystal silicon substrates via a simple thermal evaporation and vapour-phase transport method under different process temperatures from 500 to 1000 °C. The detailed and in-depth analysis of the experimental results shows that the growth of ZnO nanostructures at process temperatures of 500, 800, and 1000 °C is governed by different growth mechanisms. At a low process temperature of 500 °C, the ZnO nanostructures feature flat and smooth tips, and their growth is primarily governed by the vapour-solid mechanism. At an intermediate process temperature of 800 °C, the ZnO nanostructures feature cone-shape tips, and their growth is primarily governed by the self-catalyzed and saturated vapour–liquid–solid mechanism. At a high process temperature of 1000 °C, the alloy tip appears on the front side of the ZnO nanostructures, and their growth is primarily governed by the common catalyst-assisted vapour–liquid–solid mechanism. It is also shown that the morphological, structural, optical, and compositional properties of the synthesized ZnO nanostructures are closely related to the process temperature. These results are highly relevant to the development of light-emitting diodes, chemical sensors, energy conversion devices, and other advanced applications.

p-type doping of ZnO by means of high-density inductively coupled plasmas

A custom-designed inductively coupled plasma assisted radio-frequency magnetron sputtering deposition system has been used to fabricate N-doped p-type ZnO (ZnO:N) thin films on glass substrates from a sintered ZnO target in a reactive Ar + N2 gas mixture. X-ray diffraction and scanning electron microscopy analyses show that the ZnO:N films feature a hexagonal crystal structure with a preferential (002) crystallographic orientation and grow as vertical columnar structures. Hall effect and X-ray photoelectron spectroscopy analyses show that N-doped ZnO thin films are p-type with a hole concentration of 3.32 × 1018 cm- 3 and mobility of 1.31 cm2 V- 1 s- 1. The current-voltage measurement of the two-layer structured ZnO p-n homojunction clearly reveals the rectifying ability of the p-n junction. The achievement of p-type ZnO:N thin films is attributed to the high dissociation ability of the high-density inductively coupled plasma source and effective plasma-surface interactions during the growth process.

Small gold nanoparticles as crystallization "catalysts": Effect of seed size and concentration on Au-ZnO hetero nanoparticles

This work reports the effect of seed nanoparticle size and concentration effects on heterogeneous crystal nucleation and growth in colloidal suspensions. We examined these effects in the Au nanoparticle-seeded growth of Au-ZnO hetero-nanocrystals under synthesis conditions that generate hexagonal, cone-shaped ZnO nanocrystals. It was observed that small (~ 4 nm) Au seed nanoparticles form one-to-one Au-ZnO hetero dimers and that Au nanoparticle seeds of this size can also act as crystallization ‘catalysts’ that readily promote the nucleation and growth of ZnO nanocrystals. Larger seed nanoparticles (~9 nm, ~ 11 nm) provided multiple, stable ZnO-nucleation sites, generating multi-crystalline hetero trimers, tetramers and oligomers.

Self Assembly and Electronic Structure of ZnO Nanocrystals

In this paper, we report the synthesis and self assembly of various sizes of ZnO nanocrystals. While the crystal structure and the quantum confinement of nanocrystals were mainly characterized using XRD and UV absorption spectra, the self assembly and long range ordering were studied using scanning tunneling microscopy after spin casting the nanocrystal film on the highly oriented pyrolytic graphite surface. We observe self assembly of these nanocrystals over large areas making them ideal candidates for various potential applications. Further, the electronic structure of the individual dots is obtained from the current-voltage characteristics of the dots using scanning tunneling spectroscopy and compared with the density of states obtained from the tight binding calculations. We observe an excellent agreement with the experimentally obtained local density of states and the theoretically calculated density of states.

Oxidation of methanol on the surfaces of model Cu/ZnO catalysts containing Cu1+ and Cu-0 species

Interaction of CH3OH with Cu clusters deposited on ZnO films grown on a Zn foil as well as on a ZnO(0001)Zn crystal, has been examined by X-ray photoelectron spectroscopy. On clean Cu clusters, reversible molecular adsorption or formation of CH3O is observed. However if the Cu clusters are pretreated with oxygen, both CH3O and HCOO- species are produced. Model Cu/ZnO catalyst surfaces, containing both Cu1+ and Cu-0 species, show interesting oxidation properties. On a Cu-0-rich catalyst surface, only CH3O species is formed on interaction with CH3OH. On a Cu1+-rich surface, however, HCOO- ion is the predominant species.