Photochemically-induced refractive index and fluoresence patterning on polymer films

The molecular design for large photo-induced refractive index changes in transparent visible light region was proposed and realized with norbornadiene polymers and poly(vinyl cinnamate). The patterning of pure refractive-index contract on their transparent films was made with near-field scanning optical microscopy (NSOM). Reversible fluorescence patterning on polymer films is also presented by using controlled energy transfer from a fluorescent pyromethene to a photochromic diarylethene.     

Reversible chemical patterning on stimuli-responsive polymer film: environment-responsive lithography

We report on a novel type of chemical patterning based on thin stimuli-responsive polymer films. The basic concept is the permanent storage (writing) of a pattern, which is reversibly developed and erased upon exposure to appropriate environment, e.g., solvent, pH, and temperature. The smart surface is fabricated from the mixed brush of poly(2-vinylpyridine) and polyisoprene. The mixed brush demonstrates switching behavior upon exposure to different solvents. Cross-linking of polyisoprene via illumination through a photomask results in formation of patterns with suppressed switching. Due to the contrast in switching between illuminated and dark areas, exposure of the smart surface to different solvents causes either reversible formation or erasing of chemical contrast between the illuminated and dark areas. Thus, the pattern surface can very locally attract colloidal particles or can be wetted by water only upon exposure to the special solvent which introduces the contrast between the illuminated and dark areas. Appearance of the patterns indicates particular environment and can be used for local switching of adsorption.     

Focused laser-induced marangoni dewetting for patterning polymer thin films

Highly-localized focused laser spike (FLaSk) heating of polymer thin films is a resist- and developer-free alternative to two-dimensional (2D) laser direct write for creating patterns on the single micron or, by exploiting overlap effects, submicron scale. The massive temporal and spatial thermal gradients and resulting thermal Marangoni stresses generated by FLaSk are an effective means for the directed dewetting and patterning of such films. Here, the general applicability of this technique to glassy amorphous polymer thin film systems is investigated through systematic investigation of film thickness, glass transition temperature, and polymer mobility. The results reveal that the important parameters are the film thickness (coupled to the optical heating effects through anti-reflection coating effects) and the high-temperature polymer melt mobility, allowing for generation of single features with linewidths of down to ∼1 μm. Further, the introduction of spatial mobility variations by using polymer brushes, bilayers, and microphase separated block copolymers leads to additional profile manipulation effects (i.e. spontaneous 2D pattern generation and flattened top profiles). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 225–236     

Chemical patterning of ultrathin polymer films by direct-write multiphoton lithography

We applied 2-photon laser ablation to write subdiffraction nanoscale chemical patterns into ultrathin polymer films under ambient conditions. Poly(ethylene glycol) methacrylate brush layers were prepared on quartz substrates via surface-initiated atom-transfer radical polymerization and ablated to expose the underlying substrate using the nonlinear 2-photon absorbance of a frequency-doubled Ti:sapphire femtosecond laser. Single-shot ablation thresholds of polymer films were ~1.5 times smaller than that of a quartz substrate, which allowed patterning of nanoscale features without damage to the underlying substrate. At a 1/e(2) laser spot diameter of 0.86 μm, the features of exposed substrate approached ~80 nm, well below the diffraction limit for 400 nm light. Ablated features were chemically distinct and amenable to chemical modification.     

Effects of temperature and chemical modification on polymer Langmuir films

We previously reported on a rheological study of Langmuir films of poly(tert-butyl methacrylate) (PtBMA), and this work describes further studies on this system. Here, surface pressure-area (Pi-A) isotherms and interfacial shear rheology experiments are performed to better understand the effects of two modifications: varying the temperature between 5 and 40 degrees C and introducing small amounts of carboxylic acid groups by partially hydrolyzing the polymer. Increased temperature produced isotherms with lower plateau surface pressures, Pip, and Pi values shifted to lower areas above Pip. Film properties transition from being primarily viscous to being dominated by elasticity as Pip is crossed for all temperatures studied, even as the value of Pip changes. Increasing the hydrolysis fraction leads to isotherms shifted to lower areas throughout the curve and higher Pip values. Both temperature variation and chemical modification are believed to affect the relative importance of polymer-polymer and polymer-subphase interactions.     

