Work function field

While field ion microscopy has provided an effective means to visualize surface atoms and adsorbates, field emission is the preferred technique for measurement of the energetic properties of the surface. The effect of an applied field on the rate of electron emission was described by Fowler and Nordheim [65] and is shown schematically in Fig. Vlll 5. In the absence of a field, a barrier corresponding to the thermionic work function, prevents electrons from escaping from the Fermi level. An applied field, reduces this barrier to 4> - F, where the potential V decreases linearly with distance according to V = xF. Quantum-mechanical tunneling is now possible through this finite barrier, and the solufion for an electron in a finite potential box gives... 

Fig. VIII-5. Schematic potential energy diagram for electrons in a metal with and without an applied field , work function Ep, depth of the Fermi level. (From Ref. 62.)...

Measuring the electron emission intensity from a particular atom as a function of V provides the work function for that atom its change in the presence of an adsorbate can also be measured. For example, the work function for the (100) plane of tungsten decreases from 4.71 to 4.21 V on adsorption of nitrogen. For more details, see Refs. 66 and 67 and Chapter XVII. Information about the surface tensions of various crystal planes can also be obtained by observing the development of facets in field ion microscopy [68]. 

Mobility of this second kind is illustrated in Fig. XVIII-14, which shows NO molecules diffusing around on terraces with intervals of being trapped at steps. Surface diffusion can be seen in field emission microscopy (FEM) and can be measured by observing the growth rate of patches or fluctuations in emission from a small area [136,138] (see Section V111-2C), field ion microscopy [138], Auger and work function measurements, and laser-induced desorption... 

Wlien an electrical coimection is made between two metal surfaces, a contact potential difference arises from the transfer of electrons from the metal of lower work function to the second metal until their Femii levels line up. The difference in contact potential between the two metals is just equal to the difference in their respective work fiinctions. In the absence of an applied emf, there is electric field between two parallel metal plates arranged as a capacitor. If a potential is applied, the field can be eliminated and at this point tire potential equals the contact potential difference of tlie two metal plates. If one plate of known work fiinction is used as a reference electrode, the work function of the second plate can be detennined by measuring tliis applied potential between the plates [ ]. One can detemiine the zero-electric-field condition between the two parallel plates by measuring directly the tendency for charge to flow through the external circuit. This is called the static capacitor method [59]. 

Schematic diagram showing how placing a thin layer of highly dispersed carbon onto the surface of a metal filament leads to an induced dipolar field having positive and negative image charges. The positive side is always on the metal, which is much less electronegative than carbon. This positive charge makes it much more difficult to remove electrons from the metal surface. The higher the value of a work function, the more difficult it is to remove an electron. Effectively, the layer of carbon increases the work function of the filament metal. Very finely divided silicon dioxide can be used in place of carbon.

The source requited for aes is an electron gun similar to that described above for electron microscopy. The most common electron source is thermionic in nature with a W filament which is heated to cause electrons to overcome its work function. The electron flux in these sources is generally proportional to the square of the temperature. Thermionic electron guns are routinely used, because they ate robust and tehable. An alternative choice of electron gun is the field emission source which uses a large electric field to overcome the work function barrier. Field emission sources ate typically of higher brightness than the thermionic sources, because the electron emission is concentrated to the small area of the field emission tip. Focusing in both of these sources is done by electrostatic lenses. Today s thermionic sources typically produce spot sizes on the order of 0.2—0.5 p.m with beam currents of 10 A at 10 keV. If field emission sources ate used, spot sizes down to ca 10—50 nm can be achieved. 

Shottky Emission - This is also a thermionic type of emission except that in this case, the applied electric field effectively decreases the work function of the material, and more electrons can then escape. 

High Field Emission - In this case, the electric field is high enough to narrow the work-function barrier and allow electrons to escape by tunneling through the barrier. 

Schematic energy level diagrams of a metal/polymer/metal structure before and after the layers are in contact are shown in the top two drawings of Figure 11-6. Before contact, the metals and the polymer have relative energies determined by the metal work functions and the electron affinity and ionization potential of the polymer. After contact there is a built-in electric field in the structure due to the different Schottky energy barriers of the asymmetric metal contacts. Capacitance-voltage measurements demonstrate that the metal/polymer/metal structures are fully depleted and therefore the electric field is constant throughout the bulk of the structure [31, 35]. The built-in potential, Vhh i.e. the product of the constant built-in electric field and the layer thickness may be written...

