Rehybridization of the atomic orbitals and the field electron emission from nanostructured carbon

The field electron emission, structural features, and electronic properties of carbon films obtained by chemical vapor deposition were experimentally studied. It is shown that the field electron emission from the films composed of spatially oriented carbon nanotubes and platelike graphite nanocrystals is observed for the electric field strength lower by one to two orders of magnitude as compared to the values characteristic of the metal emitters. Experimental data reported for the first time are indicative of a local decrease in the electron work function in such carbon film materials as compared to that in graphite. A model of the emission center is proposed and a mechanism of the field electron emission from nanostructured carbon is described.     

Peculiarities of electron field emission from ZnO nanocrystals and nanostructured films

ZnO microcrystals and nanocrystals were grown on silicon substrates by condensation from vapour phase. Nanostructured ZnO films were deposited by plasma enhanced metal organic chemical vapour deposition (PEMOCVD). The parameters of field emission, namely form-factor β and work function , were calculated for ZnO structures by the help of the Fowler–Nordheim equation. The work functions from ZnO nanostructured films were evaluated by a comparison method. The density of emission current from ZnO nanostructures reaches 0.6 mA/cm² at electric force F=2.110⁵ V/cm. During repeatable measurements β changes from 5.810⁴ to 2.310⁶ cm⁻¹, indicating improvement of field emission. Obtained values of work functions were 3.7±0.37 eV and 2.9–3.2 eV for ZnO nanostructures and ZnO films respectively.     

Mechanism of field electron emission from carbon nanotubes

Field electron emission (FE) is a quantum tunneling process in which electrons are injected from materials (usually metals) into a vacuum under the influence of an applied electric field. In order to obtain usable electron current, the conventional way is to increase the local field at the surface of an emitter. For a plane metal emitter with a typical work function of 5 eV, an applied field of over 1 000 V/μm is needed to obtain a significant current. The high working field (and/or the voltage between the electrodes) has been the bottleneck for many applications of the FE technique. Since the 1960s, enormous effort has been devoted to reduce the working macroscopic field (voltage). A widely adopted idea is to sharpen the emitters to get a large surface field enhancement. The materials of emitters should have good electronic conductivity, high melting points, good chemical inertness, and high mechanical stiffness. Carbon nanotubes (CNTs) are built with such needed properties. As a quasi-one-dimensional material, the CNT is expected to have a large surface field enhancement factor. The experiments have proved the excellent FE performance of CNTs. The turn-on field (the macroscopic field for obtaining a density of 10 μA/cm²) of CNT based emitters can be as low as 1 V/μm. However, this turn-on field is too good to be explained by conventional theory. There are other observations, such as the non-linear Fowler-Nordheim plot and multi-peaks field emission energy distribution spectra, indicating that the field enhancement is not the only story in the FE of CNTs. Since the discovery of CNTs, people have employed more serious quantum mechanical methods, including the electronic band theory, tight-binding theory, scattering theory and density function theory, to investigate FE of CNTs. A few theoretical models have been developed at the same time. The multi-walled carbon nanotubes (MWCNTs) should be assembled with a sharp metal needle of nano-scale radius, for which the FE mechanism is more or less clear. Although MWCNTs are more common in present FE applications, the single-walled carbon nanotubes (SWCNTs) are more interesting in the theoretical point of view since the SWCNTs have unique atomic structures and electronic properties. It would be very interesting if people can predict the behavior of the well-defined SWCNTs quantitatively (for MWCNTs, this is currently impossible). The FE as a tunneling process is sensitive to the apex-vacuum potential barrier of CNTs. On the other hand, the barrier could be significantly altered by the redistribution of excessive charges in the micrometer long SWCNTs, which have only one layer of carbon atoms. Therefore, the conventional theories based upon the hypothesis of fixed potential (work function) would not be valid in this quasi-one-dimensional system. In this review, we shall focus on the mechanism that would be responsible for the superior field emission characteristics of CNTs. We shall introduce a multi-scale simulation algorithm that deals with the entire carbon nanotube as well as the substrate as a whole. The simulation for (5, 5) capped SWCNTs with lengths in the order of micrometers is given as an example. The results show that the field dependence of the apex-vacuum electron potential barrier of a long carbon nanotube is a more pronounced effect, besides the local field enhancement phenomenon.     

