Charge Photogeneration and Transfer in Polyaniline/Titanium Dioxide Heterostructure

Abstract

The photoinduction process in a p-n heterogeneous structure should be in correlation with the electronic properties of its semiconductor components. Based on that assumption, a double layer made of polyaniline (PANi) and titanium dioxide (TiO2) on glass substrate is used to investigate the charge photogenerated and transferred in the structure. The PANi layer is made by in situ polymerization of aniline in HCl acidic aqueous medium, while the TiO2 layer is made by thermolysis of TiCl3 dilute solution. It has been found that the PANi/TiO2 double layer is a composition of a PANi emeraldine salt layer (p-type semiconductor) covered by a TiO2 rutile layer (n-type conductor), creating a p-n heterogeneous structure. Upon exposure to the excitation light, the light sensitivity of the PANi layer in the PANi/TiO2 structure reveals a response mode distinct from those of the neat PANi layer. The conductance of the PANi layer in the coupling structure shows two modes of response: (1) a negative mode, i.e., a decrease in conductance in response to the excitation light of wavelength 369, 396 and 447 nm, and (2) a positive mode, namely an increase in conductance, as with the excitation light of wavelength 667 nm. On the other hand, the neat PANi layer simply shows a single positive response to excitation light. Those response modes account for a modulation of the PANi/TiO2 depletion region that in turn depends upon the photoexcited electrons and holes in the heterostructure. The diffusion of excess photogenerated electrons and holes over the heterojunction results in an expansion or reduction of depletion width that gives rise to an increase or decrease of the PANi layer conductance, i.e., a positive or negative response, respectively. In addition, the negative mode in response to the excitation light of wavelength 447 nm (~2.8 eV) is assumed to be an impact of the PANi in extending the photoinduction of the TiO2 component into the vision range at the blue region.