Effects of surface charges and surface states of chemically modified cadmium sulfide nanoparticles immobilized to gold electrode substrate on photoinduced charge transfers

Cadmium sulfide nanoparticles (Q-CdS) modified with 2-mercaptoethanesulfona te and 2-amiaoethanethiol in a molar ratio of 2:1 were covalently immobiliz ed onto-an Au surface covered with a self-assembled monolayer of 3,3'-dithi obis(succinimidylpropionate), and the resulting electrodes were further imm obilized with Q-CdS using glutaraldehyde as a binding agent. The degree:of anodic photocurrents was greatly influenced by charged conditions of hole s cavengers used because of the presence of sulfonate groups on the Q-CdS sur faces; triethylamine having positive charges gave large photocurrents, trie thanolamine medium photocurrents, and formate small photocurrents. If Q-CdS having a large emission from their surface trap states was used, anodic ph otocurrents were depressed with increasing anodic polarization from the ons et potentials which were ca. -1.1 V vs SCE for the use of any kinds of hole scavengers, and the greatest depression appeared at -0.25 V, beyond which a steep increase in anodic photocurrents was seen. In contrast, no signific ant depression in photocurrents was observed and anodic photocurrents were monotonically increased, in the case of using Q-CdS having an intense band- gap emission. When the energetic position at the emission maximum is correl ated to the potential at which the greatest photocurrent depression appeare d, photocurrent-potential characteristics are discussed in terms of involve ments of surface states in the photoelectrode reactions.