Work function of single-walled carbon nanotubes determined by field emission microscopy

The field emission characteristics of a single micro-bundle of single-walled carbon nanotubes (SWCNTs) were investigated using field emission microscopy (FEM). Fowler–Nordheim plots revealed that the work function of the SWCNTs was reduced with increasing heating temperature, and reached a minimum value around 1000 °C, assuming that the β factor was constant during the heating process. Field emission patterns also demonstrated fine structures that were believed to be images of the cap of a SWCNT, which was in a clean state. The radius of the SWCNT micro-bundle was measured by transmission electron microscopy (TEM), and the β factor was calculated using two empirical formulae. Then, the work function of the SWCNT was determined from the slope, K, of its Fowler–Nordheim plot. The work function values were Φ₁=4.76 eV and Φ₂=4.88 eV, respectively. Received: 26 October 2001 / Revised version: 19 February 2002 / Published online: 6 June 2002     

Investigation of field electron microscope tips bombarded with microparticles at limited field emission currents

Mo, Ta, W, and Re field electron microscope (FEM) tips, bombarded with microparticles at limited field emission currents (400 MΩ resistor in series with the FEM tip) were investigated by means of FEM, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). Two groups of tips could be distinguished: One group had a slight tip radius increase to a maximum of 2.5 μm and microcraters were formed along the tip shank. The other group had no detectable tip radius change; however, there was microcrater formation near the tip apex area. FEM patterns showed surface contamination clearly. Heating such contaminated tips and tips where phosphorescent material (Zn:Cd)S had been deposited in less than monolayer concentration by evaporation from a heating coil, resulted in similar sequences of FEM patterns. A new type of microcrater with smooth crater lips could be detected in both groups. These results support the combined microparticle-field emission mechanism [1], which was proposed earlier to be responsible for melting cap and microcrater formation. Excerpts were presented at the 19th Field Emission Symposium, Urbana, Illinois (USA), August 1972.     

Field—ion microscopy observation of single—walled carbon nanotubes

Field-ion microscopy(FIM),a tool for surface analysis with atomic resolution,has been employed to observe the end structure of single-walled carbon nanotubes(SWCNTs).FIM images revealed the existence of open SWCNT ends,Amorphous carbon atoms were also observed to occur around SWCNTs and traditional field evaporation failed to remove them.Heat treatment was found to be efficacious in altering the end structures of SWCNT bundles.Carbon and oxygen atoms released from heated tungsten filament are believed to be responsible for the decoration imposed on the SWCNT ends.     

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 microscopy of adsorption and desorption of residual gas molecules on a carbon nanotube tip

Field emission of electrons from multiwall carbon nanotubes has been investigated by field emission microscopy (FEM) in ultra-high vacuum. A carbon nanotube, at the end of which at least six pentagons exist to make a closed cap, gives an FEM pattern consisting of bright pentagonal rings if the nanotube surface is clean. Adsorption of residual gas molecules is observed as bright spots in the FEM pattern, giving rise to an abrupt increase in the emission current. Adsorbed molecules seem to reside preferentially on the pentagonal sites where the strong electric field is concentrated. A heat cleaning of the emitter at about 1300 K allows the molecules to desorb, and the nanotube emitter recovers its original clean surface. It has been revealed that the adsorption and desorption of gas molecules are responsible for stepwise fluctuation of the emission current.     

Size of the localized electron emission sites on a closed multiwalled carbon nanotube

We have measured the size of the localized electron emission sites on multiwalled carbon nanotubes (MWNTs) with caps closed by a fullerenelike structure. MWNTs were individually mounted on tungsten support tips and imaged with a field emission microscope (FEM). The magnification of the FEM was calibrated using electron ray tracing and verified by comparing transmission electron microscope images. The FEM image was also tested for effects of the lateral energy spread. We found ring-shaped emission areas with three flattened sides, of a radius of 1.7±0.3 nm, and separated by 5±1 nm.     

Field emission of electrons by carbon nanotube twist-yarns

Field emission with high current density at low operating voltage was found for the yarns obtained by solid state spinning process from forest of vertically aligned multiwall carbon nanotubes. The nanotube forest was produced catalytically by CVD method. It is found that only a small fraction of carbon nanotubes from their total amount in the yarn yields to electron emission from its free end. This led to resistive heating of the emitting tubes and limiting of the emission current. The field emission microscopy pictures of MWNT yarn in free-end geometry appears to be very different from that of the conventional non-yarn carbon nanotube-based cathodes described in all previous studies. The FEM patterns are found to consist of the set of line and arc segments rather than a set of spots. Possible explanation of this effect is presented and discussed. The field emission from the lateral side of the yarns showed the self-enhanced currents increasing with operation time. We assume that this current increase may be due to untwisting and unwrapping of yarns resulted of application of the electric field. The lowest threshold field of about 0.7 V/μm was obtained after a few cycles of applied field increase. The prototypes of cathodoluminescent lamps and alphanumerical indicators based on MWNT twist-yarn cold cathodes are demonstrated. PACS 79.70.+q; 61.46.Fg; 85.45.Db     

Fine-structured field emission images originating from coherently scattering of electrons within a multi-walled carbon nanotube

High resolution field emission image of a single multi-walled carbon nanotube was studied by field emission microscopy. The images contain patterns consisting of rather ordered bright fringes. We propose a model based on coherent electron scattering to explain the observed field emission image. The emitted electrons will undergo coherent scattering within the cap region of a multi-wall carbon nanotube, which may be viewed as elastic scattering by a polycrystalline structure with an infinite size. This study is helpful for understanding the physical mechanism of field emission of carbon nanotube.     

