Low-macroscopic field emission from silicon-incorporated diamond-like carbon film synthesized by dc PECVD

Silicon-incorporated diamond-like carbon (Si-DLC) films were deposited via dc plasma-enhanced chemical vapor deposition (PECVD), on glass and alumina substrates at a substrate temperature 300 °C. The precursor gas used was acetylene and for Si incorporation, tetraethyl orthosilicate dissolved in methanol was used. Si atomic percentage in the films was varied from 0% to 19.3% as measured from energy-dispersive X-ray analysis (EDX). The binding energies of C 1s, Si 2s and Si 2p were determined from X-ray photoelectron spectroscopic studies. We have observed low-macroscopic field electron emission from Si-DLC thin films deposited on glass substrates. The emission properties have been studied for a fixed anode-sample separation of 80 μm for different Si atomic percentages in the films. The turn-on field was also found to vary from 16.19 to 3.61 V/μm for a fixed anode-sample separation of 80 μm with a variation of silicon atomic percentage in the films 0% to 19.3%. The turn-on field and approximate work function are calculated and we have tried to explain the emission mechanism there from. It was found that the turn-on field and effective emission barrier were reduced by Si incorporation than undoped DLC.     

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.     

Enhanced field emission from ZnO nanopencils by using pyramidal Si(1 0 0) substrates

Zinc oxide nanopencil arrays were synthesized on pyramidal Si(1 0 0) substrates via a simple thermal evaporation method. Their field emission properties have been investigated: the turn-on electric field (at the current density of 10 μA/cm²) was about 3.8 V/μm, and the threshold electric field (at the current density of 1 mA/cm²) was 5.8 V/μm. Compared with similar structures grown on flat Si substrates, which were made as references, the pyramidal Si-based ZnO nanopencil arrays appeared to be superior in field emission performance, thus the importance of the non-flat substrates has been accentuated. The pyramidal Si substrates could not only suppress the field screening effect but also improve the field enhancement effect during the field emission process. These findings indicated that using non-flat substrates is an efficient strategy to improve the field emission properties.     

Controlled growth and field emission properties of zinc oxide nanopyramid arrays

Single-crystalline, pyramidal zinc oxide nanorods have been synthesized in a large quantity on p-Si substrate via catalyst-free thermal chemical vapor deposition at low temperature. SEM investigations showed that the nanorods were vertically aligned on the substrate, with diameters ranging from 60 to 80 nm and lengths about 1.5 μm. A self-catalysis VLS growth mechanism was proposed for the formation of the ZnO nanorods. The field emission properties of the ZnO nanopyramid arrays were investigated. A turn-on field about 3.8 V/μm was obtained at a current density of 10 μA/cm², and the field emission data was analyzed by applying the Fowler-Nordheim theory. The stability of emission current density under a high voltage was also tested, indicating that the ZnO nanostructures are promising for an application such as field emission sources.     

Field emission properties of polymer-converted carbon films by heat treatment

Carbon films were prepared on single crystal silicon substrates by heat-treatment of a polymer-poly(phenylcarbyne) at 800 °C in Ar atmosphere. The heat-treatment caused the change of the polymer into carbon film, which exhibited good field emission properties. Low turn-on emission field of 4.3 V/μm (at 0.1 μA/cm²) and high emission current density of 250 μA/cm² (at 10 V/μm) were observed for the polymer-converted carbon films. This behavior was demonstrated to be mainly related to the microstructure of the carbon films, which consisted of fine carbon nanoparticles with high sp² bonding. The carbon films, which can be deposited simply with large areas, are promising for practical applications in field emission display.     

Field emission from patterned SnO2 nanostructures

A simple and reliable method has been developed for synthesizing finely patterned tin dioxide (SnO₂) nanostructure arrays on silicon substrates. A patterned Au catalyst film was prepared on the silicon wafer by radio frequency (RF) magnetron sputtering and photolithographic patterning processes. The patterned SnO₂ nanostructures arrays, a unit area is of ∼500 μm × 200 μm, were synthesized via vapor phase transport method. The surface morphology and composition of the as-synthesized SnO₂ nanostructures were characterized by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The mechanism of formation of SnO₂ nanostructures was also discussed. The measurement of field emission (FE) revealed that the as-synthesized SnO₂ nanorods, nanowires and nanoparticles arrays have a lower turn-on field of 2.6, 3.2 and 3.9 V/μm, respectively, at the current density of 0.1 μA/cm². This approach must have a wide variety of applications such as fabrications of micro-optical components and micropatterned oxide thin films used in FE-based flat panel displays, sensor arrays and so on.     

