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If an electron beam is directed towards a surface, it gets reflected if its potential is equal to -(E P /e + ∆Φ), the negative value of the primary energy divided by e and corrected for ∆Φ between the surface and the electron emitter (in the widest sense: cathode, electron gun, etc.). Since the surface serves here as the anode in a diode configuration, the name diode method has been chosen. This method was introduced early by P.A. Anderson [35A]. Many details of different experimental set-ups are discussed in [73K2, 79H3]. It was pointed out [85K8] that for carefully chosen conditions and for a patchy surface, i.e., a surface consisting of a composite of smaller areas of different work function, the diode method measures the same arithmetical average of Φ as the Kelvin method (see below). How to use a HREEL spectrometer for the diode method is reported in Ref.[85S3]. Vibrating capacitor method (Kelvin)The vibrating capacitor method is based on the work of Lord Kelvin [1898K] and of Zisman [32Z]. A condensor is formed of the surface to be studied and a reference electrode in front of it which are connected by a ammeter and a variable voltage source. If the capacitance between the plates (sample and reference electrode) is changed, e.g., by changing their distance, a current will flow. By compensating the Ref. p. 4.2-118] 4.2 Electron work function of metals and semiconductors Lando lt-Börnstein New Series III/42A2 4.2-7contact potential difference through the voltage source, the current can be brought to zero. Since Φ of the surface is part of the contact potential, its changes relative to the reference electrode can be measured. A more extended description can be found in Ref. [79H3]. A very versatile instrument of this kind was developed by Besocke [76B]. Data collectionData have been collected for metal as well as semiconductor substrates. In the case of metals only elemental, single-crystalline samples were considered. There are a few exceptions to this general rule. Some metallic alloys are listed in case of single-crystalline samples of well defined (stoichiometric) composition. Some data are also incorporated for evaporated, mostly polycrystalline films of materials for which no single-crystal data are available. For semiconductor substrates, adsorbate-induced workfunction changes consist of two contributions: band-bending and electron-affinity changes. Systems were discarded for which the overall change in work function was small (<0.2 eV) or for which the authors did not report a separation of the two contributions. With respect to the adsorbates, only single-component adsorption layers were considered, i.e., co-adsorbates were omitted. Furthermore, it should be noted that completeness -although intended -could not be achieved. It was learned that work-function data are very often not in the center of a publication. Work-function data even seemed to many authors too marginal to give explicitly reference to them in the title, abstract or key words. Therefore, also computer based research could not guarant...
If an electron beam is directed towards a surface, it gets reflected if its potential is equal to -(E P /e + ∆Φ), the negative value of the primary energy divided by e and corrected for ∆Φ between the surface and the electron emitter (in the widest sense: cathode, electron gun, etc.). Since the surface serves here as the anode in a diode configuration, the name diode method has been chosen. This method was introduced early by P.A. Anderson [35A]. Many details of different experimental set-ups are discussed in [73K2, 79H3]. It was pointed out [85K8] that for carefully chosen conditions and for a patchy surface, i.e., a surface consisting of a composite of smaller areas of different work function, the diode method measures the same arithmetical average of Φ as the Kelvin method (see below). How to use a HREEL spectrometer for the diode method is reported in Ref.[85S3]. Vibrating capacitor method (Kelvin)The vibrating capacitor method is based on the work of Lord Kelvin [1898K] and of Zisman [32Z]. A condensor is formed of the surface to be studied and a reference electrode in front of it which are connected by a ammeter and a variable voltage source. If the capacitance between the plates (sample and reference electrode) is changed, e.g., by changing their distance, a current will flow. By compensating the Ref. p. 4.2-118] 4.2 Electron work function of metals and semiconductors Lando lt-Börnstein New Series III/42A2 4.2-7contact potential difference through the voltage source, the current can be brought to zero. Since Φ of the surface is part of the contact potential, its changes relative to the reference electrode can be measured. A more extended description can be found in Ref. [79H3]. A very versatile instrument of this kind was developed by Besocke [76B]. Data collectionData have been collected for metal as well as semiconductor substrates. In the case of metals only elemental, single-crystalline samples were considered. There are a few exceptions to this general rule. Some metallic alloys are listed in case of single-crystalline samples of well defined (stoichiometric) composition. Some data are also incorporated for evaporated, mostly polycrystalline films of materials for which no single-crystal data are available. For semiconductor substrates, adsorbate-induced workfunction changes consist of two contributions: band-bending and electron-affinity changes. Systems were discarded for which the overall change in work function was small (<0.2 eV) or for which the authors did not report a separation of the two contributions. With respect to the adsorbates, only single-component adsorption layers were considered, i.e., co-adsorbates were omitted. Furthermore, it should be noted that completeness -although intended -could not be achieved. It was learned that work-function data are very often not in the center of a publication. Work-function data even seemed to many authors too marginal to give explicitly reference to them in the title, abstract or key words. Therefore, also computer based research could not guarant...
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