Field electron emission improvement of ZnO nanorod arrays after Ar plasma treatment

Vertically well-aligned single crystal ZnO nanorod arrays were synthesized and enhanced field electron emission was achieved after radio-frequency (rf) Ar plasma treatment. With Ar plasma treatment for 30 min, flat tops of the as-grown ZnO nanorods have been etched into sharp tips without damaging ZnO nanorod geometrical morphologies and crystallinity. After the Ar ion bombardment, the emission current density increases from 2 to 20 μA cm⁻² at 9.0 V μm⁻¹ with a decrease in turn-on voltage from 7.1 to 4.8 V μm⁻¹ at a current density of 1 μA cm⁻², which demonstrates that the field emission of the as-grown ZnO nanorods has been efficiently enhanced. The scanning electron microscopy (SEM) results, in conjunction with the results of transmission electron microscopy (TEM), Raman spectroscopy and photoluminescence observation, are used to investigate the mechanisms of the field emission enhancement. It is believed that the enhancements can be mainly attributed to the sharpening of rod tops, and the decrease of electrostatic screening effect.     

The structural and optical properties of ZnO nanorod arrays

High quality vertical-aligned ZnO nanorod arrays were synthesized by a simple vapor transport process on Si (111) substrate at a low temperature of 520 °C. Field-emission scanning electron microscopy (FESEM) showed the nanorods have a uniform length of about 1 μm with diameters of 40-120 nm. X-ray diffraction (XRD) analysis confirmed that the nanorods are c-axis orientated. Selected area electron diffraction (SAED) analysis demonstrated the individual nanorod is single crystal. Photoluminescence (PL) measurements were adopted to analyze the optical properties of the nanorods both a strong UV emission and a weak deep-level emission were observed. The optical properties of the samples were also tested after annealing in oxygen atmosphere under different temperatures, deep-level related emission was found disappeared at 600 °C. The dependence of the optical properties on the annealing temperatures was also discussed.     

Synthesis and red-shifted photoluminescence of single-crystalline ZnO nanowires

Local-oriented single-crystalline ZnO nanowires have been synthesized in large scale by a simple microemulsion method in the presence of sulfonate-polystyrene (S-PS) and dodecyl benzene sulfonic acid sodium salt (DBS). The as-prepared product is characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), infrared (IR) spectra and photoluminescence (PL) spectrum. The nanowires exhibit a local congregation and preferentially grow along the [0 0 2] facet. FT-IR spectrum indicates that S-PS is adsorbed on the surface of ZnO nanowires. The PL spectrum shows evidently red-shifted ultraviolet (UV) emission.     

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.     

Fabrication and electrical characterization of ZnO rod arrays/CuSCN heterojunctions

ZnO rod arrays/CuSCN heterojunctions are fabricated by depositing ZnO rod arrays films using two-step chemical bath deposition (CBD) and CuSCN thin films using successive ionic layer adsorption and reaction (SILAR) on ITO substrate successively. The structures and morphologies of ZnO films and CuSCN films, analyzed by X-ray diffraction (XRD) spectroscopy and metallurgical microscope, show that ZnO films are hexagonal wurtzite structure and consisted of vertical polycrystalline rods with diameter of 1 μm, CuSCN films are β-phase structure and consisted of elongated grains with length of 3 μm. Current–voltage (I–V) measurements of ZnO/CuSCN heterojunctions show good diode characteristics with rectification ratio about 48.3 at 3 V. The forward conduction is, respectively, determined by carrier recombination in the space charge region, defect-assisted tunneling and exponential distribution trap-assisted space charge limited current mechanism with the increase of forward voltage. Also, a band diagram of ZnO/CuSCN heterojunctions has been proposed to explain the transport mechanism.     

Temperature-dependent growth mode of W-doped ZnO nanostructures

We report on the effects of glass substrate temperature on the crystal structure and morphology of tungsten (W)-doped ZnO nanostructures synthesized by pulsed-laser deposition. X-ray diffraction analysis data shows that the W-doped ZnO thin films exhibit a strongly preferred orientation along a c-axis (0 0 0 L) plane, while scanning electron and atomic force microscopes reveal that well-aligned W-doped ZnO nanorods with unique shape were directly and successfully synthesized at substrate temperature of 550 °C and 600 °C without any underlying catalyst or template. Possible growth mechanism of these nanorods is suggested and discussed.     

