Work function of electrode

Blom et al. [85] stated that the l/V characteristics in LEDs based on ITO/di-alkoxy-PPVs/Ca are determined by the bulk conductivity and not by the charge carrier injection, which is attributed to the low barrier heights at the interface ITO/PPV and PPV/Ca. They observed that the current flow in so called hole-only devices [80], where the work function of electrodes are close to the valence band of the polymer, with 1TO and Au as the electrodes, depends quadratically on the voltage in a logl/logV plot and can be described with following equation, which is characteristic for a space-charge-limitcd current (SCL) flow (s. Fig. 9-26) ... 

The work function of electrodes emersed from aqueous solutions in ultra high vacuum (UHV) can be measured by means of the ultra-violet photo-electron emission spectroscopy (UPS) [KOtz-Neff-MUller, 1986]. Figure 4-27 shows the work function measured by UPS of the emersed metal electrodes of gold,... 

One should also invoke Fermi statistics. A typical tunnel curve is shown in Fig. 12 for SET model with D = 14 a.u., a = 1 a.u., the work function of electrodes W = 0.4 a.u., the Fermi energy Ee = 0.2 a.u., and the polarizability a = 200 a.u. (of Na atom). The potential drops near the interface of the source-drain electrodes, as it should for the ballistic regime. The tunnel curve has a single shallow well at a small bias voltage. When the latter increases, the well becomes deeper, and the dot is attracted to the inter-electrode gap center... 

The working mechanism of PLECs discussed earlier is responsible for their unique structures and characteristics, which have both advantages and drawbacks in performance compared to PLEDs. The PLECs exhibit a bipolar behavior due to the insensitivity to the work function of electrode. Under both forward and reverse bias, PLECs show strong electroluminescence, which has been observed in masses of PLECs constructed with various... 

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]. 

The compounds obtained in solid state have the general formula [MefSCNf JR., (R-cations of cyanine dyes) and could be embedded into polyvinylchloride matrix. Using the matrix as work element of electrodes shows the anionic function concerning the anionic thiocyanate complexes of Pd, Hg, Zn and the response to sepai ately present thiocyanate and metallic ions is not exhibited. 

In a light-emitting MSM structure the two metal electrodes selected such that the work functions of the electrodes are near the edge of the valence band (VB) and the conducting band (CB) of the semiconductor, respectively, so that oppositely charge carriers are injected from the opposite electrodes. An ohmic and a rectifying contact is therefore formed in the MSM structure (see Fig. 9-22). 

The metallic electrode materials are characterized by their Fermi levels. The position of the Fermi level relative to the eneigetic levels of the organic layer determines the potential barrier for charge carrier injection. The workfunction of most metal electrodes relative to vacuum are tabulated [103]. However, this nominal value will usually strongly differ from the effective workfunction in the device due to interactions of the metallic- with the organic material, which can be of physical or chemical nature [104-106]. Therefore, to calculate the potential barrier height at the interface, the effective work function of the metal and the effective ionization potential and electron affinity of the organic material at the interface have to be measured [55, 107],... 

The simplest and most widely used model to explain the response of organic photovoltaic devices under illumination is a metal-insulaior-metal (MIM) tunnel diode [55] with asymmetrical work-function metal electrodes (see Fig. 15-10). In forward bias, holes from the high work-function metal and electrons from the low work-function metal are injected into the organic semiconductor thin film. Because of the asymmetry of the work-functions for the two different metals, forward bias currents are orders of magnitude larger than reverse bias currents at low voltages. The expansion of the current transport model described above to a carrier generation term was not taken into account until now. 

Figure 9-19. Bund diagram of LPPP with hole traps and gold electrodes with Va<- vacuum level. Ec conduction band, Eva valence band. E, Fermi level. . baudgup energy. and , " trap depths. ,( ) trap distribution, X electron affmity, and All work function of the gold electrodes.

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. 

The materials used as the electron and hole injecting electrodes play a crucial role in the overall performance of the device and therefore cannot be neglected even in a brief review of the materials used in OLEDs. The primary requirements for the function of the electrodes is that the work function of the cathode be sufficiently low and that of the anode sufficiently high, to enable good injection of electrons and holes, respectively. In addition, at least one electrode must be sufficiently transparent to permit the exit of light from the organic layer. 

A thin layer deposited between the electrode and the charge transport material can be used to modify the injection process. Some of these arc (relatively poor) conductors and should be viewed as electrode materials in their own right, for example the polymers polyaniline (PAni) [81-83] and polyethylenedioxythiophene (PEDT or PEDOT) [83, 841 heavily doped with anions to be intrinsically conducting. They have work functions of approximately 5.0 cV [75] and therefore are used as anode materials, typically on top of 1TO, which is present to provide lateral conductivity. Thin layers of transition metal oxide on ITO have also been shown [74J to have better injection properties than ITO itself. Again these materials (oxides of ruthenium, molybdenum or vanadium) have high work functions, but because of their low conductivity cannot be used alone as the electrode. 