Parker [55] studied the IN properties of MEH-PPV sandwiched between various low-and high work-function materials. He proposed a model for such photodiodes, where the charge carriers are transported in a rigid band model. Electrons and holes can tunnel into or leave the polymer when the applied field tilts the polymer bands so that the tunnel barriers can be overcome. It must be noted that a rigid band model is only appropriate for very low intrinsic carrier concentrations in MEH-PPV. Capacitance-voltage measurements for these devices indicated an upper limit for the dark carrier concentration of 1014 cm"3. Further measurements of the built in fields of MEH-PPV sandwiched between metal electrodes are in agreement with the results found by Parker. Electro absorption measurements [56, 57] showed that various metals did not introduce interface states in the single-particle gap of the polymer that pins the Schottky contact. Of course this does not imply that the metal and the polymer do not interact [58, 59] but these interactions do not pin the Schottky barrier. 

For PPV-imine and PPV-ether the oxidation potential, measured by cyclic voltammetry using Ag/AgCl as a reference are ,M.=0.8 eV and 0.92 eV, respectively. By adopting the values 4.6 eV and 4.8 eV for the work functions of a Ag/AgCl and an 1TO electrode, respectively, one arrives at zero field injection barriers of 0.4 and 0.55 eV. These values represent lower bounds because cyclic voltammetry is carried out in polar solvents in which the stabilization cncigy of radical ions exceeds that in a polymer film, where only electronic polarization takes place. E x values for LPPP and PPPV are not available but in theory they should exceed those of PPV-imine and PPV-ether. 

Measurements [113,368] of interfacial (contact) potentials or calculated values of the relative work functions of reactant and of solid decomposition product under conditions expected to apply during pyrolysis have been correlated with rates of reaction by Zakharov et al. [369]. There are reservations about this approach, however, since the magnitudes of work functions of substances have been shown to vary with structure and particle size especially high values have been reported for amorphous compounds [370,371]. Kabanov [351] estimates that the electrical field in the interfacial zone of contact between reactant and decomposition product may be of the order of 104 106 V cm 1. This is sufficient to bring about decomposition. 

Owing to the rapid development of the field from an experimental point of view, and the persistence of discussions on some of the aspects outlined above, a chapter on the pzc that includes a discussion of the relation between the electrochemical and the ultrahigh vacuum (UHV) situation in reference to the conditions at the pzc seems timely. This review of the literature will not be exhaustive but selective, taking into account the compilations already existing. In any case, the objective is to evaluate the existing data in order to recommend the most reliable. Finally, the data on pzc will be discussed in comparison with electron work function values. The role and significance of work functions in electrochemistry were discussed by Trasatti6 in 1976. 

Figure 6.16. Different modes of adsorption of CHjOH on Pt under ultra-high vacuum (left) and in aqueous solutions (right) showing the effect of local electrostatic field and surface work function on the mode of adsorption.100 Reprinted with permission from the American Chemical Society.

Conversely, an atom in Fig. 6.23 with an affinity level that initially is empty becomes partly occupied upon adsorption. Hence, charge is transferred from the metal to the atom. This sets up a dipole that increases the surface contribution to the work function. This is the case for adsorbed halides, which will be negatively charged at the surface. We will later see that such dipole fields can explain promotion and inhibition effects caused by various adsorbates in catalysis. 

In general, the peculiarities of the surface effects in thin semiconductors, for which application of semi-infinite geometry becomes incorrect were examined in numerous papers. As it has been shown in studies [101, 113, 121 - 123] the thickness of semiconductor adsorbent becomes one of important parameters in this case. Thus, in paper [121] the relationship was deduced for the change in conductivity and work function of a thin semiconductor with weakly ionized dopes when the surface charge was available. Paper [122] examined the effect of the charge on the temperature dependence of the work function and conductivity of substantially thin adsorbents. Papers [101, 123] focused on the dependence of the surface conductivity and value of the surface charge as functions of the thickness of semiconductor and value of the surface band bending caused by adsorption and application of external field. 

The significance and impact of surface science were now becoming very apparent with studies of single crystals (Ehrlich and Gomer), field emission microscopy (Sachtler and Duell), calorimetric studies (Brennan and Wedler) and work function and photoemission studies (M.W.R.). Distinct adsorption states of nitrogen at tungsten surfaces (Ehrlich), the facile nature of surface reconstruction (Muller) and the defective nature of the chemisorbed oxygen overlayer at nickel surfaces (M.W.R.) were topics discussed. 

Specimens for field emission sources are of a very fine needle shape, usually in the form of tungsten wire with a tip radius of <0.1 pm (Figure 5.4). Application of a potential of lkV thus generates a field of 106V/m which lowers the work function barrier sufficiently for electrons to tunnel out of the tungsten. FEG electron microscopes usually employ a gun potential of 3-4 keV. 

Work function in field emission. J. chem. Physics 21, 1869—1876 (1953). 

---