Electrochemical synthesis of a novel hybrid nanocomposite based on Co3O4 nanoparticles embedded in PANI- camphor sulfonic Acid matrix for optoelectronic applications

Abstract

In this study, we report on the preparation and characterization of Co3O4 nanoparticles (NPs) embedded in polyaniline-Camphor Sulfonic Acid (PANI-CSA) polymer matrix via electrochemical polymerization method. Developing conductive organic films with tunable optical properties are crucial for many novel optoelectronic applications. Thus, incorporation of metallic oxide nanoparticles (Co3O4 NPs) into polymer matrix (PANI-CSA) represents an alternative approach to address these desired features. As a result of careful optimization of several growth conditions, PANI-CSA/Co3O4 hybrid nanocomposites with high crystalline and homogeneous structures were successfully synthesized on ITO substrates. The impact of Co3O4 NPs concentrations on the structural and optical properties has been extensively investigated. A variety of structural and optical techniques, including FTIR, UV-VIS spectroscopy, and XRD, were employed to characterize the prepared hybrid nanocomposites. The initial findings and analysis reveal that the integration of Co3O4 NPs into PANI-CSA matrix have a trifunctional role in reducing π-polaron and Urbach energies (EU) whereas increasing π-π* band gaps. A further increase in NPs concentration up to 12 wt % results in continuous increase in the absorbance bands and absorption coefficients, indicating improved optical properties as compared to the control sample (PANI-CSA without NPs). The observed redshifts in absorbance band positions are attributed to narrowing of the optical band gap caused by interactions between PANI-CSA chains and Co3O4 NPs. FTIR spectra confirmed the exact chemical composition of PANI-CSA/Co3O4 nanocomposites, exhibiting broadened and less intense peaks compared to the control sample, indicating their interaction at the molecular levels. Additionally, XRD measurements indicate that no peaks of other phases were detected in all nanocomposites, demonstrating their purity and crystallinity. Finally, A single oscillator model by Wemple-DiDomenico (WDD) coupled with a Sellmeier dispersion relation based on one term has been utilized to model the typical electronic transition excitation energies, dispersion energies, optical conductivities, and many other optical desperation parameters for PANI-CSA and PANI-CSA/Co3O4 at various concentrations. For instance, in response to increased NPs content, linear optical susceptibility, third-order nonlinear optical susceptibility, and nonlinear refractive index decrease. In contrast, the ratio of free carriers to effective mass (N/m) increased from 4.73 × 1039 to 4.91 × 1039 m−3 kg−1 with increasing NPs concentration. Based on the observed results, these hybrid nanocomposites possess improved properties, indicating their potential use as active materials in a variety of novel optoelectronic applications.