Modulation of field emission properties of vertically aligned ZnO nanorods with aspect ratio and number density

Vertically aligned ZnO nanorod arrays with different aspect ratios were synthesized by hybrid wet chemical route. Modulation of the field emission properties (FE) with aspect ratio of ZnO nanorods was examined. With the increase in the aspect ratio, the emission current density increases from 0.02 to 8 μA/cm² at 7.0 V/μm. Turn-on voltage was seen to decrease from 9.6 to 7 V/μm at a current density of 10 μA/cm² with the increase in aspect ratio in the ZnO films. The interrelation between the FE characteristics (emission thresholds, current density, surface uniformity, etc.) and microstructure of the ZnO nanostructure obtained from scanning electron microscopy (SEM) and atomic force microscopy (AFM) was discussed. Quality of the ZnO nanorods was also examined by using Raman spectroscopy and Fourier transformed infrared spectroscopy (FTIR). It was found that the observed enhancements of FE characteristics could mainly be attributed to the increase in aspect ratio and associated number density of ZnO nanorods.     

Enhanced field emission characteristics of zinc oxide mixed carbon nano-tubes films

A composite material of Zinc oxide and carbon nano-tubes (ZnO-CNTs) paste was synthesized by mixing multi-wall CNTs, ZnO nano-grains and organic vehicles. The microstructures and the morphologies of screen-printed films were characterized by field-emission scanning electron microscope. Results show that ZnO flakes geometrically matched with CNTs by filling into the interspaces of CNTs or directly covering upon CNTs. The field emission characteristics of films are found to be greatly effected by ZnO nano-grains. Especially, the turn-on electric field of ZnO-CNT film (1.17 V/μm) which is far lower than that of usual CNT films (1.70 V/μm). Furthermore, except that better emission stability is achieved, brightness and emission uniformity are notably enhanced as well. It can be speculated that the special microstructures of ZnO mixed CNT films dominate the enhanced electrical conductivity, thermal conductivity, and effective emitters.     

ZnO nanostructures with different morphologies and their field emission properties

Zinc oxide (ZnO) products with the morphologies of balls, nunchakus and belts have been synthesized from aqueous solutions by adjusting the reagent concentration and reaction time. The X-ray diffraction (XRD) peaks of the products were indexed to ZnO materials, but exhibited different relative intensities for the (0 0 2) diffraction peak. Field emission (FE) measurements showed that the turn-on and threshold field for the ZnO nanonunchakus were 3.01 ± 0.005 and 5.47 ± 0.005, 3.71 ± 0.005 and 6.43 ± 0.005 V/μm, respectively, for the ZnO nanobelts, revealing that the products have comparable FE properties with those of the reported ZnO nanowires and carbon nanotubes (CNTs).     

The effect of substrate surface roughness on ZnO nanostructures growth

The ZnO nanowires have been synthesized using vapor-liquid-solid (VLS) process on Au catalyst thin film deposited on different substrates including Si(1 0 0), epi-Si(1 0 0), quartz and alumina. The influence of surface roughness of different substrates and two different environments (Ar + H₂ and N₂) on formation of ZnO nanostructures was investigated. According to AFM observations, the degree of surface roughness of the different substrates is an important factor to form Au islands for growing ZnO nanostructures (nanowires and nanobelts) with different diameters and lengths. Si substrate (without epi-taxy layer) was found that is the best substrate among Si (with epi-taxy layer), alumina and quartz, for the growth of ZnO nanowires with the uniformly small diameter. Scanning electron microscopy (SEM) reveals that different nanostructures including nanobelts, nanowires and microplates have been synthesized depending on types of substrates and gas flow. Observation by transmission electron microscopy (TEM) reveals that the nanostructures are grown by VLS mechanism. The field emission properties of ZnO nanowires grown on the Si(1 0 0) substrate, in various vacuum gaps, were characterized in a UHV chamber at room temperature. Field emission (FE) characterization shows that the turn-on field and the field enhancement factor (β) decrease and increases, respectively, when the vacuum gap (d) increase from 100 to 300 μm. The turn-on emission field and the enhancement factor of ZnO nanowires are found 10 V/μm and 1183 at the vacuum gap of 300 μm.     

Photoluminescence and field emission properties of Sn-doped ZnO microrods

Sn-doped ZnO (SZO) microrods have been fabricated by a thermal evaporation method. Effect of Sn dopant on the microstructure, morphological and composition of as-prepared SZO microrods have been investigated by X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. The influence of the doping concentration on the morphological of the microrods has been investigated. Photoluminescence (PL) of these SZO microrods exhibits a weak ultraviolet (UV) emission peak at around 382 nm and the strong green emission peak at around 525 nm at room temperature. Field emission measurements demonstrate that the SZO possess good performance with a turn-on field of ∼1.94 V/μm and a threshold field of ∼3.23 V/μm, which have promising application as a competitive cathode material in FE microelectronic devices.     