Electron-beam-induced topographical, chemical, and structural patterning of amorphous titanium oxide films

Electrolytically deposited amorphous TiO2 films on steel are remarkably sensitive to electron beam (e-beam) irradiation at moderate energies at 20 keV, resulting in controlled local oxide reduction and crystallization, opening the possibility for local topographical, chemical, and structural modifications within a biocompatible, amorphous, and semiconducting matrix. The sensitivity is shown to vary significantly with the annealing temperature of as-deposited films. Well-defined irradiation conditions in terms of probe current IP (5 microA) and beam size were achieved with an electron probe microanalyzer. As shown by atomic force and optical microscopy, micro-Raman spectroscopy, wavelength-dispersive X-ray (WDX), and Auger analyses, e-beam exposure below 1 Acm-2 immediately leads to electron-stimulated oxygen desorption, resulting in a well-defined volume loss primarily limited to the irradiated zone under the electron probe and in a blue color shift in this zone because of the presence of Ti2O3. Irradiation at 5 Acm(-2) (IP = 5 microA) results in local crystallization into anatase phase within 1 s of exposure and in reduction to TiO after an extended exposure of 60 s. Further reduction to the metallic state could be observed after 60 s of exposure at approximately 160 Acm(-2). The local reduction could be qualitatively sensed with WDX analysis and Auger line scans. An estimation of the film temperature in the beam center indicates that crystallization occurs at less than 150 degrees C, well below the atmospheric crystallization temperature of the present films. The high e-beam sensitivity in combination with the well-defined volume loss from oxygen desorption allows for precise electron lithographic topographical patterning of the present oxides. Irradiation effects leading to the observed reduction and crystallization phenomena under moderate electron energies are discussed.     

Grayscale patterning of polymer thin films with nanometer precision by direct-write multiphoton photolithography

The fabrication of arbitrary grayscale patterns in poly(ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) thin films is demonstrated. Patterns are formed by ablative direct-write multiphoton lithography using a sample scanning microscope and 870-nm light from a mode-locked Ti:sapphire laser. The surface profiles of all etched samples are characterized by atomic force microscopy. Grayscale patterns are produced by modulating the laser focus during etching. Quantitative models describing the etch depth as a function of laser power and focus are presented and employed to reproducibly control film patterning. PEDOT:PSS is found to be etched by a combination of linear and nonlinear optical processes. Sensitization by PEDOT in the composite is concluded to facilitiate removal of PSS. An ultimate etch depth precision of 1 nm is achieved.     

Preparation of new photosensitive TiO2 gel films using chemical additives including nitrogen and their patterning

TiO₂ gel films were prepared from titanium tetra-n-butoxide chemically modified with benzoylacetoanilide including nitrogen by the sol-gel method. The obtained gel film showed an absorption band, characteristic of the chelate ring, at 325 nm. The absorption band disappeared almost completely with UV-irradiation (2.7 J cm⁻²) using a high pressure mercury lamp. This indicates that the gel film exhibits photosensitivity. The decomposition rate of the chelate ring was the fastest in the photosensitive TiO₂ gel films which we have examined. Using the photosensitivity, fine patterns (about 5 μm) could be fabricated by UV-irradiation through a mask and leaching.     

Microscale plasma-initiated patterning of electrospun polymer scaffolds

Microscale plasma-initiated patterning (μPIP) is a novel micropatterning technique used to create biomolecular micropatterns on polymer surfaces. The patterning method uses a polydimethylsiloxane (PDMS) stamp to selectively protect regions of an underlying substrate from oxygen plasma treatment resulting in hydrophobic and hydrophilic regions. Preferential adsorption of the biomolecules onto either the plasma-exposed (hydrophilic) or plasma-protected (hydrophobic) regions leads to the biomolecular micropatterns. In the current work, laminin-1 was applied to an electrospun polyamide nanofibrillar matrix following plasma treatment. Radial glial clones (neural precursors) selectively adhered to these patterned matrices following the contours of proteins on the surface. This work demonstrates that textured surfaces, such as nanofibrillar scaffolds, can be micropatterned to provide external chemical cues for cellular organization.     

Marangoni effects on evaporative lithographic patterning of colloidal films

We investigate the effects of Marangoni stresses on the evaporative lithographic patterning of colloidal films (Harris, D. J.; Hu, H.; Conrad, J. C.; Lewis, J. A. Phys. Rev. Lett. 2007, 98 (14), 148301). Films are dried beneath a mask that induces periodically varying regions of free and hindered evaporation. Direct imaging reveals that silica microspheres suspended within an organic solvent exhibit recirculating flows induced by temperature and surface tension gradients that arise during drying. The films display remarkable pattern formation with a majority of the particles deposited in the masked regions. Above a critical colloid volume fraction, recirculating flows are suppressed, leading to particle deposition in unmasked regions of high evaporative flux.     

