Spin-cast Thin Films Research Articles

Microstructural influence on thermal stability of ferroelectric properties in P(VDF-TrFE) spin cast thin films

Ferroelectric polymers, like poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)), find applications across various fields due to their unique mechanical and electrical properties. This study investigates the impact of thermal loading up to 90 °C on the ferroelectric characteristics of two distinct microstructures, spherulite-like and rice-like, formed during the thermal annealing after deposition of P(VDF-TrFE) thin films. Thermal cycles revealed a reduced ferroelectric activity in spherulite-like sample, in contrast to the ferroelectric stability observed in the rice-like counterparts. XRD analyses indicate that this behaviour is due to a crystalline phase stabilization of the γ-2b phase in the spherulite-like thin films. Furthermore, energy characteristics investigations highlighted a better performance of the pristine spherulite-like compared to the rice-like microstructure. All in all, despite these performance differences, our findings remark that careful considerations are needed in potential applications of P(VDF-TrFE) thin films where reliability and precision across a wide range of operating temperatures are required.

Periodic Photobleaching with Structured Illumination for Diffusion Imaging.

The use of periodically structured illumination coupled with spatial Fourier-transform fluorescence recovery after photobleaching (FT-FRAP) was shown to support diffusivity mapping within segmented domains of arbitrary shape. Periodic "comb-bleach" patterning of the excitation beam during photobleaching encoded spatial maps of diffusion onto harmonic peaks in the spatial Fourier transform. Diffusion manifests as a simple exponential decay of a given harmonic, improving the signal to noise ratio and simplifying mathematical analysis. Image segmentation prior to Fourier transformation was shown to support pooling for signal to noise enhancement for regions of arbitrary shape expected to exhibit similar diffusivity within a domain. Following proof-of-concept analyses based on simulations with known ground-truth maps, diffusion imaging by FT-FRAP was used to map spatially-resolved diffusion differences within phase-separated domains of model amorphous solid dispersion spin-cast thin films. Notably, multi-harmonic analysis by FT-FRAP was able to definitively discriminate and quantify the roles of internal diffusion and exchange to higher mobility interfacial layers in modeling the recovery kinetics within thin amorphous/amorphous phase-separated domains, with interfacial diffusion playing a critical role in recovery. These results have direct implications for the design of amorphous systems for stable storage and efficacious delivery of therapeutic molecules.

Neutron reflectivity study on the nanostructure of PMMA chains near substrate interfaces based on contrast variation accompanied with small molecule sorption.

In the case of poly(methyl methacrylate) (PMMA) thin films on a Si substrate, thermal annealing induces the formation of a layer of PMMA chains tightly adsorbed near the substrate interface, and the strongly adsorbed PMMA remains on the substrate, even after washing with toluene (hereinafter called adsorbed sample). Neutron reflectometry revealed that the concerned structure consists of three layers: an inner layer (tightly bound on the substrate), a middle layer (bulk-like), and an outer layer (surface) in the adsorbed sample. When an adsorbed sample was exposed to toluene vapor, it became clear that, between the solid adsorption layer (which does not swell) and bulk-like swollen layer, there was a "buffer layer" that could sorb more toluene molecules than the bulk-like layer. This buffer layer was found not only in the adsorbed sample but also in the standard spin-cast PMMA thin films on the substrate. When the polymer chains were firmly adsorbed and immobilized on the Si substrate, the freedom of the possible structure right next to the tightly bound layer was reduced, which restricted the relaxation of the conformation of the polymer chain strongly. The "buffer layer" was manifested by the sorption of toluene with different scattering length density contrasts.