Light emission from carbon nanofilaments/nanotubes at field electron emission

The spatial distribution of light emission has been studied in planar field electron emitters with long and sparse carbon nanofilaments/nanotubes. The photographic recording of light emission of the emitting nanofilaments/nanotubes is shown to be efficient to determine the position of individual nanofilaments/ nanotubes in different emitter surface areas, as well as to highlight the nanofilaments/nanotube agglomerate distribution over the emitter surface, which mainly contributes to its emission.     

Ab initio study of field emission from graphitic ribbons

We have performed first-principles calculations on field emission (FE) from graphitic ribbons within the time-dependent density-functional theory. An important finding is that dangling bond states localized at clean edges are major contributors to FE current. H termination makes the FE current small due to the disappearance of the dangling-bond states. FE is found not to occur from the edge state of a H-terminated zigzag ribbon even when the state is at the Fermi level. The results of the FE current from graphitic ribbons give approximately 1 microA for maximum of FE current from a circular edge of graphitic sheets with approximately 1 nm diameter of an open-ended multiwalled carbon nanotube under a high electric field of approximately 1 V/A.     

Morphology and temperature-dependent electron field emission from vertically aligned carbon nanofibers

Effects of temperature and the aspect ratio on the electron field emission properties of vertically aligned carbon nanofibers in thin-film form were studied in detail. Vertically aligned carbon nanofibers have been synthesized on silicon substrates via a direct current plasma enhanced chemical vapor deposition technique. Surface morphologies of the films were studied by an atomic force microscope. It was found that the length of the nanofibers increased and the diameter decreased as the thickness of the Ni catalyst film decreased. The threshold field for the electron field emission was found to be in the range from 4.3 to 5.4 V/μm for carbon nanofibers having different aspect ratios. The threshold field for carbon nanofibers having diameter ∼ 200 nm and aspect ratio ∼7.5 was found to decrease from 4.8 to 2.1 V/μm when the temperature was raised from 27 to 350 °C. This dependence was due to the change in work function of the nanofibers with temperature. The field enhancement factor, the current density and the effective work function were calculated and used to explain the emission mechanism. PACS 81.07.De; 61.10.-i; 79.70.+q; 73.30.+y     

Influence of cesium atoms on the field electron emission from multi-walled carbon nanotubes

It has been shown that the deposition of cesium atoms on multi-wall carbon nanotubes abruptly increases the current of the field electron emission, decreases the threshold electric field by a factor of three (to 0.8 V/m), and decreases the work function to 2.1–2.3 eV. It has been found that the flowing of the large emission current I ≥ 2 × 10^?6 A leads to a change in the current-voltage characteristics and a decrease in the emission current. This effect has been explained by escape of cesium atoms from the tips of most nanotubes into the nanotube depth due to desorption or intercalation. At the same time, the low work function is retained for some nanotubes, probably, due to the stronger bonding of Cs atoms with these nanotubes.     

Effect of temperature on the electron field emission from aligned carbon nanofibers and multiwalled carbon nanotubes

Effect of temperature and aspect ratio on the field emission properties of vertically aligned carbon nanofiber and multiwalled carbon nanotube thin films were studied in detail. Carbon nanofibers and multiwalled carbon nanotube have been synthesized on Si substrates via direct current plasma enhanced chemical vapor deposition technique. Surface morphologies of the films have been studied by a scanning electron microscope, transmission electron microscope and an atomic force microscope. It is found that the threshold field and the emission current density are dependent on the ambient temperature as well as on the aspect ratio of the carbon nanostructure. The threshold field for carbon nanofibers was found to decrease from 5.1 to 2.6 V/μm when the temperature was raised from 300 to 650 K, whereas for MWCNTs it was found to decrease from 4.0 to 1.4 V/μm. This dependence was due to the change in work function of the nanofibers and nanotubes with temperature. The field enhancement factor, current density and the dependence of the effective work function with temperature and with aspect ratio were calculated and we have tried to explain the emission mechanism.     