Preparation and field emission properties of carbon nanotubes cold cathode using melting Ag nano-particles as binder

A new preparation process for carbon nanotubes (CNTs) cold cathode was studied through the replacement of traditional organic or inorganic binder with Ag nano-particles. This method has the advantages of low preparation temperature and fine electrical contact between CNTs paste and substrate. A mixture paste of CNTs, Ag nano-particles and other organic solvents was spreaded on Si substrate. By melting and connecting of Ag nano-particles after sintered 30 min at 250 °C, a flat CNTs films with good field emission properties was obtained. The measurements reveal that the turn on electric field and the threshold electric field of as-prepared CNTs cathode are 2.1 and 3.9 V/μm respectively and the field emission current density is up to 41 mA/cm² at an applied electric field of 4.7 V/μm.     

Synthesis of Cu-ZnO and C-ZnO nanoneedle arrays on zinc foil by low temperature oxidation route: Effect of buffer layers on growth, optical and field emission properties

Different densities of ZnO nanoneedle films have been prepared by pre-coated zinc foils with thin layer of copper and carbon followed by thermal oxidation at 400 °C in air. The X-ray diffraction patterns show well defined peaks, which could be indexed to the wurtzite hexagonal phase of ZnO. The scanning electron microscope images clearly reveal formation of ZnO needles on the entire substrate surface. The X-ray photoelectron spectroscopy studies indicate that Cu and C ions are incorporated into the ZnO lattice. Photoluminescence studies evaluate different emission bands originated from different defect mechanism. From the field emission studies, the threshold field, required to draw emission current density of ∼100 μA/cm², is observed to be 2.25 V/μm and 1.57 V/μm for annealed zinc foil pre-coated with copper and carbon, respectively. The annealed film with copper layer exhibits good emission current stability at the pre-set value of ∼100 μA over a duration of 4 h. The results show that buffer layer is an important factor to control the growth rate, resulting in different density of ZnO needles, which leads to field emission properties. This method may have potential in fabrication of electron sources for high current density applications.     

Efficient field emission from coiled carbon nano/microfiber on copper substrate by dc-PECVD

Crystalline coiled carbon nano/micro fibers in thin film form have been synthesized via direct current plasma enhanced chemical vapor deposition (PECVD) on copper substrates with acetylene as a carbon precursor at 10 mbar pressure and 750 °C substrate temperature. The as-prepared samples were characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). XRD pattern as well as selected area electron diffraction (SAED) pattern showed that the samples were crystalline in nature. SEM and HRTEM studies showed that as synthesized coiled carbon fibers are having average diameter ∼100 nm and are several micrometers in length. The as-prepared samples showed moderately good electron field emission properties with a turn-on field as low as 1.96 V/μm for an inter-electrode distance 220 μm. The variation of field emission properties with inter-electrode distance has been studied in detail. The field emission properties of the coiled carbon fibrous thin films are compared with that of crystalline multiwalled carbon nanotubes and other carbon nanostructures.     

Flame synthesis of carbon nanotubes for panel field emission lamp

Multi-walled carbon nanotubes (CNTs) were synthesized on the surfaces of Ni-alloy plated Fe-wires with the diameter of 2 mm using a conventional laboratory ethanol (C₂H₅OH) flame method at 560 °C. SEM showed that the product had bush-shaped micron-structures with diameters from 100 to 450 nm and lengths of over 1.0 μm. TEM revealed that the micron-structures were composed of multi-walled nanotube bundles with the diameters of about 50 nm. The test on the diode configuration field emission of the Fe-wire arrays was performed. The onset electric field was 2.95 V/μm and the emission current can reach 50 mA/cm² at an electric field of 9 V/μm. The average fluctuation of the emission current density was less than 7%. The result suggests that the field emission was uniform and the present technique was feasible to fabricate Panel Field Emission Lamp (PFEL) with arrays of carbon nanotubes. PFEL has the advantages of high luminescence as well as stability, and thus, it can be used to replace ordinary lights.     

