Functional patterned coatings by thin polymer film dewetting.

An approach for the fabrication of functional polymer surface coatings is introduced, where micro-scale structure and surface functionality are obtained by means of self-assembly mechanisms. We illustrate two main applications of micro-patterned polymer surfaces obtained through dewetting of bilayers of thin polymer films. By tuning the physical and chemical properties of the polymer bilayers, micro-patterned surface coatings could be produced that have applications both for the selective attachment and patterning of proteins and cells, with potential applications as biomaterials, and for the collection of water from the atmosphere. In all cases, the aim is to achieve functional coatings using approaches that are simple to realize, use low cost materials and are potentially scalable.

Single Crystal, Luminescent Carbon Nitride Nanosheets Formed by Spontaneous Dissolution.

A primary method for the production of 2D nanosheets is liquid-phase delamination from their 3D layered bulk analogues. Most strategies currently achieve this objective by significant mechanical energy input or chemical modification but these processes are detrimental to the structure and properties of the resulting 2D nanomaterials. Bulk poly(triazine imide) (PTI)-based carbon nitrides are layered materials with a high degree of crystalline order. Here, we demonstrate that these semiconductors are spontaneously soluble in select polar aprotic solvents, that is, without any chemical or physical intervention. In contrast to more aggressive exfoliation strategies, this thermodynamically driven dissolution process perfectly maintains the crystallographic form of the starting material, yielding solutions of defect-free, hexagonal 2D nanosheets with a well-defined size distribution. This pristine nanosheet structure results in narrow, excitation-wavelength-independent photoluminescence emission spectra. Furthermore, by controlling the aggregation state of the nanosheets, we demonstrate that the emission wavelengths can be tuned from narrow UV to broad-band white. This has potential applicability to a range of optoelectronic devices.

Impact of Aggregation on the Photochemistry of Fullerene Films: Correlating Stability to Triplet Exciton Kinetics.

The photochemistry and stability of fullerene films is found to be strongly dependent upon film nanomorphology. In particular, PC61BM blend films, dispersed with polystyrene, are found to be more susceptible to photobleaching in air than the more aggregated neat films. This enhanced photobleaching correlated with increased oxygen quenching of PC61BM triplet states and the appearance of a carbonyl FTIR absorption band indicative of fullerene oxidation, suggesting PC61BM photo-oxidation is primarily due to triplet-mediated singlet oxygen generation. PC61BM films were observed to undergo photo-oxidation in air for even modest (≤40 min) irradiation times, degrading electron mobility substantially, indicative of electron trap formation. This conclusion is supported by observation of red shifts in photo- and electro-luminescence with photo-oxidation, shown to be in agreement with time-dependent density functional theory calculations of defect generation. These results provide important implications on the environmental stability of PC61BM-based films and devices.

Evidence for ion migration in hybrid perovskite solar cells with minimal hysteresis.

Ion migration has been proposed as a possible cause of photovoltaic current-voltage hysteresis in hybrid perovskite solar cells. A major objection to this hypothesis is that hysteresis can be reduced by changing the interfacial contact materials; however, this is unlikely to significantly influence the behaviour of mobile ionic charge within the perovskite phase. Here, we show that the primary effects of ion migration can be observed regardless of whether the contacts were changed to give devices with or without significant hysteresis. Transient optoelectronic measurements combined with device simulations indicate that electric-field screening, consistent with ion migration, is similar in both high and low hysteresis CH3NH3PbI3 cells. Simulation of the photovoltage and photocurrent transients shows that hysteresis requires the combination of both mobile ionic charge and recombination near the perovskite-contact interfaces. Passivating contact recombination results in higher photogenerated charge concentrations at forward bias which screen the ionic charge, reducing hysteresis.

Protein micropatterns by PEG grafting on Dewetted PLGA films.