Field electron emission from carbon nanotubes in the presence of a weak high-frequency electric field

Series of narrow peaks in the frequency range of f ≈ 50–1200 MHz have been revealed in the frequency responses of the emission current from carbon nanotubes in the presence of a weak high-frequency electric field. The analysis makes it possible to attribute these peaks to resonance of the first and second harmonics of forced mechanical vibrations of carbon nanotubes in a high-frequency electric field. The determined Q factor of nanotubes is in the range of 100–300.     

Stable electron field emission from carbon nanotubes emitter transferred on graphene films

Carbon nanotubes (CNTs) arrays grown by microwave plasma enhanced chemical vapor deposition (MPCVD) method was transferred onto the substrate covered with graphene layer obtained by thermal chemical vapor deposition (CVD) technology. The graphene buffer layer provides good electrical and thermal contact to the CNTs. The field emission characteristics of this hybrid structure were investigated in this study. Compared with the CNTs arrays directly grown on the silicon substrate, the hybrid emitter shows better field emission performance, such as high emission current and long-term emission stability. The presence of this graphene layer was shown to improve the field emission behavior of CNTs. This work provides an effective way to realize stable field emission from CNTs emitter and similar hybrid structures.     

Low-threshold field electron emission from carbon nanoclusters formed upon cold destruction of graphite

The field-emission characteristics of carbon nanoclusters (graphenes, nanotubes, their compositions with microdiamonds) produced by the cold destruction of natural graphite are studied. The structure of a coating of carbon nanoclusters on a tungsten cathode is examined by field emission microscopy, transmission electron microscopy, and electron diffraction. The high-intensity stable field emission of these clusters is shown to be characterized by a low field threshold. The mechanism of the low-threshold emission from carbon nanoclusters is discussed.     

Confinement of the field electron emission to atomic sites on ultra sharp tips

The spatially controlled field assisted etching method for sharpening metallic tips, in a field ion microscope (FIM), is used to study the evolution of the field emission when the tip apex radius is decreased below 1 nm. Unlike the conventional image formation in a field emission microscope (FEM), we demonstrate that at this scale the field emission is rather confined to atomic sites. A single atom apex fabricated at the end of such tips exhibits an outstanding brightness compared to other atomic tips. The measurements have been repeated for two double atom tips, with different atom-atom separations, and images of atomic field emission localization have also been obtained. We have found that the field emission intensity alternates between adjacent atoms when the applied voltage is gradually increased beyond a threshold value.     

Field emission patterns with atomic resolution of single-walled carbon nanotubes by field emission microscopy

Electron emission properties of single-walled carbon nanotubes (SWCNTs) assembled on a tungsten tip were investigated using field emission microscopy (FEM). The transmission electron microscopy (TEM) micrograph confirmed the existence of an SWCNT bundle on the W tip. Under appropriate experimental conditions,a series of FEM patterns with atomic resolution were obtained. These patterns arose possibly from the field emission of the open end of an individual (16,0) SWCNT protruding from the SWCNT bundle. The magnification factor and the resolution under our experimental conditions were calculated theoretically. If the value of the compression factor β was set at β= 1.76, the calculated value of the magnification factor was in agreement with the measured value. The resolving powerof FEM was determined by the resolution equation given by Gomer. The resolutionof 0.277 nm could be achieved under the typical electric field of 5.0×107 V/cm, which was close to the interatomic separation 0.246 nm between carbon atoms along the zigzag edge at the open end for the (16, 0) SWCNT. Consequently, our experimental results were further supported by our theoretical calculation.     

