Thermionic emission from fullerenes

We investigate the time dependence of carbon cluster ions, formed via thermionic emission from photoexcited fullerenes (C₆₀ and C₇₀). By pulsing the extraction field, we are able to observe delayed ions formed as late as 100 µs after excitation at 532 nm, 355 nm, or 266 nm. All even-sized clusters in the range 36 n 70 undergo thermionic emission.     

Thermionic emission from the fullerenes

Delayed ionisation of the fullerenes is reported over a timescale of up to 16 µs and compared to the Klots' model for thermionic emission [1]. The laser fluence dependence of the observed time constants for ionisation and the measured dependence on cluster size are in good agreement with model predictions giving strong evidence for the thermionic nature of the ionisation process.     

Thermionic emission from giant fullerenes

The kinetics of cluster formation in supersonic jets is examined by numerical integration of the master equation system. Some general characteristics of cluster kinetics could be formulated. Excellent agreement between experimental curves of p-cresol (H₂O)_{0, 1, 2, 3} formation as function of H₂O pressure and the corresponding calculated curves were obtained assuming successive cluster formation. From the kinetic curves, an unambiguous assignment of cluster size was possible which agreed with mass-resolved REMPI measurements. The fit of the rate coefficients shows the formation of p-cresol (H₂O)₁ to be faster than p-cresol (H₂O)₂ and p-cresol (H₂O)₃.     

A novel circuit for independent control of electron energy and emission current of a hot cathode electron source

The implementation of a non-linear combination of two reference voltages to control the anode voltage in the previously described biasing system of an electron source with a hot cathode allows elimination of the correlation between the emission current and the accelerating voltage. The presented system is highly suitable for applications in electron-impact mass spectrometers, ionization gauges and other instruments (for example, electron microscopes).     

Direct delocalization for calculating electron transfer in fullerenes

A method is introduced for simple calculation of charge transfer between very large solvated organic dimers (fullerenes here) from isolated dimer calculations. The individual monomers in noncentrosymmetric dimers experience different chemical environments, so that the dimers do not necessarily represent bulk‐like molecules. Therefore, we apply a delocalizing bias directly to the Fock matrix of the dimer system, and verify that this is almost as accurate as self‐consistent solvation. As large molecules like fullerenes have a plethora of excited states, the initially excited state orbitals are thermally populated, so that the rate is obtained as a thermal average over Marcus thermal transfers. © 2013 Wiley Periodicals, Inc.     

A paradigmatic change: linking fullerenes to electron acceptors

The potential of Lu(3)N@C(80) and its analogues as electron acceptors in the areas of photovoltaics and artificial photosynthesis is tremendous. To this date, their electron-donating properties have never been explored, despite the facile oxidations that they reveal when compared to those of C(60). Herein, we report on the synthesis and physicochemical studies of a covalently linked Lu(3)N@C(80)-perylenebisimide (PDI) conjugate, in which PDI acts as the light harvester and the electron acceptor. Most important is the unambiguous evidence--in terms of spectroscopy and kinetics--that corroborates a photoinduced electron transfer evolving from the ground state of Lu(3)N@C(80) to the singlet excited state of PDI. In stark contrast, the photoreactivity of a C(60)-PDI conjugate is exclusively governed by a cascade of energy-transfer processes. Also, the electron-donating property of the Lu(3)N@C(80) moiety was confirmed through constructing and testing a bilayer heterojunction solar cell device with a PDI and Lu(3)N@C(80) derivative as electron acceptor and electron donor, respectively. In particular, a positive photovoltage of 0.46 V and a negative short circuit current density of 0.38 mA are observed with PDI/Ca as anode and ITO/Lu(3)N@C(80) as cathode. Although the devices were not optimized, the sign of the V(OC) and the flow direction of J(SC) clearly underline the unique oxidative role of Lu(3)N@C(80) within electron donor-acceptor conjugates toward the construction of novel optoelectronic devices.     

Current stimulated electron and photon emission from adlayer-covered nanomaterials

We review experimental investigations of the effect of electropositive and organic overlayers on electron and light emission from nanodispersed (metal and semiconductor) thin films excited by the conduction current. Possible mechanisms of the emission are discussed.     

Vibrationally promoted electron emission from low work-function metal surfaces

We observe electron emission when vibrationally excited NO molecules with vibrational state v, in the range of 9 < or = v < or =18, are scattered from a Cs-dosed Au surface. The quantum efficiency increases strongly with v, increasing up to 10(-2) electrons per NO (v) collision, a value several orders of magnitude larger than that observed in experiments with similar molecules in the ground vibrational state. The electron emission signal, as a function of v, has a threshold where the vibrational excitation energy slightly exceeds the surface work function. This threshold behavior strongly suggests that we are observing the direct conversion of NO vibrational energy into electron kinetic energy. Several potential mechanisms for the observed electron emission are explored, including (1) vibrational autodetachment, (2) an Auger-type two-electron process, and (3) vibrationally promoted dissociation. The results of this work provide direct evidence for nonadiabatic energy-transfer events associated with large amplitude vibrational motion at metal surfaces.     