Investigation of electrical and ammonia sensing characteristics of Schottky barrier diode based on a single ultra-long ZnO nanorod

Novel ultra-long ZnO nanorods, with lengths about 0.5-1.5 mm and diameters ranging from 100 to 1000 nm, in mass production have been synthesized via the vapor-phase transport method with CuO catalyst at 900 °C. Rectifying Schottky barrier diodes have been fabricated by aligning a single ultra-long ZnO nanorod across paired Ag electrodes. The resulting current-voltage (I-V) characteristics of the SBD exhibit a clear rectifying behavior. The ideality factor of the diode is about 4.6, and the threshold voltage is about 0.54 V at room temperature (300 K). At the same time the detailed I-V characteristics have been investigated in the temperature range 423-523 K. In addition, after exposure of the Schottky diodes to NH₃, the forward and reverse currents increase rapidly, indicating a high sensitivity to NH₃ gas.     

Photoluminescence and Raman analysis of novel ZnO tetrapod and multipod nanostructures

Novel ZnO tetrapod and multipod nanostructures were successfully synthesized in bulk quantity through thermal evaporation method. The morphologies and structures of the ZnO nanostructures were characterized by scanning electron microscopy, X-ray diffraction and transmission electron microscopy. The results revealed that the ZnO nanostructures consisted of tetrapods and multipods with tower-like legs. The ZnO nanostructures were of high purity and were well crystallized with wurtzite structure. The preferred growth direction of legs was found to be the [0 0 0 1] direction. Possible growth mechanisms were proposed for the formation of the ZnO nanostructures. Room temperature photoluminescence (PL) spectra showed that the as-synthesized ZnO nanostructures had a strong green emission centered at 495 nm and a weak ultraviolet emission at 383 nm. Raman spectroscopy was also adopted to explore the structural quality of the ZnO nanostructures.     

Nanointegration of ZnO with Si and SiC

The study is dedicated to some aspects of the controlled heteroepitaxial growth of nanoscaled ZnO structures and an investigation of their general and dimension mediated properties. ZnO nanostructures were synthesized by optimized MOCVD process via two growth approaches: (i) catalyst free self-organized growth of ZnO on Si substrates and (ii) ZnO heteroepitaxy on p-type hexagonal 4H-SiC substrates. The SiC substrate was prepared by sublimation epitaxy and served as a template for the ZnO epitaxial growth. The epitaxial growth of n-ZnO on p-SiC resulted in a regular matrix of well-faceted hexagonally shaped ZnO single crystals. The achievement of ZnO integration with Si encompasses controlled growth of vertically oriented nanosized ZnO pillars. The grown structures were characterized by transmission electron microscopy and microphotoluminescence. Low concentration of native defects due to a stoichiometry balance, advanced optical emission, (excitonic type near-band-edge emission and negligible defect related luminescence) and continuous interfaces (epitaxial relationship ZnO_[0 0 0 1]/SiC_[0 0 0 1]) are evidenced. The ZnO nanopillars were further probed as field emitters: the grown structures exhibits advanced field emission properties, which are explained in term of dimensionality and spatial uniformity of the nanopillars. The present results contribute to understanding and resolving growth and device related issues of ZnO as a functional nanostructured material.     

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.     

Synthesis, field emission and glucose-sensing characteristics of nanostructural ZnO on free-standing carbon nanotubes films

Free-standing multiwall carbon nanotubes (MWNTs) films were coated, using chemical vapor deposition method, with a thin layer of nanostructural ZnO. The morphology and crystal structure of the as-grown products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman scattering analyses. Field emission (FE) results demonstrated that the needle-like and spherical ZnO-MWNTs composite structure films possessed good performance with a turn-on field of 1.3, 2.2 V μm⁻¹ and a threshold field of 2.6, 4.5 V μm⁻¹, respectively. The glucose-sensing characteristic has also been studied. The multi-layer electrode (PDDA/GOx/ZnO/MWNTs) exhibited significant electrocatalysis to the oxidation and reduction of H₂O₂ than the PDDA/GOx/MWNTs electrode, which provided wide potential applications in clinical, environmental, and food analysis.     