碳纳米管的变温场发射

考察了温度变化对沉积在钨丝针尖上的碳纳米管场发射的影响，发现碳纳米管场发射电流随温度升高而增大，场发射电流的稳定性基本没有变化. 多根碳纳米管的场发射特性随温度变化出现偏离Fowler-Nordheim理论的现象，这种现象可能来自碳纳米管的不均匀性.     

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.     

Interaction of hydrogen with palladium surface: FIM and FEM studies

In the present paper, we focus on the geometrical and electronic changes in palladium surface structure which appeared during its interaction with hydrogen in the presence of an external electric field. The interaction process was examined by using the field ion microscopy (FIM) as well as the field emission microscopy (FEM) techniques. In order to study the geometrical changes in substrate surface structure, the distance distribution function (DDF) was constructed on the basis of FIM patterns of both a clean and hydrogen-covered palladium surface. The electronic changes were examined by the measurement of the total energy distribution (TED) of electrons emitted from the palladium tip surface. The most pronounce examples of such changes are an expansion of the equilibrium interatomic distance in palladium surface and a shift of the Fermi level of the metal. These changes may be explained among others by palladium hydrides formation. This process is the most efficient if the field strength exceeds 23 V/nm.     

Localized multiphoton emission of femtosecond electron pulses from metal nanotips

Intense multiphoton electron emission is observed from sharp (approximately 20 nm radius) metallic tips illuminated with weak 100-pJ, 7-fs light pulses. Local field enhancement, evidenced by concurrent nonlinear light generation, confines the emission to the tip apex. Electrons are emitted from a highly excited nonequilibrium carrier distribution, resulting in a marked change of the absolute electron flux and its dependence on optical power with the tip bias voltage. The strong optical nonlinearity of the electron emission allows us to image the local optical field near a metallic nanostructure with a spatial resolution of a few tens of nanometers in a novel tip-enhanced electron emission microscope.     

单根准直碳纳米纤维的场发射特性

采用等离子体增强热灯丝化学气相沉积方法，以甲烷和氢气为反应气体，在钨丝衬底上制备出准直的碳纳米纤维(CNFs)，其生长密度小于10.6cm-2，长度为6—30μm，直径为60—100nm.并采用自制的双探针扫描电子显微镜系统，对所生长的单根CNF作了场发射特性研究.结果表明，其场发射开启电压约为5V/μm，相应的发射电流达到20μA/cm2，同时，对不同长度的CNFs及单根CNF不同位置的场发射研究表明，场发射电流的大小不仅与材料本身的功函数、外电场场强、材料的微观结构以及宏观的几何结构有关，而且电子在输运过程中所受到的散射也是决定场发射电流大小的关键因素. 关键词： 碳纳米纤维 化学气相沉积 场发射 扫描电子显微镜     

碳纳米管场致发射中的空间电荷效应

采用微波等离子体化学气相沉积(MWPCVD)方法成功制备以碳纳米管束为单元的场致发射阵列,获得很好的场致发射电流发射特性,在电流密度较大时,发现I-V特性偏离由Fowler-Nordheim公式计算出的结果。采用Electron Beam Simulation(EBS)软件进行模拟分析发现:在电流密度较低时,I-V特性能很好与F-N公式吻合。但碳纳米管尖端电流密度大于106A/cm2时,碳纳米管尖端处的有效电场强度受空间电荷的影响比较明显,进而对碳纳米管的场致发射特性显现出不可忽略的影响,此时碳纳米管的发射电流密度开始受到空间电荷的限制。     

Field electron emission in graphite-like films

Results of investigation of carbon films deposited with the use of gas-phase chemical reactions in the plasma of a dc discharge are presented. Films obtained at different parameters of the deposition process varied widely in their structure and phase composition, from polycrystalline diamond to graphite-like material. Comparative study of the structure and phase composition of the films using Raman spectroscopy, cathodoluminescence, electron microscopy, and diffractometry, as well as the obtained field electron emission characteristics, have shown that the threshold value of the electric field strength for electron emission decreases with a decrease in the size of diamond crystallites and growth of the fraction of non-diamond carbon. The lowest threshold fields (less than 1.5 V/μm) are obtained for films consisting mainly of graphite-like material. A model based on the experimental data is proposed, which explains the mechanism of field electron emission in carbon materials.     