Investigating Neurogenic Differentiation of Dental Pulp Stem Cells Using PLA and Graphene Thin-Film and Electrospun Fiber Scaffolds in Vitro

Dental pulp derived cells are pluripotent stem cells which can be differentiated along odontogenic, osteogenic, adipogenic, or neurogenic lineages. Odontogenic and osteogenic differentiation, in the absence of dexamethasone, have been shown to be highly dependent on substrate morphology and mechanics. Here we focus on neurogenic differentiation, using the protocol described by A. Arthur et al., and its dependence on substrate nature. DPSCs were cultured on PLA, a biodegradable polymer approved for internal use. The upregulation of genetic markers was compared with that of cells plated on standard TCP. The role of substrate morphology was investigated by plating on electrospun fibers approximately 2.0 ± 1.0 μm in diameter and on spin-cast thin films. The influence of graphene was investigated through the addition of 3% and 10% graphene nanoparticles to the films and fibers respectively. The aspect ratio of the cells was measured using confocal microscopy. Cells grown on graphene containing substrates had larger aspect ratios than their non-graphene counterparts, and cells grown on microfibers were longer than their counterparts on the flat films. But the cell aspect ratio did not necessarily correlate with genetic differentiation. The results after 21 days of incubation indicated that early markers (TBP, β-III tubulin), decreased uniformly on all substrates relative to day 0, with the largest decrease occurring on the PLA flat film with graphene. The late stage marker, NEFM, which indicates differentiation, was upregulated to a significantly larger extent on all PLA substrates. No difference was observed between the fibers and the flat film in the absence of graphene, thus morphology did not play a significant role on this polymer. Addition of graphene did not affect the outcome on the fibers, but significantly suppressed the gene expression on the flat films. These results indicate that PLA is a promising scaffold material for neurogenic differentiation.

Influence of solvent and molecular weight in wrinkle formation in spin-cast polystyrene thin films

The surface morphology of polystyrene thin films formed from various molecular weight polystyrene and solvent conditions is studied. When spin-cast from tetrahydrofuran (THF) wrinkles are formed at the extremities that have periodicity with wavelengths in the μm range and amplitudes in the nm range but varies with molecular weight. A mixed solvent system consisting of THF and dimethylformamide (DMF) leads to periodic structures only with THF-rich compositions. THF and DMF have similar properties relevant to spin-casting: density, surface tension, molecular weight, and viscosity but different boiling points and room temperature vapor pressures, demonstrating that formation periodicity requires a volatile solvent. The formation of the surface structures is attributed to the Marangoni effect and the film thicknesses and wave parameters are shown to be consistent with literature models.

Self-Organization of Triblock Copolymer Melt Chains Physisorbed on Non-neutral Surfaces.

We here report the self-organization process of poly(styrene-b-ethylene/butadiene-b-styrene) (SEBS) triblock copolymer chains physically adsorbed on a non-neutral surface. Spin-cast SEBS thin films were prepared on silicon (Si) substrates and then annealed at a high temperature far above the bulk glass transition temperatures of the two constituent blocks. To reveal the buried interfacial structure, we utilized solvent rinsing processes and a suite of surface-sensitive techniques including ellipsometry, X-ray reflectivity, atomic force microscopy, and grazing incidence small angle X-ray scattering. We revealed that the SEBS chains form two different chain structures on the substrate simultaneously: (i) “flattened chains” with the average height of 2.5 nm but without forming microdomain structures; (ii) “loosely adsorbed chains” with the average height of 11.0 nm and the formation of perpendicularly oriented cylindrical microdomains to the substrate surface. In addition, the kinetics to form the perpendicular-oriented cylinder was sluggish (∼200 h) and proceeded via multistep processes toward the equilibrium state. We also found that the lateral microdomain structures were distorted, and the characteristic lengths of the microdomains were slightly different from the bulk even after reaching “quasiequilibrium” state within the observed time window. Furthermore, we highlight the vital role of the adsorbed chains in the self-assembling process of the entire SEBS thin film: a long-range perturbation associated with the adsorbed chains propagates into the film interior, overwhelming the free surface effect associated with surface segregation of the lower surface tension of polystyrene blocks.