An improved planar-gate triode with CNTs field emitters by electrophoretic deposition

An improved planar-gate triode with carbon nanotubes (CNTs) field emitters has been successfully fabricated by conventional photolithography, screen printing and electrophoretic deposition (EPD). In this structure, cathode electrodes and ITO arrays linked with gate electrodes were interdigitated and paralleled on the same plane although the gate electrodes and cathode electrodes were isolated by dielectric layer, a so-called improved planar-gate triode structure. An electrophoretic process was developed to selectively deposit CNTs field emitters onto cathode electrodes in the CNTs suspension by an applied voltage between the gate electrodes and cathode electrodes. The optical microscopy and FESEM image showed that the CNTs emitters with the uniform packing density were selectively defined onto the cathode electrodes. In addition, field emission characteristics of an improved planar-gate triode with CNTs field emitters were investigated. The experiment results indicated that the turn-on voltage of this triode structure at current density of 1 μA/cm² was approximately 55 V. The anode current and gate current came to 396 μA and 325 μA, at gate voltage and anode voltage of 100 V and 4000 V, respectively and at the anode-cathode spacing of 2000 μm. The emission image became brighter and the luminous image with dot matrix on the anode plate obviously increased with the increase of the gate voltage. Moreover, the emission current fluctuation was smaller than 5% for 11 h, which indicated that the improved planar-gate triode has a good field emission performance and long lifetime.     

Field emission characteristics of carbon nanotubes post-treated with high-density Ar plasma

The field emission characteristics of carbon nanotubes (CNTs) grown by thermal chemical vapor deposition (CVD) and subsequently surface treated by high-density Ar plasma in an inductively coupled plasma reactive ion etching (ICP-RIE) with the various plasma powers were measured. Results indicate that, after treated by Ar plasma with power between 250 and 500 W, the emission current density of the CNTs is enhanced by nearly two orders of magnitude (increased from 0.65 to 48 mA/cm²) as compared to that of the as-grown ones. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to investigate the structural features relevant to the modified field emission properties of CNTs. The SEM images of CNTs subjected to a 500 W Ar plasma treatment exhibit obvious damages to the CNTs. Nevertheless, the turn-on fields decreased from 3.6 to 2.2 V/μm, indicating a remarkable field emission enhancement. Our results further suggest that the primary effect of Ar plasma treatment might be to modify the geometrical structures of the local emission region in CNTs. In any case, the Ar plasma treatment appears to be an efficient method to enhance the site density for electron emission and, hence markedly improving the electric characteristics of the CNTs.     

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.     

Surface morphology and optical properties of ZnO epilayers grown on Si(1 1 1) by metal organic chemical vapor deposition

Heteroepitaxial ZnO epilayers were grown on Si(1 1 1) substrates using a vertical geometry atmospheric pressure metal organic chemical vapor deposition (AP-MOCVD) system. The growth temperature was varied from 550 °C to 650 °C in steps of 25 °C. The ZnO growth rate and surface morphology were strong functions of the growth temperature and ranged from ∼0.16 μm/h to 1.36 μm/h. The surface morphology of the ZnO films changed from granular to sharp tips as the growth temperature increased. The effect of buffer thickness was also examined, and was found to have a strong effect on the optical properties of the ZnO. An optimized growth condition for ZnO epilayers was found at 625 °C, producing a FWHM in the room temperature photoluminescence (PL) spectrum of 4.5 nm and a preferred growth orientation along the (0 0 2) direction.Transmission electron microscopy images and selected area diffraction patterns showed excellent crystalline quality of both the buffer and ZnO overlayer. When non-optimized growth temperatures were employed, post-growth annealing was found to greatly enhance the ratio of band-edge to deep level emission.     

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 of zinc oxide nanosheet thin films and their improved field emission and photoluminescence properties by annealing processing

ZnO nanosheet thin films have been synthesized through a solvothermal route. These obtained nanosheets disperse quasi-vertically and homogenously on the copper substrates and range in thickness from 80 nm to 250 nm. The as-grown nanosheet thin films were then annealed in the oxygen-presented atmosphere. Field emission plots indicate that the value of turn-on field is reduced from 2.86 V/μm to 1.52 V/μm and the corresponding value of threshold field decreases from 7.19 V/μm to 4.45 V/μm after annealing processing. Room temperature photoluminescence spectrum from the sample annealed at 850 °C in almost pure oxygen atmosphere shows only UV emission and a blue shift while the visible light band is unobservable compared with those of the other two samples, indicating that the crystalline quality of the obtained zinc oxide nanosheet thin films is greatly improved through annealing treatment. This solution approach combined with annealing treatment can, therefore, be regarded as a convenient route to fabricate high-quality crystalline ZnO nanomaterials.     