Friend et at. studied the influence of electrodes with different work-functions on the performance of PPV photodiodes 143). For ITO/PPV/Mg devices the fully saturated open circuit voltage was 1.2 V and 1.7 V for an ITO/PPV/Ca device. These values for the V c are almost equal to the difference in the work-function of Mg and Ca with respect to 1TO. The open circuit voltage of the ITO/PPV/A1 device observed at 1.2 V, however, is considerably higher than the difference of the work-function between ITO and Al. The Cambridge group references its PPV with a very low dark carrier concentration and consequently the formation of Schottky barriers at the PPV/Al interface is not expected. The mobility of the holes was measured at KT4 cm2 V-1 s l [62] and that for the electrons is expected to be clearly lower. 

Equation (17) shows the relationship between electrode potentials and electronic energy. The electrode potential is measured by the electron work function of the metal, modified by the contact with the solution (solvent). This establishes a straightforward link, not only conceptually but also experimentally, between electrochemical and UHV situations.6,32 In many cases, electrochemical interfaces are synthesized in UHV conditions55-58 by adding the various components separately, with the aim possibly of disentangling the different contributions. While the situation can be qualitatively reproduced, it has been shown above that there may be quantitative differences that are due to the actual stmctural details. 

It was shown in Section I that the potential of zero charge is related to the electron work function of the electrode metal by Eq. (27) ... 

As discussed in Section I.3(i), AX indicates the variation in the work function of a metal as an interface is created by bringing a solid and a liquid in contact. In principle, it should be possible to compare AX values with A values measured directly in gas phase experiments. This is the aim of UHV synthesis of the electrochemical double layer868 in which the electrode interface is created molecule by molecule, starting with the bare metal surface. It is thus possible to obtain evidence of ion-water interactions that can be envisaged from electrochemical measurements but that are not directly demonstrable. Wagner55 has given a recent comprehensive review of electrochemical UHV experiments. 

C.G. Vayenas, On the work function of the gas exposed electrode surfaces in solid state electrochemistry, J. Electroanal. Chem. 486, 85-90 (2000). 

Figure 4.2J. Effect of catalyst-electrode potential Uwr on the work function of the gas exposed catalyst-electrode surface. Open symbols open circuit operation varying gas composition. Closed symbols closed circuit operation C2H4,02, He and NH3, 02, He mixtures.54,55 Reprinted from ref. 55 with permission from Elsevier Science.

Work function, a quantity of great importance in surface science and catalysis, plays a key role in solid state electrochemistry and in electrochemical promotion. As will be shown in Chapter 7 the work function of the gas-exposed surface of an electrode in a solid electrolyte cell can be used to define an absolute potential scale in solid state electrochemistry. 

Figure 5.15. Work function of working (W) and reference (R) electrode, Ow and R, as a function of catalyst potential cUwr for the systems (a) Pt(W)-Au(R) and (b) Pt(W)-Ag(R). Symbols and conditions as in Fig. 5.14.32 Reproduced by permission of The Electrochemical Society.

Equation (5.19) shows that the emf eUV of solid electrolyte cells provides a direct measure of the difference in work function of the two gas-exposed, i.e., catalytically active, electrode surfaces. Thus, solid electrolyte cells are work function probes for their gas exposed electrode surfaces. This was shown in Figures 5.15 and 5.16. 

Equations (5.18) and (5.19), particularly the latter, have only recently been reported and are quite important for solid state electrochemistry. Some of then-consequences are not so obvious. For example consider a solid electrolyte cell Pt/YSZ/Ag with both electrodes exposed to the same P02, so that Uwr = 0. Equation (5.19) implies that, although the work functions of a clean Pt and a clean Ag surface are quite different (roughly 5.3 eV vs 4.7 eV respectively) ion backspillover from the solid electrolyte onto the gas exposed electrode surfaces will take place in such a way as to equalize the work functions on the two surfaces. This was already shown in Figs. 5.14 and 5.15. 

Significant observations regarding the origin of NEMCA have been also made using Ultra-violet Photoelectron Spectroscopy (UPS) with Pt and Ag electrodes deposited on YSZ. In this case the work function of the electrode can be determined from the cutoff energy of secondary electrons (Fig. 5.43).24,68 As shown in Fig. 5.8b the change in the work function of the gas-exposed Ag surface is very close to the imposed electrode potential change AUwr. 

For the case of Ag it was found that both anodic and cathodic polarization lead to the creation of small insulated particles on the YSZ surface. Both the Fermi level and the work function of the insulated Ag particles was found to change with Ag electrode overpotential but the changes are smaller than on the continuous Ag film.24... 

The significant point is that PEEM, as clearly presented in Figures 5.45 to 5.47, has shown conclusively that follows reversibly the applied potential and has provided the basis for space-and time-resolved ion spillover studies of electrochemical promotion. It has also shown that the Fermi level and work function of the solid electrolyte in the vicinity of the metal electrode follows the Fermi level and work function of the metal electrode, which is an important point as analyzed in Chapter 7. 

---