RESUMO
Deposition of functionalized nanoparticles onto solid surfaces has created a new revolution in electronic devices. Surface adsorbates such as ionic surfactants or additives are often used to stabilize such nanoparticle suspensions; however, little is presently known about the influence of such surfactants and additives on specific electronic and chemical functionality of nanoparticulate electronic devices. This work combines experimental measurements and theoretical models to probe the role of an ionic surfactant in the fundamental physical chemistry and electronic charge carrier behavior of photodiode devices prepared using multicomponent organic electronic nanoparticles. A large capacitance was detected, which could be subsequently manipulated using the external stimuli of light, temperature, and electric fields. It was demonstrated that analyzing this capacitance through the framework of classical semiconductor analysis produced substantially misleading information on the electronic trap density of the nanoparticles. Electrochemical impedance measurements demonstrated that it is actually the stabilizing surfactant that creates capacitance through two distinct mechanisms, each of which influenced charge carrier behavior differently. The first mechanism involved a dipole layer created at the contact interfaces by mobile ions, a mechanism that could be replicated by addition of ions to solution-cast devices and was shown to be the major origin of restricted electronic performance. The second mechanism consisted of immobile ionic shells around individual nanoparticles and was shown to have a minor impact on device performance as it could be removed upon addition of electronic charge in the photodiodes through either illumination or external bias. The results confirmed that the surfactant ions do not create a significantly increased level of charge carrier traps as has been previously suspected, but rather, preventing the diffusion of mobile ions through the nanoparticulate film and their accumulation at contacts is critical to optimize the performance.
RESUMO
In this study we have optimised the preparation conditions for large-volume nanoparticle inks, based on poly(3-hexylthiophene) (P3HT):indene-C60 multiadducts (ICxA), through two purification processes: centrifugal and crossflow ultrafiltration. The impact of purification is twofold: firstly, removal of excess sodium dodecyl sulfate (SDS) surfactant from the ink and, secondly, concentration of the photoactive components in the ink. The removal of SDS was studied in detail both by a UV-vis spectroscopy-based method and by surface tension measurements of the nanoparticle ink filtrate; revealing that centrifugal ultrafiltration removed SDS at a higher rate than crossflow ultrafiltration even though a similar filter was applied in both cases (10,000 Da Mw cut-off). The influence of SDS concentration on the aqueous solar nanoparticle (ASNP) inks was investigated by monitoring the surface morphology/topography of the ASNP films using atomic force microscopy (AFM) and scanning electron microscopy (SEM) and photovoltaic device performance as a function of ultrafiltration (decreasing SDS content). The surface morphology/topography showed, as expected, a decreased number of SDS crystallites on the surface of the ASNP film with increased ultrafiltration steps. The device performance revealed distinct peaks in efficiency with ultrafiltration: centrifuge purified inks reached a maximum efficiency at a dilution factor of 7.8 × 104, while crossflow purified inks did not reach a maximum efficiency until a dilution factor of 6.1 × 109. This difference was ascribed to the different wetting properties of the prepared inks and was further corroborated by surface tension measurements of the ASNP inks which revealed that the peak efficiencies for both methods occurred for similar surface tension values of 48.1 and 48.8 mN m-1. This work demonstrates that addressing the surface tension of large-volume ASNP inks is key to the reproducible fabrication of nanoparticle photovoltaic devices.