Positive electron affinity of fullerenes: Its effect and origin

The universal variation pattern of the total energy of various fullerenes including single-walled carbon nanotubes with respect to their extra charge is revealed by the density-functional-theory calculations. The parabolic energy-charge curve with its lowest energy value corresponding to a negatively charged fullerene indicates that these carbon materials have positive electron affinity and are not in the most stable state. The positive electron affinity seems to originate from the pi-electrons and is found to be related to the aggregation property of fullerenes.     

Single electron emission from the closed-tips of single-walled carbon nanotubes

The single electron emission behaviors and characteristics from the well-defined quantized energy levels, corresponding to localized electronic states at the dome-structure tips, in single-walled carbon nanotubes (SWNTs) are investigated and illuminated by use of the energy level emission model in combination with the first-principles calculations on the electronic structures. Under the external electric field, the confined electrons are emitted simultaneously from each quantized energy level by virtue of the resonant tunneling effects. With increasing applied voltage, the emission current increases monotonically and exponentially up to the first peak value, and then steps into the increasing and decreasing "sawtoothlike" variations in sequence. The negative differential resistance or conductivity and the maximum current for SWNTs are simulated. The influences of localized electronic states and curvatures of the different closed tips on the single electron emission behaviors of SWNTs are evaluated and discussed. Also a few issues and applications relevant to electron emission of carbon nanotubes are addressed.     

Soft X-ray radiation-induced electron emission from the surface of polarized ferroelectrics

Additional electron emission that reflects specific properties of ferroelectrics was detected after the negatively charged surface of these preliminarily polarized materials was exposed to soft X-radiation (hv) ≤3 kV). The properties of this emission, which is referred to as anomalous electron emission (AEE) and is excited in single-crystal and ceramic samples, are studied with a standard X-ray photoelectron spectrometer. It is shown that the parameters of AEE spectra correlate with the characteristics of the materials. The conclusions of the phenomenological theory of the phenomenon are in satisfactory agreement with the experimental results. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 6, pp. 1031–1036, November–December, 1998     

Derivatized fullerenes bearing multiple electron donors: synthesis and charge transfer properties

A series of methano-C60 adducts bearing up to six electron donating N,N-dimethylaniline units (denoted as D compounds), along with their analogues without the dimethylamino groups as references (R compounds), were synthesized. The redox properties of the D compounds in solutions were evaluated spectroscopically in reference to the R compounds. According to UV/vis absorption results, there are obviously ground-state intramolecular charge-transfer complexes in the D series, and the charge-transfer effects apparently become saturated with only two donor units in the molecule. The photoinduced intramolecular electron-transfer properties of the D compounds were investigated via fluorescence measurements. The emission from intramolecular exciplexes can be found only in the D molecule with two electron donor units. Throughout the D series, the fluorescence properties are highly sensitive to the solvent polarity, with the emission completely quenched for all of the molecules in a polar solvent like methylene chloride. Mechanistic implications of the results are discussed.     

Relationship between reduction potentials and electron affinities of fullerenes and their derivatives

A linear relationship was found between the first reduction potentials (E°_red) and electron affinities (EA) for fullerenes C₆₀ and C₇₀, their hydro- and fluoro-derivatives, and aromatic hydrocarbons: E°_red = –3.04 + 0.81·EA. This equation was used to estimate the unknown values of EA = 2.45 eV for C₆₀H₂, 2.47 eV for C₇₀H₂, –0.15 eV for C₇₀H_36—38, –0.41 eV for C₇₀H_44—46, and E°_red = –1.74—–1.91 V (vs. Fc^0/+) for C₆₀H₁₈.     

The vibration-rotation emission spectrum of hot BeF2

The high-resolution infrared emission spectrum of BeF2 vapor at 1000 degrees C was rotationally analyzed with the assistance of large-scale ab initio calculations using the coupled-cluster method including single and double excitations and perturbative inclusion of triple excitations, in conjunction with correlation-consistent basis sets up to quintuple-zeta quality. The nu3 fundamental band, the nu1+nu2, nu1+nu3, and 2nu2+nu3 combination bands, and 18 hot bands were assigned. The symmetric stretching (nu1), bending (nu2), and antisymmetric stretching (nu3) mode frequencies were determined to be 769.0943(2), 342.6145(3), and 1555.0480(1) cm-1, respectively, from the band origins of the nu3, nu1+nu3, and nu1+nu2 bands. The observed vibrational term values and B rotational constants were fitted simultaneously to an effective Hamiltonian model with Fermi resonance taken into account, and deperturbed equilibrium vibrational and rotational constants were obtained for BeF2. The equilibrium rotational constant (Be) was determined to be 0.235 354(41) cm-1, and the associated equilibrium bond distance (re) is 1.3730(1) A. The results of our ab initio calculations are in remarkably good agreement with those of our experiment, and the calculated value was 1.374 A for the equilibrium bond distance (re). As in the isoelectronic CO2 molecule, the Fermi resonance in BeF2 is very strong, and the interaction constant k122 was found to be 90.20(4) cm-1.     

