Solvent vapor annealing for controlled pore expansion of block copolymer-assembled inorganic mesoporous films

Mesoporous inorganic thin films are promising materials architectures for a variety of high-value applications, ranging from optical coatings and purification membranes to sensing and energy storage devices. Having precise control over the structural parameters of the porous network is crucial for expanding their applicability. To this end, the use of block copolymers (BCP) as sacrificial structure-directing agents via micelle co-assembly is a particularly attractive route, since the resultant pore size is directly related to scaling laws for the radius of gyration of the pore-forming macromolecule. However, tailoring the molecular weight of the BCP via bespoke synthesis is an elaborate process that requires precise control over highly sensitive reactions conditions. Alternative methods have emerged, based on supramolecular assembly or the addition of different swelling agents, but, to-date, these present a negative impact on the structural order and pore size dispersity of the final inorganic mesoporous films. In this work, we propose a novel and effective method for control over pore size, porosity and structural order, which relies on a synergistic combination of BCP selective swelling via solvent vapor annealing (SVA) and locking of the structure by condensation of the inorganic sol-gel precursors. The results obtained in this work for TiO2 establish SVA as a new, straightforward, simple, and powerful route efor the fabrication of mesoporous thin-film materials with controllable structural characteristics.

Solvent-structured PEDOT:PSS surfaces: fabrication strategies and nanoscale properties

We present the preparation of nanostructured conducting PEDOT:PSS thin films by solvent vapor annealing (SVA), using the low boiling point solvent tetrahydrofuran (THF). An Atomic Force Microscopy (AFM) study allowed the observation of distinct nanostructure development as a function of solvent exposure time. Moreover, the nanostructures’ physical properties were evaluated by nanomechanical, nanoelectrical, and nano-FTIR measurements. In this way, we were able to differentiate the local response of the developed phases and to identify their chemical nature. The combination of these techniques allowed to demonstrate that exposure to THF is a facile method to effectively and selectively modify the surface nanostructure of PEDOT:PSS, and thereafter its final properties. Moreover, our nanoscale studies provided evidence about the molecular rearrangements that PEDOT:PSS suffers during nanostructure fabrication, a fundamental fact in order to expand the potential applications of this polymer in thermoelectric and optoelectronic devices.

Secondary Dopants of Electrically Conducting Polyanilines

Secondary dopants and the doping methods were identified for increasing the electrical conductivity of a highly processable and a primarily doped polyaniline dinonylnaphthalene sulfonic acid (PANI-DNNSA). The secondary doping was carried out using film, solution, and vapor doping methods. The doping methods and functional groups of secondary dopants were observed to play a critical role for inducing electrical characteristics of polyaniline. When secondary film doping method and p-toluenesulfonic acid were used, the electrical conductivity of the secondary doped polyaniline was measured to be increased from 0.16 to 334 S/cm. A novel vapor annealing doping method was developed to incorporate secondary dopants into solution cast polyaniline films.

Electron-to Hole Transport Change Induced by Solvent Vapor Annealing of Naphthalene Diimide Doped with Poly(3-Hexylthiophene)

Herein we report on fabrication and properties of organic field-effect transistors (OFETs) based on the spray-coated films of N,N′-dioctyl naphthalene diimide (NDIC8) doped with 2.4 wt% of poly (3-hexylthiophene) (P3HT). OFETs with the untreated NDIC8:P3HT films revealed electron conductivity [μe* = 5 × 10–4 cm2×(Vs)−1]. After the annealing in chloroform vapor the NDIC8:P3HT films revealed the hole transport only [μh* = 0.9 × 10–4 cm2×(Vs)−1]. Due to the chemical nature and energy levels, the hole transport was not expected for NDIC8-based system. Polarized optical- and scanning electron microscopies indicated that the solvent vapor annealing of the NDIC8:P3HT films caused a transition of their fine-grained morphology to the network of branched, dendritic crystallites. Grazing incidence wide-angle X-ray scattering studies indicated that the above transition was accompanied by a change in the crystal structure of NDIC8. The isotropic crystal structure of NDIC8 in the untreated film was identical to the known crystal structure of the bulk NDIC8. After the solvent annealing the crystal structure of NDIC8 changed to a not-yet-reported polymorph, that, unlike in the untreated film, was partially oriented with respect to the OFET substrate.