Abstract
Photoactivities at inorganic/Organic/Interfaces (IOI) consisting of Zn-doped WO3 (Zn-WO3) /Poly 4-(Thiophen-3-yl) aniline (P3ThA) assemblies were investigated in nanoparticle suspensions and in thin solid film forms. The effects of P3ThA modifier on the photoelectrochemical behavior of the IOI were investigated using [Fe(CN)6]4- as a photoactive donor of hydrated electrons. Results show that the adsorption process of [Fe(CN)6]3- (photolysis product) controls the photoactivity outcomes of the IOI assemblies. P3ThA shows a greater heterogeneous photochemical response than native Zn-WO3. The band alignment between Zn-WO3 and P3ThA is of a p-p junction straddling gap type, where the charge transfer process is achieved through a hole transfer mechanism. The interface activities were explained by analyzing the IOI junction characteristics such as electron affinity, work function and hole/electron barrier heights. The creation of hybrid sub-band states close to the Fermi energy level at the interface was suggested. The aqueous nano-systems retained moderate stability as indicated by the reproducibility of their photocatalytic activities. Both [Fe(CN)6]4- and P3ThA contributed to the stability of the native Zn-WO3 surfaces.
Highlights
The quest for improving the solar to electrical energy conversion efficiencies in photovoltaic assemblies involved many techniques including the creation of the hybrid Inorganic/Organic interfaces or [IOI] (Wang Y. et al 2011, Kasem K. et al, 2008, Thomas K.G. et al 2003)
The band alignment between Zn-doped WO3 (Zn-WO3) and P3ThA is of a p-p junction straddling gap type, where the charge transfer process is achieved through a hole transfer mechanism
In the present work we report some of the photoelectrochemical behavior of 3ThA as the organic part of IOI assembly consists of Zn-doped WO3 /P3ThA nanoparticles
Summary
The quest for improving the solar to electrical energy conversion efficiencies in photovoltaic assemblies involved many techniques including the creation of the hybrid Inorganic/Organic interfaces or [IOI] (Wang Y. et al 2011, Kasem K. et al, 2008, Thomas K.G. et al 2003). Creating effective IOI requires energy coordination between the organic and inorganic interfaces for efficient charge transfer and separation as in heterojunction-type assemblies. Surface modification caused by formation of IOIs, can be a very effective way to create or eliminate defects and alter the energy band at inorganic /organic interfaces. This will alter the donor /acceptor character of the IOI assemblies. The proposed structure of P3ThA is illustrated in Figure 1 inset C Both polymer based aniline and polymer based thiophene have moderate to low band gap characters. In the present work we report some of the photoelectrochemical behavior of 3ThA as the organic part of IOI assembly consists of Zn-doped WO3 /P3ThA nanoparticles. Results correlate of the information about electronegativity [EA], Electron affinity [ κ ] , work function [Ф], barrier height [φ] band gap [Eg] and energy band alignments for components of the IOI
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