Optoelectronic and photovoltaic properties of graphene quantum dot–polyaniline nanostructures

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Abstract
In aqueous dispersions of graphene quantum dots (GQDs) produced by a sono-Fenton method, aniline is in situ polymerized to produce different polyaniline (PANI)–GQD hybrids (PAGD) without using external dopant. FTIR studies indicate that the carboxylic acid groups of the GQDs dope PANI well. The UV-Vis spectra exhibit a π to polaron band transition of the PAGD hybrids and show a gradual red shift with increasing intensity for increasing amounts of GQDs due to the gradual uncoiling and increase of polarons in the doped PANI chains. The fluorescence intensity of the GQDs is drastically quenched in the PAGD hybrids suggesting effective charge transfer between the GQDs and PANI chains. The X-ray diffraction study suggests the presence of a lamellar structure with a lamellar thickness of 13.57 Å. The morphologies of the PAGD hybrids studied using field emission scanning electron microscopy exhibit a change from flakes to rods with increasing GQD concentration, which has been attributed to the change from a flat to cylindrical lamella formation. The thermogravimetric analysis result indicates that, in comparison to HCl-doped PANI, the PAGD hybrids exhibit better thermal stability. In the PAGD composites the dc conductivity increases by three orders compared to that of the GQDs due to polaron formation in the PANI chains. The current–voltage (I–V) characteristics of the PAGD composites indicate semiconducting behaviour and on irradiation with light an almost reversible photoresponse occurs. Dye-sensitized solar cells (DSSCs) fabricated with the PAGD hybrids and N719 dye indicate a highest power conversion efficiency (PCE) of 3.12%. Impedance data of the PAGD hybrids exhibit semicircular Cole–Cole plots indicating the presence of a resistance (R)–capacitance (C) circuit where the capacitance is in parallel to the bulk resistance which increases with increasing GQD concentration. The Debye plot and the dielectric permittivity values also support the variation of the photovoltaic properties of the PAGD hybrids. The impedance spectra of the DSSCs indicate the presence of three semicircles exhibiting a complex equivalent circuit composed of three R–C circuits, and analysis of the data yields the lifetime values of photo-injected electrons supporting the PCE variation of the PAGD hybrids.

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