Molecular glasses of azobenzene for holographic data storage applications

A series of D-N=N-A type molecular glasses where the electron acceptor part (A) contains several electron withdrawing substituents, but the electron donating part (D) of the glassy azochromophores contains amorphous phase promoting non-conjugated bulky triphenyl or hydroxyl groups have been synthesized and investigated. Results showed that the azodye physical properties depend not only on the incorporated electron withdrawing substituents but are also influenced by the bonding type of covalently attached bulky moieties. Synthesized glassy azocompounds showed glass transition temperatures up to 106 °C and thermal stability up to 312 °C.The ability to form holographic gratings in spin-cast thin films of the glassy azodyes was investigated using 532 nm and 633 nm lasers obtaining diffraction efficiency up to 57%, self-diffraction efficiency up to 15% and photosensitivity as high as 3.7 J/(cm2%). Surface relief grating (SRG) depths reached 1.1 μm and in some cases even exceeded the thickness of the films.

Substrate-Dependent Physical Aging of Confined Nafion Thin Films.

The humidity-induced physical aging, or structural relaxation, of spin-cast Nafion thin films on gold, carbon, and native oxide silicon (n-SiO2) substrates was examined using spectroscopic ellipsometry (SE). Physical aging rates, β, were calculated from the change in measured sample thickness, h, upon exposure to controlled humidity. Three Nafion films, h = 188, 57, and 27 nm, deposited on gold substrates demonstrated an increased β with decreasing thickness due to confinement. The Nafion film on n-SiO2, h = 165 nm, also showed a humidity-induced aging, while a Nafion film deposited on carbon, h = 190 nm, exhibited no measurable humidity-induced aging. The reported rate of aging was related to the strength of the polymer/substrate interactions during film formation. Strong interactions between Nafion and the gold and n-SiO2 substrates anchored the thin film to the substrate during film formation, resulting in a nonequilibrium as-cast film and subsequent relaxation upon exposure to water vapor until complete plasticization. Weak interactions between the carbon substrate and Nafion resulted in fully relaxed as-cast films which displayed no relaxation upon hydration.

Elongated phase separation domains in spin-cast polymer blend thin films characterized using a panoramic image.

Polymer thin films with micro/nano-structures can be prepared by a solvent evaporation induced phase separation process via spin-casting a polymer blend, where the elongated phase separation domains are always inevitable. The striation defect, as a thickness nonunifomity in spin-cast films, is generally coexistent with the elongated domains. Herein, the morphologies of polymer blend thin films are recorded from the spin-cast center to the edge in a panoramic view. The elongated domains are inclined to appear at the ridge regions of striations with increasing radial distance and align radially, exhibiting a coupling between the phase separation morphology and the striation defect that may exist. We demonstrate that the formation of elongated domains is not attributed to shape deformation, but is accomplished in situ. A possible model to describe the initiation and evolution of the polymer blend phase separation morphology during spin-casting is proposed.

Irreversible Adsorption Governs the Equilibration of Thin Polymer Films.

We demonstrate that the enhanced segmental motion commonly observed in spin cast thin polymer films is a nonequilibrium phenomenon. In the presence of nonrepulsive interfaces, prolonged annealing in the liquid state allows, in fact, recovering bulk segmental mobility. Our measurements prove that, while the fraction of unrelaxed chains increases upon nanoconfinement, the dynamics of equilibration is almost unaffected by the film thickness. We show that the rate of equilibration of nanoconfined chains does not depend on the structural relaxation process but on the feasibility to form an adsorbed layer. We propose that the equilibration of the thin polymer melts is driven by the slow relaxation of interfacial chains upon irreversible adsorption on the confining walls.

Detection of Ultralow Concentrations of Non-emissive Conjugated Polymer Aggregates via Fluorescence Correlation Spectroscopy.

The aggregation of conjugated polymers in common organic solvents is investigated using fluorescence correlation spectroscopy (FCS), burst analysis, and microscopy. Poly(3-hexylthiophene) and poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] are both shown to form weakly bonded non-emissive aggregates in toluene that persist even at picomolar concentrations. These aggregates decrease the bulk emission intensity in solution but do not affect the fluorescence spectra or lifetimes, consistent with a static quenching mechanism. Passing the solutions through a syringe filter causes an increase in the number of emitters as measured by FCS, indicating that this process dissociates the aggregates. Films cast from solutions that have been filtered are more uniform and significantly more emissive than those made from unfiltered solutions. These results show that FCS is a highly sensitive probe of non-emissive aggregates in solution that have a deleterious effect on the emission properties and overall quality of spin-cast thin films, even at sub-nanomolar concentrations.

