Reverse Currents, Electron and Hole Injection

Little is known about the mechanisms that cause the three other current extrema ]2 to J4. The kinetic and diffusional contributions of the characteristic currents Ji to J4 show a different concentration dependence. While the diffusion current is found to be roughly proportional to Cp, the kinetic current shows an exponent of 2 2.5 [Ha3]. No dependence of the characteristic currents to ]4 on doping kind and density is observed. This indicates again that to ]4 depend on mass transport and reaction kinetics rather than on charge supply. For n-type electrodes, of course, strong illumination is necessary in order to generate a sufficient number of minority carriers to support the currents. 

The second current maximum J3 corresponds to an oxide thickness at which tunneling of charge carriers becomes negligible, as shown in Fig. 4.7. At the bias corresponding to J3 the formation of anodic oxides in electrolyte-free HF shows a change of growth kinetics, as shown in Fig. 5.2. 

The existence of two types of mobile charge carriers in semiconductors enables us to distinguish between a majority charge carrier transferred from the electrode into the electrolyte and a minority charge carrier injected from the electrolyte into the electrode. Minority carrier injection causes significant reverse currents, but may also contribute to the total current under forward conditions. 

Electron Injection under Anodic Bias without Illumination 

If an n-type electrode is kept in the dark, the anodic dark current depends on properties of the semiconductor as well as on the chemical composition of the electrolyte. Measurements of dark current density need a defect-free Si surface. Scratches, barely visible to the eye, may increase the dark current by orders of magnitude. For the dark current density of a defect-free silicon electrode a dependence on the chemical environment is observed. 

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