Area effect of patterned carbon nanotube bundle on field electron emission characteristics

Patterned carbon nanotube (CNT) bundles were fabricated using thermal chemical vapor deposition (CVD) method. Patterns of different diameters and distances were defined on Si(100) substrates using photolithography. CNT bundle height was controlled using different acetylene (C₂H₂) flow times. The inter-bundle distance of CNTs to CNT bundle height ratio was maintained at approximately 2, a number predicted to have a maximum field emission for CNT, and left the patterned CNT bundle area as a variable parameter. The relationship between CNT bundle area and the field electron emission characteristics was studied. The lowest threshold electric field (E_th) of 0.7 V/μm was obtained when the total area of patterned CNT bundles was approximately 46%. The result shows that there is an optimal CNT bundle area for electron field emission.     

Selective growth, characterization, and field emission performance of single-walled and few-walled carbon nanotubes by plasma enhanced chemical vapor deposition

Single-walled carbon nanotubes (SWCNTs) and few-walled carbon nanotubes (FWCNTs) have been selectively synthesized by plasma enhanced chemical vapor deposition at a relative low temperature (550 °C) by tuning the thickness of iron catalyst. The parametric study and the optimization of the nanotube growth were undertaken by varying inductive power, temperature, catalyst thickness, and plasma to substrate distance. When an iron film of 3-5 nm represented the catalyst thickness for growing FWCNT arrays, SWCNTs were synthesized by decreasing the catalyst thickness to 1 nm. The nanotubes were characterized by field emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. Electron field emission properties of the nanotubes indicate that the SWCNTs exhibit lower turn-on field compared to the FWCNTs, implying better field emission performance.     

碳纳米管/硅纳米孔柱阵列的场发射性能

"通过热化学气相沉积的方法将碳纳米管生长到硅纳米孔柱阵列衬底上．采用场发射扫描电子显微镜、透射电子显微镜、高分辨透射电子显微镜、拉曼光谱和X射线能谱对所制备的样品形貌、组成进行了分析．结果发现：所制备产物为一种具有面积大、准周期性的碳纳米管/硅巢状阵列复合结构．能谱分析表明碳纳米管仅含有碳元素．对样品进行场发射性能测试表明该结构开启电压为1.3 MV/m,当外加电压为4.26 MV/m,发射电流为5 mA/cm2．由FN公式计算相应的场增强因子约为1.1￡104．碳纳米管/硅纳米孔柱阵列好的场发射性能被归     

High-field electron emission of carbon nanotubes grown on carbon fibers

Carbon nanotubes with uniform density were synthesized on carbon fiber substrate by the floating catalyst method. The morphology and microstructure were characterized by scanning electron microscopy and Raman spectroscopy. The results of field emission showed that the emission current density of carbon nanotubes/carbon fibers was 10 μA/cm² and 1 mA/cm² at the field of 1.25 and 2.25 V/μm, respectively, and the emission current density could be 10 and 81.2 mA/cm² with the field of 4.5 and 7 V/μm, respectively. Using uniform and sparse density distribution of carbon nanotubes on carbon fiber substrate, the tip predominance of carbon nanotubes can be exerted, and simultaneously the effect of screening between adjacent carbon nanotubes on field emission performance can also be effectively decreased. Therefore, the carbon nanotubes/carbon fibers composite should be a good candidate for a cold cathode material.     

Kinetic instabilities during the NO(x) reduction with hydrogen on Pt crystals studied with field emission on the nanoscale

This paper reviews field emission studies of kinetic instabilities occurring during the catalytic reduction of nitric oxide (NO) and nitrogen dioxide (NO(2)) by hydrogen on three-dimensional platinum crystals. Emphasis is placed on revealing that both field ion microscopy (FIM) and field electron microscopy (FEM) can image such instabilities under truly in situ reaction conditions with a lateral resolution on the nanoscale. In particular, oscillatory behavior with rapid ignition from a state of low to a state of high catalytic activity is demonstrated for both NO and NO(2) reduction. Results of a local chemical probing during FIM studies of the NO+H(2) reaction are also shown and provide clear evidence for the oscillatory behavior of water (detected as H(2)O(+) and H(3)O(+)) formation and for diffusion supply of NO into surface regions emptied during the stage of high catalytic activity. The rapid ignition ("surface explosion") of the catalytic cycle is discussed on the basis of an autocatalytic mechanism of the NO decomposition. On the (001) plane of the Pt crystal small island formation is seen to occur during the low-activity state of the catalytic cycle. Islands have a size equivalent to approximately 3 nm, move independently from each other, and do not merge when colliding. A tentative model is discussed associating islands with patches of hydroxyl groups. Very regular oscillatory behavior is demonstrated for the NO(2) reduction using FEM. Advantages as well as shortcomings of the FEM/FIM experimental approach are discussed and an outlook on future studies using local chemical probing will be given wherever appropriate. (c) 2002 American Institute of Physics.