Fabrication and properties of film-under-gate field emission arrays with SnO2 emitters for flat lamp

The film-under-gate field emission arrays (FEAs) have been fabricated on the glass substrates by conventional photolithography, anodic oxidation and lift-off method. SnO₂ emitters were deposited on the cathode electrodes of under-gate triode by screen printing. The image of film-under-gate field emission arrays with SnO₂ emitters was measured by the optical microscopy and field emission scanning electron microscopy (FESEM). The electric field distributions and electron trajectories of film-under-gate triode were simulated in the same anode voltage and different gate voltage by ANSYS. I-V characteristics of film-under-gate triode with SnO₂ emitters were investigated. It indicated that the SnO₂ emitters by screen printing uniformly distributed on the surface of cathode electrodes. The maximum anode current in this triode structure could come to 385 μA and the highest lightness was approximately 270 cd/m² as the gate and anode voltage was 140 V and 2000 V, respectively, at the anode-cathode spacing of 1100 μm. Moreover, the emission current fluctuation was less than 5% for 8 h. It showed that the fabricated device has a good stability of field emission performance and long lifetime, which may lead to practical applications for field emission electron source based on flat lamp for back light units (BLUs) in liquid crystal display (LCD).     

Enhanced field emission and patterned emitter device fabrication of metal-tetracyanoquinodimethane nanowires array

Ag(TCNQ) and Cu(TCNQ) nanowires were synthesized via vapor-transport reaction method at a low temperature of 100 °C. Field emission properties of the as-obtained nanowires on ITO glass substrates were studied. The turn-on electric fields of Ag(TCNQ) and Cu(TCNQ) nanowires were 9.7 and 7.6 V/μm (with emission current of 10 μA/cm²), respectively. The turn-on electric fields of Ag(TCNQ) and Cu(TCNQ) nanowires decreased to 6 and 2.2 V/μm, and the emission current densities increased by two orders at a field of 8 V/μm with a homogeneous-like metal (e.g. Cu for Cu(TCNQ)) buffer layer to the substrate. The improved field emission is due to the better conduct in the nanowires/substrate interface and higher internal conductance of the nanowires. The patterned field emission cathode was then fabricated by localized growing M-TCNQ nanowires onto mask-deposited metal film buffer layer. The emission luminance was measured to be 810 cd/m² at a field of 8.5 V/μm.     

Electrochemical synthesis of Cu/ZnO nanocomposite films and their efficient field emission behaviour

The Cu/ZnO nanocomposite films have been synthesized by cathodic electrodeposition and characterized using X-ray diffractometer (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), photoluminescence (PL) and field emission microscope (FEM). The XRD pattern shows a set of well defined diffraction peaks, which could be indexed to the wurtzite hexagonal phase of ZnO. In addition, characteristic diffraction peaks corresponding to Cu and Zn are also observed. The SEM image shows formation of two-dimensional (2D) hexagonal sheets randomly distributed and aligned almost normal to the substrate. Uniformly distributed small clusters of Cu nanoparticles possessing average diameter of ∼25 nm, as revealed from the TEM image, are seen to be present on these 2D ZnO sheets. The selected area electron diffraction (SAED) image confirms the nanocrystalline nature of the Cu particles. From the field emission studies, carried out at the base pressure of ∼1 × 10⁻⁸ mbar, the turn-on field required for an emission current density of 0.1 μA/cm² is found to be 1.56 V/μm and emission current density of ∼100 μA/cm² has been drawn at an applied field of 3.12 V/μm. The Cu/ZnO nanocomposite film exhibits good emission current stability at the pre-set value of ∼10 μA over a duration of 5 h. The simplicity of the synthesis route coupled with the better emission properties propose the electrochemically synthesized Cu/ZnO nanocomposite film emitter as a promising electron source for high current density applications.     

Field emission property of copper nitride thin film deposited by reactive magnetron sputtering

Copper nitride (Cu₃N) thin film was deposited on silicon (Si) substrate by reactive magnetron sputtering method. X-ray diffraction measurement showed that the film was composed of Cu₃N crystallites with anti-ReO₃ structure and exhibited preferential orientation of [1 0 0] direction. The field emission (FE) result showed that Cu₃N film had a turn-on electric field of about 3 V/μm at a current density of 1 μA/cm² and a current density of 700 μA/cm² was obtained at the electric field of 24 V/μm. The emission mechanism inferred by Fowler-Nordheim (FN) plot is shown as following: thermal electron emission at low field region and tunneling electron emission at high field region.     

Superhydrophobic surfaces based on dandelion-like ZnO microspheres

This study presents a simple method to fabricate superhydrophobic surface based on ZnO nanoneedles. ZnO nanoneedles had been constructed on zinc layers by immersing in an aqueous NH₄OH solution at 80 °C. The ZnO films were characterized by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy. The ZnO films exhibited excellent superhydrophilicity (contact angle for water was 0°), while they changed wettability to superhydrophobicity with a water contact angle greater than 150° after further chemical modification with n-dodecanoic acid. The procedure reported here only needs readily available reagents and laboratory equipments, which can be applied to various substrates of any size and shape.