Photocurrent anodic

In dc amplification, the signal pulses from the phototube anode are converted into photocurrent and the voltage drop produced is read and the output displayed on a recorder. 

Figure 16 shows such PMC peaks in the depletion region for electrodes of Si,9 WSez8 and ZnO.12 They all appear near the onset of anodic photocurrents. They have different shapes, which, however, can easily be explained with the assumption of potential-dependent interfacial charge-transfer and charge recombination rates. 

Figured 16. PMC peaks in the depletion region near the onset of anodic photocurrents for Si,9 WSe2,8 and Zn0.iaThe clearly reduced width of the ZnO peak can be seen.

Figure 40. PMC peak measured with a ZnO single-crystal electrode in a microwave resonator near the onset of the anodic photocurrent.5...

Photocells The basic construction of a photocell is illustrated in Figure 17. A photocurrent flows when the photocathode is illuminated, this is proportional to the intensity of illumination if the supply potential has been chosen to be higher than the saturation potential. A minimal potential is required between the photocathode and the anode in order to be able to collect the electrons that are emitted. The sensitivity is independent of frequency up to 10 Hz. The temperature sensitivity of evacuated photocells is very small. The dark current (see below) is ca. 10 " A[l]. 

Peter LM, Reid ID, Scharifker BR (1981) Electrochemical adsorption and phase formation on mercury in sulphide ion solutions. 1 Electroanal Chem 119 73-91 Da Silva Pereira MI, Peter LM (1982) Photocurrent spectroscopy of semiconducting anodic films on mercury. J Electroanal Chem 131 167-179... 

The (photo)electrochemical behavior of p-InSe single-crystal vdW surface was studied in 0.5 M H2SO4 and 1.0 M NaOH solutions, in relation to the effect of surface steps on the crystal [183]. The pH-potential diagram was constructed, in order to examine the thermodynamic stability of the InSe crystals (Fig. 5.12). The mechanism of photoelectrochemical hydrogen evolution in 0.5 M H2SO4 and the effect of Pt modification were discussed. A several hundred mV anodic shift of the photocurrent onset potential was observed by depositing Pt on the semiconductor electrode. 

Because of the excess holes with an energy lower than the Fermi level that are present at the n-type semiconductor surface in contact with the solution, electron ttansitions from the solution to the semiconductor electrode are facilitated ( egress of holes from the electrode to the reacting species ), and anodic photocurrents arise. Such currents do not arise merely from an acceleration of reactions which, at the particular potential, will also occur in the dark. According to Eq. (29.6), the electrochemical potential, corresponds to a more positive value of electrode potential (E ) than that which actually exists (E). Hence, anodic reactions can occur at the electrode even with redox systems having an equilibrium potential more positive than E (between E and E ) (i.e., reactions that are prohibited in the dark). 

Photoirradiation of the modified electrode with nanoclusters of Cj qN alone or the mixture of C oN and MePH afforded anodic photocurrents. The photocurrent action spectrum was in fair agreement with the absorption spectrum of the THF-H2O (2 1) mixed solution containing nanoclusters of the mixture of CfioN and MePH or C oN alone. These results strongly indicate that the photocurrents can be ascribed to photoexcitation of the nanoclusters of C qN. ... 

In conclusion it should be mentioned that the same type of effects are possible for p-type electrodes. In this case an anodic dark current occurs whereas the photocurrent corresponds to an electron transfer via the conduction band (cathodic plEiotocurrent). 

The photocurrent is cathodic or anodic depending on the sign of the minority charge carriers injected from the semiconductor electrode into the electrolyte, i.e. the n-semiconductor electrode behaves as a photoanode and... 

Halmann reported in 1978 the first example of the reduction of carbon dioxide at a p-GaP electrode in an aqueous solution (0.05 M phosphate buffer, pH 6.8).95 At -1.0 V versus SCE, the initial photocurrent under C02 was 6 mA/ cm2, decreasing to 1 mA/cm2 after 24 h, while the dark current was 0.1 mA/cm2. In contrast to the electrochemical reduction of C02 on metal electrodes, formic acid, which is a main product at metal electrodes, was further reduced to formaldehyde and methanol at an illuminated p-GaP. Analysis of the solution after photoassisted electrolysis for 18 and 90 h showed that the products were 1.2 x 10-2 and 5 x 10 2 M formic acid, 3.2 x 10 4 and 2.8 x 10-4 M formaldehyde, and 1.1 x 10-4 and 8.1xlO 4M methanol, respectively. The maximum optical conversion efficiency calculated from Eq. (23) for production of formaldehyde and methanol (assuming 100% current efficiency) was 5.6 and 3.6%, respectively, where the bias voltage against a carbon anode was -0.8 to -0.9 V and 365-nm monochromatic light was used. In a later publication,4 these values were given as ca. 1% or less, where actual current efficiencies were taken into account [Eq. (24)]. 

If the same experiment is performed with an n-type Si electrode under identical illumination intensity the anodic photocurrent is found to be larger than for the p-type electrode under cathodic conditions. This increase is small (about 10%) for current densities in excess of JPS. Figure 3.2 shows that in this anodic regime injected electrons are also detected at p-type electrodes. This allows us to interpret the 10% increase in photocurrent observed at n-type electrodes as electron injection during anodic oxide formation and dissolution. 

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