Spore-terminated cantilevers for chemical patterning on complex architectures

Atomic force microscope tips terminated with spore cells are used to directly pattern onto glass and tissue surfaces. The spore cells act as sponges and eliminate the need to use microfabricated ink reservoirs during lithography.     

Controlled deposition of structured polymer films: chemical and rheological factors in chitosan film formation

The technique of "spread coating" has been used to create thin films from solutions of deacetylated and butyl-modified chitosan polymer, and the effect of deposition rate on film thickness has been characterized. Results show that films of controlled thickness can be reproducibly produced and that hydrophobic modification of the polymer can extend the range over which a linear response between film thickness and deposition rate is achieved. Viscometry and fluorescence spectroscopy were also employed to characterize the micellar characteristics of solutions of both deacetylated and butyl-modified chitosan polymer. Although both deacetylated and butyl-modified chitosan solutions were found to have inter- and intramolecular interactions, as well as hydrophobic domains able to incorporate fluorophores, deacetylated chitosan was found to be more interconnected via intermolecular interactions at higher concentrations. These results are important as having the ability to understand how the introduction of hydrophobic modification, a technique shown to introduce solution-based micelle structure and micellar aggregates that support enzyme immobilization, affects film thickness and morphology of spread coated thin films will aid the long-term development and deployment of chitosan-based biofuel cell electrodes.     

Photoreactions and lateral patterning in Langmuir and Langmuir-Blodgett films

Reversible morphological changes occur with photoisomerization of azobenzene in Langmuir-Blodgett (LB) films complexed with polycations, which contradicts an implicit assumption of the concept of free volume that two-dimensional film structures are preserved during the photoisomerization. J-aggregates of chromophores are formed by two processes. The first process is "light-induced J-aggregation" in which photoisomerized molecules form J-aggregates. The other process is "triggered J-aggregation," in which photoisomerization of one of the components triggers J-aggregation of another chemical species in the mixed films. Both processes of J-aggregation are in many cases accompanied by large morphological changes of the films. However, LB films fabricated using processes under isobaric conditions do not change their morphology during light-induced J-aggregation and are patterned with J-aggregates using ultraviolet illumination through a photomask. Phase separation in mixed LB films gives rise to two-dimensional patterns, which are used to fabricate templates by using an amphiphilic silane-coupling agent as one of the components in the mixed LB films. Nanopatterns are also fabricated.     

Rupture of thin films with resonant substrate patterning

We study the stability and rupture of thin liquid films on patterned substrates. It is shown that striped patterning on a length scale comparable to that of the spinodal instability leads to a resonance effect and an imperfect bifurcation of equilibrium film shapes. Weakly nonlinear analysis gives predictions for film shapes, stability, growth rates, and rupture times, which are confirmed by numerical solution of the thin-film equation. Film behavior is qualitatively different in the resonant patterning regime, but with sufficiently large domains rupture occurs on a spinodal length scale regardless of patterning. Instabilities transverse to the patterning are examined and shown to behave similarly as disturbances to films on uniform substrates. We explain some previously reported effects in terms of the imperfect bifurcation.     

Charge driven, electrohydrodynamic patterning of thin films

In electrohydrodynamic patterning, electrical forces and surface tension acting at the interface between two fluids sandwiched between silicon wafers compete to set the period of pillar arrays, gratings, and concentric rings. Shrinking the period to deep submicron lengths requires a precise understanding of the source of the electric field. Previous modeling efforts have assumed that applied voltages, contact potentials, and static charge drive the flow. Here we show the location of that charge and the tangential stress it engenders to impact profoundly how the period and growth rate depend on the dielectric contrast and the relative film thickness. The pillar-to-pillar spacing scales inversely proportional to the charge density, and densities of approximately 1 mC/m(2) (approximately 1 charge/100 nm(2)) suffice to produce micron sized pillars.     

Confinement of surface patterning in azo-polymer thin films

Azobenzene polymer thin films are known to spontaneously generate surface patterns in response to incident light gradients. This peculiar process is investigated in terms of the dynamics of the various azobenzene photomotions, which occur on different length scales. In particular, the formation and thermal erasure of surface relief gratings are measured as a function of film thickness and by using combinatorial samples with thickness gradients. The thermal erasure of gratings in this system provides a direct measure of the glass-transition temperature, which is found to deviate substantially from the bulk value. Thin azo films exhibit a glass transition up to 50 K higher than the bulk. These dynamical measurements allow the authors to probe the length scale of mass transport, which is found to be approximately 150 nm. Furthermore, surface mass transport is completely arrested in thin films<40 nm. According to these results, mass transport involves the coordinated motion of many polymer chains in the depth of the sample, rather than surface diffusion of individual chains.