Carbon nanofibers and multiwalled carbon nanotubes from camphor and their field electron emission

Vertically aligned carbon nanofibers (CNF) and multiwalled carbon nanotubes (MWCN) have been synthesized from camphor by catalytic thermal CVD method on Co and Co/Fe thin films (for CNF) and on silicon substrates using a mixture of camphor and ferrocene (for MWCN). CNF and MWCN are studied by field emission scanning electron microscopy, high-resolution transmission electron microscopy, visible Raman spectroscopy, X-ray diffraction in order to get insight into the microstructure and morphology of these materials. Field electron emission study indicates turn-on field of about 2.56, 3.0 and 6.5 V/μm for MWCN, Co/CNF and Co/Fe/CNF films, respectively. The best performance of MWCN in field electron emission among the materials studied can be due to the highest aspect ratio, good graphitization and good density.     

Visualization of field induced ferroelectric electron emission from TGS using emission electron microscopy

Field induced electron emission from triglycinesulfate (TGS) has been investigated using parallel imaging electron emission microscopy (EEM). The emission phenomenon has been induced by applying an ac electrical field up to 2 kV/mm to a single crystal of approximately 0.1 mm thickness. Emission patterns have been observed as a function of the applied field amplitude and of the crystal temperature. At voltages below the coercive field, no emission is visible. When approaching the Curie temperature, emission gradually disappears. This indicates an electron emission mechanism relying on the existence of a switchable ferroelectric phase. The information content of the images is discussed, an interpretation is given on the basis of existing theories. PACS 68.37.-d; 77; 77.80.Fm; 77.80.-e     

Frequency characteristics of field electron emission from long carbon nanofilaments/nanotubes in a weak AC electric field

Frequency characteristics of field electron emission from long carbon nanofilaments/nanotubes in strong dc and weak ac electric fields have been investigated. A series of narrow peaks with a quality factor of up to 1100 has been discovered in the frequency range of hundreds of kilohertz. The analysis has shown that these peaks are probably associated with mechanical oscillations of the carbon nanofilaments/nanotubes driven by the ac electric field.     

Secondary electron emission from thin carbon films

For the purpose of investigating how secondary electrons are produced in carbon, the correlation between energy-loss events and secondary electrons was studied experimentally by using the coincidence method. If a secondary electron is detected in coincidence with an electron transmitted through a thin film which has lost an amount of energy E, then the process causing this energy loss results in the production of secondary electrons. We established the existence of these coincidences and have taken inelastic and coincidence spectra for films of different thickness. We found that in carbon secondary electrons are predominantly produced as a result of energy losses of about 20 eV, with an efficiency of about 5%. The escape depth of secondary electrons was also estimated to be approximately 30 Å.     

Intense electron emission from carbon fiber cathodes

We studied the emission properties of carbon fiber cathodes. These cathodes were made either of a single carbon fiber or of carbon fabric, or of an array of carbon fiber bundles. It was found that an intense emission of electrons occurs from a plasma which is formed on the carbon fiber surface as a result of a flashover process. In addition, the time delay in the appearance of the electron emission with respect to the start of the accelerating voltage pulse was found to depend strongly on the voltage growth rate. A simple model of the plasma formation is suggested. Received 12 March 2001     

Mechanism of field emission from carbon materials

Field emission in diamond and graphite-like polycrystalline films is investigated experimentally. It is shown that the emission efficiency increases as the nondiamond carbon phase increases; for graphite-like films the threshold electric field is less than 1.5 V/μm, and at 4 V/μm the emission current reaches 1 mA/cm², while the density of emission centers exceeds 10⁶ cm⁻². A general mechanism explaining the phenomenon of electron field emission from materials containing graphite-like carbon is proposed. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 1, 56–60 (10 July 1998)     

No enhanced electron emission from high-density atomic collision cascades in metals

Ion-induced secondary electron emission was studied for vanadium and niobium cluster ions at incident energies between 12.5 and 25 keV. The number of electrons ejected per incident atomic particle was found to be solely a function of the velocity, being independent of the number of atoms in the cluster. In spite of the extremely high energy densities created by cluster ion impact, there is no enhanced electron emission from collision spikes. This is discussed in terms of energy coupling between the system of lattice atoms and that of the electrons in the solid.