Theory of ballistic electron emission microscopy

The present status of theories for interpreting experimental ballistic electron emission microscopy (BEEM) data is reviewed. Current formalisms may be divided into two broad classes: one-electron theories, where carriers do not exchange energy with other excitations in the solid, and scattering approaches, where such losses are considered. While the former theories have been formulated with the help of Green's functions (GFs), the latter have relied more on simulation by Monte-Carlo techniques. For the one-electron approach, we discuss why the originally suggested free propagation of carriers (e.g., ballistic electrons) does not offer a consistent interpretation of the experimental database and should be replaced instead by considering the coherent propagation of electrons interacting with the periodic potential in the metal base. Bridging towards the scattering formalisms, it is shown how GFs incorporating a complex self-energy are still a feasible approach, when only a single inelastic source of scattering (e.g., electron–electron (e–e) interaction) is operative. Within this one-electron scheme, the importance of an accurately computed transmission coefficient at the metal-semiconductor interface is stressed, when aiming to obtain absolute BEEM currents. Analyzing results from scattering techniques, it is argued that this coefficient should be modified to take into account the back-injection of electrons from the semiconductor into the metal. A general expression for BEEM currents is given that can be used to simulate results in real-space, reciprocal-space or energy-space (spectroscopy with BEEM). Some experimental results are discussed in relation to the theories presented.     

Photo-induced electron emission from 17beta-estradiol and progesterone and possible biological consequences

It was established for the first time, that the sexual hormones 17beta-estradiol (17betaE2) and progesterone (PRG) are able to emit electrons from their excited single state in water-ethanol mixtures. The yield of the "solvated electrons" (e(s)(-)) depends on the substrate concentration, the ratio of water-alcohol-mixtures and the temperature. The e(s)(-) yield obtained from 17betaE2 is by two orders of magnitude higher than this of PRG. The possible relationship of the resulting hormone transients from 17betaE2 leading via specific metabolites to breast cancer is discussed.     

Three-stage transformation pathway from nanodiamonds to fullerenes

The dynamics of structure evolution of nanodiamonds ranging from 22 to 318 atoms of various shapes is studied by density functional tight-binding molecular dynamics. The spherical and cubic nanodiamonds can be transformed into fullerene-like structures upon heating. A number of the transformed fullerenes consist of pentagons and hexagons only. Others contain squares, heptagons, and octagons. One simulated fullerene is an isomer of C(60). The temperature of the transformation depends on the size, shape, and orientation of initial cluster. To be transformed into onion-like fullerenes, the spherical nanodiamonds should have 200 atoms or more, while the cubic ones require 302 atoms or more. The time-resolved energy profiles of all the transformations clearly reveal three-stage transformation character. During the first stage, the energy reduces quickly due to converting sp(3) carbon with dangling bond at the surface into sp(2) one, and the formation of partial sp(2) envelope wrapping the cluster. For the second stage, energy decreases slowly. The remaining interior carbon atoms come to the surface through the hole in the sp(2) envelope, and similar amount of sp(3) and sp(2) atoms coexist. The third stage involves the closure of holes, accompanied by the detachment of C(2) molecules and carbon chains from the edges. The energy decreases relatively fast in this stage. The proposed three-stage transformation pathway holds for all the simulations performed in this work, including those with the instant heating.     

Dialkoxymethano[60]fullerenes as electron acceptors in thin-film organic solar cells

This study presents the synthesis, characterization, and electrochemical properties of four new dialkoxymethanofullerenes, as well as their performance in organic solar cells (OSCs) devices. Dialkoxymethanofullerenes were synthesized in 27%–32% yield by thermolysis of dialkoxyoxadiazolines and reaction with C₆₀ under reflux in toluene. The prepared compounds were then characterized and used for the first time as electron-acceptor materials in thin-film bulk heterojunction OSCs with PBTZT-stat-BDTT-8 as the electron donor material. The devices made with ethoxy-hexyloxymethanofullerene and methoxy-hexyloxymethanofullerene exhibited optimal power conversion efficiencies (PCEs) of 3.79% and 4.65%, with open-circuit voltage of 0.832 and 0.831 V, respectively. In contrast, the devices made with ethoxy-ethoxymethanofullerene and methoxy-ethoxymethanofullerene exhibited very low PCEs of <0.01% for both, indicating a large impact of the substituents on device performance.     

Enhanced electron field emission from ZnO nanoparticles-embedded DLC films prepared by electrochemical deposition

ZnO nanoparticles-embedded diamond-like amorphous (DLC) carbon films have been prepared by electrochemical deposition. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) results confirm that the embedded ZnO nanoparticles are in the wurtzite structure with diameters of around 4 nm. Based on Raman measurements and atomic force microscope (AFM) results, it has been found that ZnO nanoparticles embedding could enhance both graphitization and surface roughness of DLC matrix. Also, the field electron emission (FEE) properties of the ZnO nanoparticles-embedded DLC film were improved by both lowering the turn-on field and increasing the current density. The enhancement of the FEE properties of the ZnO-embedded DLC film has been analyzed in the context of microstructure and chemical composition.