Growth and electrical properties of ZnO nanorod arrays prepared by chemical spray pyrolysis

Chemical spray pyrolysis was applied to grow ZnO nanorod arrays from zinc chloride solutions with pH=2 and 5 on glass/ITO substrate at 480 and 550 °C. The obtained structures were characterized by their morphological, electrical and PL properties. According to SEM, deposition of acidic solutions retards coalescence of the growing crystals. The charge carrier density in ZnO nanorods was determined from the C-V characteristics of ZnO/Hg Schottky barrier. Carrier densities ∼10¹⁵ cm⁻³ and slightly above 10¹⁶ cm⁻³ were recorded for ZnO deposited at 550 and 480 °C, respectively. According to PL studies, intense UV-emission is characteristic of ZnO independent of growth temperature, the concentration of oxygen vacancy related defects is lower in ZnO nanorods deposited at 550 °C. Solution pH has no influence on carrier density and PL properties.     

Two-dimensional zinc oxide nanostructure

Transparent two-dimensional ultralong and ultrabroad single crystal zinc oxide (ZnO) nanosheets were directly synthesized by a simple solid vapor deposition process under lead oxide (PbO) atmosphere. The nanosheets are well grown single crystals with thickness of about 50-70 nm, breadth of 50-100 μm and length of 4-6 mm. The growth mode of the ultrabroad nanosheets displays a unique aspect that (001) planes form the narrowest facets of the nanosheets, which is completely different from other belt-like nanostructures of ZnO. Control experiments show that PbO play an important role in the vapor-solid growth process of ZnO nanosheets.     

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.     

Effects of buffer layer annealing temperature on the structural and optical properties of hydrothermal grown ZnO

ZnO was deposited on bare Si(1 0 0), as-deposited, and annealed ZnO/Si(1 0 0) substrates by hydrothermal synthesis. The effects of a ZnO buffer layer and its thermal annealing on the properties of the ZnO deposited by hydrothermal synthesis were studied. The grain size and root mean square (RMS) roughness values of the ZnO buffer layer increased after thermal annealing of the buffer layer. The effect of buffer layer annealing temperature on the structural and optical properties was investigated by photoluminescence, X-ray diffraction, atomic force microscopy, and scanning electron microscopy. Hydrothermal grown ZnO deposited on ZnO/Si(1 0 0) annealed at 750 °C with the concentration of 0.3 M exhibits the best structural and optical properties.     

Fabrication and optical properties of 3D composite photonic crystals of core-shell structures

Three-dimensional (3D) composite colloidal photonic crystals with SiO₂ core and ZnO shell were fabricated on borosilicate glass (BSG) substrate by a two-stage deposition method. Scanning electron microscopy (SEM) measurements show that both the pre-deposited SiO₂ and SiO₂/ZnO core-shell structures are oriented with their (1 1 1) axes parallel to the substrates. Optical measurement reveals that the periodic arrays exhibit a photonic band gap in the (1 1 1) direction. The optical properties of SiO₂/ZnO core-shell structures strongly depend on the size dispersions of colloidal spheres and the intrinsic defects in the sample.     

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.     

Atomic layer deposition coating of ZnO shell for GaN-ZnO core-sheath heteronanowires

We have synthesized GaN-core/ZnO-shell nanowires and investigated effects of the ZnO coating. The X-ray diffraction pattern showed that as-synthesized samples are composed of GaN and ZnO. Transmission electron microscopy indicated that the deposited ZnO shell layer is poly-crystalline. The photoluminescence (PL) spectrum of GaN has been changed by the ZnO coating, where emission bands centered at roughly 1.9 eV, 2.5 eV, and 3.3 eV were newly added to the emissions from core GaN nanowires. We found that overall PL intensity has been significantly increased by coating the ZnO shell layers.     

Twinned tabour-like ZnO: Surfactant-, template-free synthesis and gas sensing behaviors

The twinned tabour-like ZnO microstructures have been successfully synthesized via a solvothermal method without the assistant of any additive and template. The as-prepared products are characterized by X-ray diffraction, field emission scanning electron microscope, and high-resolution transmission electron microscope. The ZnO microcrystals grow symmetrically, and are wurtzite structure. The tabour, with a diameter of about 8.5 μm, grows along the c axis. The time-dependent morphology evolution of the ZnO microcrystal presents every single ZnO tabour is composed by many single crystal units. A possible formation mechanism of these complex hierarchical structures is investigated by adjusting the reaction time. In addition, the twinned ZnO tabours exhibit excellent ethanol-sensing properties at 250 °C. The highest response is 6.4-20 ppm ethanol. The response of the sensor rapidly increases with the increasing concentration of ethanol, until the ethanol reaching 200 ppm. The response of the sensor to 200 ppm ethanol is about 24.64 with the response time of 3 s.     

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.