The Kelvin Probe experiment uses a nondestructive method to determine the relative work function difference between the probe and the sample. Work function describes the energy required to liberate an electron from the surface of a conductor; electrochemists often interpret this as the difference from an electrode’s Fermi Level, average energy of electrons, and that of vacuum.
A metal microprobe is positioned close to the surface of the sample (on the order of 100-microns). If the microprobe and sample are of different metals, there is an energy difference between their electrons. The microprobe is then electrically shorted to the sample, through internal electronics of the system. As a consequence, one metal forms a positive charge on its surface and the other metal forms a negative charge on its surface. The probe and sample are separated by a dielectric (air), so a capacitor is formed. The probe is then vibrated and "backing potential" or "nulling potential" is then applied sufficient to minimize this capacitance. At the applied voltage that causes the capacitance to go to zero, the original state is achieved. This value is recorded and charted.
Experiments are typically performed in ambient gaseous conditions, but several published examples use humidified environments. The underlying conducting sample can have an organic coating or paint applied.