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.     

Synthesis of amorphous carbon nanowalls by DC-PECVD on different substrates and study of its field emission properties

Amorphous carbon thin films with quasi vertical nanowall-like morphologies have been synthesized via direct current plasma enhanced chemical vapor deposition on both copper and silicon substrates with acetylene as a carbon precursor. The deposition temperature and pressure were maintained at 750 °C and 5 mbar respectively. The morphology of the as-prepared samples has been investigated with the help of a field emission scanning electron microscope and an atomic force microscope, both revealing nanowall-like morphologies with thicknesses of the walls ∼6-15 nm. The as-prepared carbon nanowalls showed good field electron emission with a turn-on field as low as 1.39 V/μm. The effect of inter-electrode distance on the field electron emission has also been studied in detail.     

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.     

Field electron emission from HfNxOy thin films deposited by direct current sputtering

HfN_xO_y thin films were deposited on Si substrates by direct current sputtering at room temperature. The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). SEM indicates that the film is composed of nanoparticles. AFM indicates that there are no sharp protrusions on the surface of the film. XRD pattern shows that the films are amorphous. The field electron emission properties of the film were also characterized. The turn-on electric field is about 14 V/μm at the current density of 10 μA/cm², and at the electric field of 24 V/μm, the current density is up to 1 mA/cm². The field electron emission mechanism of the HfN_xO_y thin film is also discussed.     

Ion-induced secondary electron emission from ZnS thin films deposited by closed-spaced sublimation

ZnS thin films were deposited on soda lime glass and aluminum substrates by close-spaced sublimation technique. The change in composition, structural and optical properties of the films was investigated as a function of the substrate temperature. The deposited films were stoichiometric and crystalline in nature having cubic structure oriented only along (1 1 1) plane. The energy band gap of the films deposited at the substrate temperature of 150, 250 and 350 °C was 3.52, 3.58 and 3.63 eV respectively. These films were then bombarded with 2-10 keV energy pulsed Ar⁺ beam and their electron yield was determined from impinging ion and emitted electron currents. The electron yield of ZnS films was much high as compared to the metals. The electron yield of ZnS films increased with energy of the incident ion and got saturated at about 8 keV. The most important result of this study was that the electron yield of ZnS films having same composition was different. Monte Carlo simulations performed to interpret these experimental findings showed that the dissimilar electron yields of ZnS films is due to the combined effect of energy band gap, surface barrier potential and density of the films.     

Field emission behavior of cuboid zinc oxide nanorods on zinc-filled porous silicon

Single-crystalline zinc oxide (ZnO) nanorods with cuboid morphology have been prepared on the zinc-filled porous silicon substrate using a vapor phase transport method. Field-emission measurements showed that the turn-on field and threshold field of the cuboid ZnO nanorods film were about 3.2 and 8.2 V/μm respectively. From the emitter surface, a homogeneous emission image was observed with emission site density (ESD) of ∼10⁴ cm⁻². The better emission uniformity and the high ESD may be attributed to a large number of ZnO nanocrystallites as emitter on the surface of the nanorod end contributing to emission.     

Growth of carbon nanofibers on aligned zinc oxide nanorods and their field emission properties

Carbon nanofibers were grown by electrodeposition technique onto aligned zinc oxide (ZnO) nanorods deposited by hybrid wet chemical route on glass substrates. X-ray diffraction traces indicated very strong peak for reflections from (0 0 2) planes of ZnO. The Raman spectra were dominated by the presence of G band at about 1597 cm⁻¹ corresponding to the E_2g tangential stretching mode of an ordered graphitic structure with sp² hybridization and a D band at about 1350 cm⁻¹ originating from disordered carbon. Fourier transformed infrared studies indicated the presence of a distinct characteristic absorption peak at ∼511 cm⁻¹ for Zn-O stretching mode. Photoluminescence spectra indicated band edge luminescence of ZnO at ∼3.146 eV along with a low intensity peak at ∼0.877 eV arising out of carbon nanofibers. Field emission properties of these films and their dependence on the CNF coverage on ZnO nanorods are reported here. The average field enhancement factor as determined from the slope of the FN plot was found to vary between 1 × 10³ and 3 × 10³. Both the values of turn-on field and threshold field for CNF/ZnO were lower than pure ZnO nanorods.     