Semifluorinated Synergistic Nonfouling/Fouling-Release Surface.

The preparation of a fluorine-containing synergistic nonfouling/fouling-release surface, using a b-PFMA-PEO asymmetric molecular brush possessing both poly(ethylene glycol) (PEO) and poly(2,2,2-trifluoroethyl methacrylate) (PFMA) side chains densely distributed on the same repeat unit along the polymeric backbone, is reported. On the basis of the poly(Br-acrylate-alkyne) macroagent comprising two functionalities (alkynyl and 2-bromopropionate), which is prepared by reversible addition-fragmentation chain transfer homopolymerization of a new trifunctional acrylate monomer of Br-acrylate-alkyne, b-PFMA-PEO asymmetric molecular brushes are obtained by concurrent atom transfer radical polymerization and Cu-catalyzed azide/alkyne cycloaddition "click" reaction in a one-shot system. A spin-cast thin film of the b-PFMA-PEO asymmetric molecular brush exhibits a synergistic antifouling property, in which PEO side chains endow the surface with a nonfouling characteristic, whereas PFMA side chains display the fouling-release functionality because of their low surface energy. Both protein adsorption and cell adhesion tests provided estimates of the antifouling activity of the asymmetric molecular brush surfaces, which was demonstrated to be influenced by the degree of polymerization of the backbone and the length of the PEO and PFMA side chains. With compositional heterogeneities, all asymmetric molecular brush surfaces show considerable antifouling performance with much less protein adsorption (at least 45% off, up to 75% off) and cell adhesion (at least 70% off, up to 90% off) in comparison with a bare surface.

Voltage-induced Infrared Absorption from a Spin-cast Thin Film of Ferroelectric Poly(vinvlidene fhioride-co-trifluoroethvlene) (P(VDF-TrFE))

Voltage-induced infrared spectra of annealed spin-cast thin films of ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) (molar ratio, 3:1) were measured in a stepwise cyclic external electric field. Most of the observed infrared bands originated from the β ferroelectric crystalline phase. The voltage-induced spectral changes were decomposed into zeroth- (original), first-, and second-derivative spectra, and were attributed to the rotational motions of the polymer chains and the vibrational Stark effect. The values of the original spectral absorbance change ratios, ΔA/A, for the 849-cm-1 band (CF2 symmetric stretching, a1) and the 884-cm-1 band (CH2 rocking, b2) of the film exhibited double minimum and maximum peak hysteresis loops, respectively. The intensity of each band increased or decreased suddenly near a coercive field of ±0.6 MV/cm. These sudden intensity changes were attributed to the rotational inversion of the polymer chains that are associated with ferroelectricity.

Poly(3-hexylthiophene)/gold nanoparticle nanocomposites: relationship between morphology and electrical conductivity

The morphology and electrical properties of gold nanoparticles (AuNP) layer vacuum-deposited onto spin-cast thin films of poly(3-hexylthiophene), P3HT, were studied. The electrical conductivity was measured during temperature cycling and related to the morphology of the same composite structures, which was monitored by transmission electron microscopy (TEM) and extra-high resolution scanning electron microscopy (XHR SEM). Comparison to the analogous polystyrene/AuNP layers was made to distinguish the role of the polymer support on the morphology and electrical properties of the nanoparticles assembly. Gold deposited in a very thin layer formed a nanoparticles-like island structure with the morphology depending on the effective thickness of the deposited layer and on its subsequent thermal treatment. A stabilizing effect of the thiophene–gold interaction on the nanoparticles morphology was observed.