The ability to control protein and cell positioning on a microscopic scale is crucial in many biomedical applications, such as single cell studies. We have developed and investigated the grafting of poly(ethylene glycol) (PEG) brushes onto poly(d,l-lactide-co-glycolide) (PLGA) thin films, which can be micropatterned by exploiting their spontaneous dewetting on top of polystyrene (PS) films. Dense PEG brushes with excellent protein repellence were achieved on PLGA by using cloud point grafting conditions, and selective adsorption of proteins on the micropatterned substrates was achieved by exploiting the different affinity protein adsorption onto the PEG brushes and the PS holes. PEG-grafted PLGA films showed better resistance against spontaneous degradation in buffer than bare PLGA films, due to passivation by the thin PEG coating. The simplicity of dewetting and subsequent grafting approaches, coupled with the ability to coat and pattern nonplanar substrates give rise to possible applications of PEG-grafted PLGA films in single cell studies and cell cultures for tissue engineering.

Competition between dewetting and cross-linking in poly(N-vinylpyrrolidone)/polystyrene bilayer films.

We investigated the dewetting of metastable poly(N-vinylpyrrolidone) (PNVP) thin films (45 nm) on top of polystyrene (PS) thin films (58 nm) as a function of annealing temperature and molecular weight of PS (96 and 6850 kg/mol). We focused on the competition between dewetting, occurring as a result of unfavorable intermolecular interactions at the PNVP/PS interface, and spontaneous cross-linking of PNVP, occurring during thermal annealing, as we recently reported (Telford, A. M.; James, M.; Meagher, L.; Neto, C. ACS Appl. Mater. Interfaces 2010, 2, 2399-2408). Using optical microscopy, we studied how the dewetting morphology and dynamics at different temperatures depended on the relative viscosity of the top PNVP film, which increased with cross-linking time, and of the bottom PS film. In the PNVP/PS96K system, cross-linking dominated over dewetting at temperatures below 180 °C, reducing drastically nucleated hole density and their maximum size, while above 180 °C the two processes reversed, with complete dewetting occurring at 200 °C. On the other hand, the PNVP/PS6850K system never achieved advanced dewetting stages as the dewetting was slower than cross-linking in the investigated temperature range. In both systems, dewetting of the PNVP films could be avoided altogether by thermally annealing the bilayers at temperatures where cross-linking dominated. The cross-linking was characterized quantitatively using neutron reflectometry, which indicated shrinkage and densification of the PNVP film, and qualitatively through selective removal of the bottom PS film. A simple model accounting for progressive cross-linking during the dewetting process predicted well the observed hole growth profiles and produced estimates of the PNVP cross-linking rate coefficients and of the activation energy of the process, in good agreement with literature values for similar systems.

Thermally cross-linked PNVP films as antifouling coatings for biomedical applications.

Protein repellent coatings are widely applied to biomedical devices in order to reduce the nonspecific adhesion of plasma proteins, which can lead to failure of the device. Poly(N-vinylpyrrolidone) (PNVP) is a neutral, hydrophilic polymer with outstanding antifouling properties often used in these applications. In this paper, we characterize for the first time a cross-linking mechanism that spontaneously occurs in PNVP films upon thermal annealing. The degree of cross-linking of PNVP films and their solubility in water can be tailored by controlling the annealing, with no need for additional chemical treatment or irradiation. The physicochemical properties of the cross-linked films were investigated by X-ray photoelectron spectroscopy, infrared spectroscopy, neutron and X-ray reflectometry, ellipsometry, and atomic force microscopy, and a mechanism for the thermally induced cross-linking based on radical formation was proposed. The treated films are insoluble in water and robust upon immersion in harsh acid environment, and maintain the excellent protein-repellent properties of unmodified PNVP, as demonstrated by testing fibrinogen and immunoglobulin G adsorption with a quartz crystal microbalance. Thermal cross-linking of PNVP films could be exploited in a wide range of biotechnological applications to give antifouling properties to objects of any size, essentially making this an alternative to high-tech surface modification techniques.