Kelvin probe method

For calculating the space-charge conductance (j(F,) we need to know the density of states g E) and the surface potential F,. Under favorable conditions, F, of a free surface can be obtained by the Kelvin probe method or from the saturation value of the surface photovoltage. These methods will be illustrated with some preliminary results obtained on a-Si H. We then shall discuss metastable light-induced changes of the surface potential and conductance. 

The state of the polymer surface and the polymer/elec-trolyte interface can be probed by measurement of the work function after initial polarization of the polymer-coated electrode in a liquid electrolyte. The latter is then withdrawn from the electrolyte ( emersed") under potential control, and then the work function measurement is performed [159,160]. The emersion procedure is schematized in Fig. 20.32. A widely used strategy for the work function measurement is based on the vibrating capacitor plate or the Kelvin probe method [161]. These methods rely on the fact that between two conducting and connected surfaces there exists a contact potential difference (CPD) because of the difference in work functions [162]. Changes in capacitance are induced by periodic vibration of one of the capacitor plates around its equilibrium position. The resulting ac current i is detected with a phase-sensitive detector and is given by... 

Fig. 20.33 Operating principle of the Kelvin probe method for measuring the work function.

Historically, the first and most important capacitance method is the vibrating capacitor approach implemented by Lord Kelvin in 1897. In this technique (now called the Kelvin probe), the reference plate moves relative to the sample surface at some constant frequency and tlie capacitance changes as tlie interelectrode separation changes. An AC current thus flows in the external circuit. Upon reduction of the electric field to zero, the AC current is also reduced to zero. Originally, Kelvin detected the zero point manually using his quadrant electrometer. Nowadays, there are many elegant and sensitive versions of this technique. A piezoceramic foil can be used to vibrate the reference plate. To minimize noise and maximize sensitivity, a phase-locked... 

The technique of photoemission electron spectroscopy (PEEM) is a particularly attractive and important one for spatially resolved work function measurements, as both the Kelvin probe technique and UPS are integral methods with very poor ( mm) spatial resolution. The PEEM technique, pioneered in the area of catalysis by Ertl,72-74 Block75 76 and Imbihl,28 has been used successfully to study catalytic oscillatory phenomena on noble metal surfaces.74,75... 

The relative work function and the relative electrode potential of electrodes in aqueous solutions and in inactive gases can be measured by a vibrating capacitor technique called Kelvin s method [Samec-Johnson-Doblhofer, 1992]. The Kelvin method estimates the difference in the work function between a test electrode and a Kelvin probe (KF) by measuring the applied voltage V at which the difference in the outer potential ij s- l KP between the test electrode and the Kelvin probe becomes zero (V = liJs - i Kp) as shown in Pig. 4—28. 

Let us pause and take an inventory of the situation up to this point. (1) We have a plausible mechanism of modulation of both components of WF of a selective layer (palladium) and (2) we have at least two methods of measurement of this effect, the macroscopic Kelvin probe and a field-effect transistor. However, the placement of the selective layer within the structure used for either measurement determines whether the effect is observable. In order to explain this caveat, we add another layer of the same metal M between Pd and the insulator in the structure shown in Fig. 6.33. This would correspond to the real life situation when we would try to connect a selective layer by a wire to the IGFET or a Kelvin Probe. It is not necessary to perform the same cycle as we did in Fig. 6.33. Instead, we add the individual energy contributions in the cycle, which begins and ends at the silicon Fermi level (moving again anticlockwise) ... 

The variation of the work function in the vertical direction of multilayers was investigated by Kelvin probe force microscopy (KPFM) on a fracture cross-section of a film deposited on a silicon substrate, shown in Fig. 2.18. This method is described in detail in [184]. A variation of the work function of about 60-100 meV is clearly seen from the bright-dark contrast as well... 

A further spatially resolved method, also based on work function contrast, is scanning Kelvin probe microscopy (SKPM). As an extended version of atomic force microscopy (AFM), additional information on the local surface potential is revealed by a second feedback circuit. The method delivers information depending on the value (p (p(x) + A x). Here, A(zS(x) is the difference in work function between the sample and the AFM tip and cp(x) is the local electric potential [12]. (p x) itself gives information on additional surface charges due to... 

For all nc-AFM measurements, a Kelvin probe force microscopy (KPFM) feedback controller was additionally activated for simultaneous topographic imaging [19]. In order to compensate for electrically or electronically induced artefacts, an ac voltage was applied between tip and sample and used in combination with lock-in techniques and a feedback controller to compensate for the contact potential difference (CPD) between tip and sample. With this method, nc-AFM is assiued to image the sample topography without any artefacts originating from different local surface potentials [20]. 

Second, channel potential measurements by Kelvin probe force microscopy and the four-probe method, which are described later in this chapter, indicate that the contact resistances and temperature dependences associated with the individual source and drain electrodes are nearly identical. From a thermionic emission... 

Characterizing these many aspects of microstructure is necessary to establish relationships between primary chemical structure, processing, and performance. Currently, the most commonly used methods are scanning probe microscopy techniques such as atomic force microscopy (AFM) or kelvin probe force microscopy... 

As the nature of the electrified interface dominates the kinetics of corrosive reactions, it is most desirable to measure, e.g., the drop in electrical potential across the interface, even where the interface is buried beneath a polymer layer and is therefore not accessible for conventional electrochemical techniques. The scanning Kelvin probe (SKP), which measures in principle the Volta potential difference (or contact potential difference) between the sample and a sensing probe (which may consist of a sharp wire composed of a conducting, stable phase such as graphite or gold) by the vibrating condenser method, is the only technique which allows the measurement of such data and therefore aU modern models which deal with electrochemical de-adhesion reactions are based on such techniques [1-8]. Recently, it has been apphed mainly for the measurement of electrode potentials at polymer/metal interfaces, especially polymer-coated metals such as iron, zinc, and aluminum alloys [9-15]. The principal features of a scanning Kelvin probe for corrosion studies are shown in Fig. 31.1. 

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