A simple growth route towards ZnO thin films and nanorods

Highly orientated ZnO thin films and the self-organized ZnO nanorods can be easily prepared by a simple chemical vapor deposition method using zinc acetate as a source material at the growth temperature of 180 and 320 °C, respectively. The ZnO thin films deposited on Si (100) substrate have good crystallite quality with the thickness of 490 nm after annealing in oxygen at 800 °C. The ZnO nanorods grown along the [0001] direction have average diameter of 40 nm with length up to 700 nm. The growth mechanism for ZnO nanorods can be explained by a vapor-solid (VS) mechanism. Photoluminescence (PL) properties of ZnO thin films and self-organized nanorods were investigated. The luminescence mechanism for green band emission was attributed to oxygen vacancies and the surface states related to oxygen vacancy played a significant role in PL spectra of ZnO nanorods.     

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.     

Luminescence and structure of ZnO-ZnS thin films prepared by oxidation of ZnS films in air and water vapor

Effect of water vapor quantity at oxidation of undoped ZnS films on structural and luminescent properties of the obtained films was investigated. The films were deposited onto glass substrates by electron beam evaporation. ZnO-ZnS layers were prepared by thermal oxidization of ZnS films at 600 °C in dry or wet atmospheres. The films were characterized by X-ray diffraction, atomic force microscopy and photoluminescence spectroscopy. As-deposited ZnS films were sphalerite crystal structure. The “dry annealing” led to the ZnS phase transition from sphalerite to wurtzite structure and from ZnS to ZnO for a small fraction of the film. After the “wet annealing” the amount of ZnO phase with wurtzite structure growing along the 〈0 0 0 2〉 direction varied from 25% to 95% in dependence on the water vapor quantity. Photoluminescent spectrum at room temperature exhibits green emission with maximum at 2.4 eV. A strong influence of the water vapor on shape and intensity of the emission was observed. Photoluminescent spectra at 22 K consisted of two bands—high-energy band at 2.1-2.4 eV and low energy band at 1.7-1.8 eV. Location and intensity ratio depended on the preparation conditions.     

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.     

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.     

Growth of carbon nanotubes on stainless steel substrates by DC-PECVD

We report on the fabrication of carbon nanotubes (CNTs) on Ni-coated stainless steel (SUS) substrates by using dc plasma enhanced chemical vapor deposition. The synthesized CNTs have the diameter of about 30 nm and the length of about 1.2 μm. To verify the effects of SUS substrates on the growth of CNTs, CNTs had also been grown on Ni-coated Si substrates. CNTs grown on the SUS substrates were more uniform compared with those grown on the Si substrates. Field emission properties of the CNT films were measured in the diode configuration, and the turn-on electric field of 3.87 V/μm and field enhancement factor β of about 1737 were obtained from the synthesized CNTs at the gap of 500 μm between the SUS substrate and the anode. These results have not only clarified the effects of the substrate on the growth of CNTs, but also shown the potential of CNTs in field emission applications, especially CNT-based cold-cathode X-ray tubes.     

Characterization and luminescent properties of SiO2:ZnS:Mn and ZnS:Mn nanophosphors synthesized by a sol-gel method

ZnS and SiO₂-ZnS nanophosphors, with or without different concentration of Mn²⁺ activator ions, were synthesized by using a sol-gel method. Dried gels were annealed at 600 °C for 2 h. Structure, morphology and particle sizes of the samples were determined by using X-ray diffraction (XRD), highresolution transmission electron microscopy (HRTEM) and field emission scanning electron microscopy (FESEM). The diffraction peaks associated with the zincblende and the wurtzite structures of ZnS were detected from as prepared ZnS powders and additional diffraction peaks associated with ZnO were detected from the annealed powders. The particle sizes of the ZnS powders were shown to increase from 3 to 50 nm when the powders were annealed at 600 °C. An UV-Vis spectrophotometer and a 325 nm He-Cd laser were used to investigate luminescent properties of the samples in air at room temperature. The bandgap of ZnS nanoparticles estimated from the UV-Vis data was 4.1 eV. Enhanced orange photoluminescence (PL) associated with ⁴T₁→⁶A₁ transitions of Mn²⁺ was observed from as prepared ZnS:Mn²⁺and SiO₂-ZnS:Mn²⁺ powders at 600 nm when the concentration of Mn²⁺ was varied from 2-20 mol%. This emission was suppressed when the powders were annealed at 600 °C resulting in two emission peaks at 450 and 560 nm, which can be ascribed to defects emission in SiO₂ and ZnO respectively. The mechanism of light emission from Mn²⁺, the effect of varying the concentration on the PL intensity, and the effect of annealing are discussed.