Role of Solution Structure in Self-Assembly of Conjugated Block Copolymer Thin Films

Conjugated block copolymers provide a pathway to achieve thermally stable nanostructured thin films for organic solar cells. We characterized the structural evolution of poly(3-hexylthiophene)-block-poly(diketopyrrolopyrrole–terthiophene) (P3HT-b-DPPT-T) from solution to nanostructured thin films. Aggregation of the DPPT-T block of P3HT-b-DPPT-T was found in solution by small-angle X-ray scattering with the P3HT block remaining well-solvated. The nanostructure in thin films was determined using a combination of wide and small-angle X-ray scattering techniques as a function of processing conditions. The structure in solution controlled the initial nanostructure in spin-cast thin films, allowing subsequent thermal annealing processes to further improve the ordering. In contrast to the results for thin films, nanostructural ordering was not observed in the bulk samples by small-angle X-ray scattering. These results suggest the importance of controlling solvent induced aggregation in forming nanostructured th...

Surface Structure of Semicrystalline Naphthalene Diimide–Bithiophene Copolymer Films Studied with Atomic Force Microscopy

The crystallization behavior, the surface structure, and the nanomechanical properties of a semiconducting polymer play a crucial role in understanding the charge injection process, the transport of the charge carriers and the processability of the material. Here we study the semiconducting copolymer poly([N,N′-bis(2-octyldodecyl)-11-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-12 bithiophene)) (P(NDI2OD-T2)) and investigate the influence of annealing conditions on its surface structure through intermittent contact mode atomic force microscopy (AFM) and AFM-based measurements of amplitude–phase–distance (APD) curves. For spin-cast thin films as well as for films annealed at temperatures up to 320 °C, we find that the edges of crystalline lamellae are exposed at the surface. A 1.2 nm thick layer of alkyl side chains covers the film surface as indicated by the tip indentation. This suggests that charge injection into P(NDI2OD-T2) films is not hindered by a surface layer of amorphous mater...

Penetration and exchange kinetics of primary alkyl amines applied to reactive poly(pentafluorophenyl acrylate) thin films

We investigated the mechanism of primary amine-induced post-polymerization modification of active ester polymer thin films composed of pentafluorophenyl acrylate (PFPA) polymers. The most important physical parameters in the post-polymerization modification are the molecular weight of the PFPA polymers and the aliphatic chain length of the primary amines. The effects of these two parameters on the penetration depth, as well as the exchange kinetics were systematically studied by neutron reflectivity and quartz crystal microbalance with dissipation, accompanied by the measurement of surface morphological changes by an atomic-force microscopy and optical microscopy. The spin-cast PFPA polymer thin films showed distinctive differences in the exchange kinetics, as well as the penetration depth of amines as a function of the PFPA polymer molecular weight. The aliphatic chain length of primary alkyl amines markedly influenced the penetration kinetics into low-molecular weight poly(PFPA) films, whereas there was no significant penetration effect on the high-molecular weight films. The high-molecular weight of the poly(PFPA) films led to the deceleration of the dissolution of amine-functionalized polymer chains in a good solvent. The results of this study may provide a good physical background for developing reactive poly(PFPA) thin film platforms based on simple and quantitative post-modification with amine-containing molecules. The poly(pentafluorophenyl acrylate) thin film provides a reactive surface platform through facile post-modification with primary alkyl amines. We report the effect of the most important parameters in this reaction, molecular weight of the reactive polymers and the aliphatic chain length of primary amines, on the degree of exchange of the thin films. The studies with neutron reflectivity and quartz crystal microbalance offer physical backgrounds for developing versatile functional thin films based on this chemistry, in terms of penetration and exchange kinetics as a function of molecular weight of reactive ester polymers and primary amines.

Solar heat reflective coating formed of polystyrene chains bearing 4-vinylpyridine-rich end segments

Incorporation of a minor dose of 4-vinylpyridine (4-VP) into an end segment of polystyrene (PS) chain by emulsion copolymerization yields a copolymer molecule P(4-VP/S) with weak surface-activity. The spin cast thin films of P(4-VP/S) display enhanced solar light reflectance of R = 80–90% compared with its PS homopolymer counterpart. It is imperative to use dimethylformamide (DMF) as casting solvent because the hydrophilic nature of DMF induces core-to-grain assembling while dried in humid air, leading to a nodular film matrix. A rise of 4-VP dose in P(4-VP/S) causes a breath-figure patterned matrix instead and consequently an obvious reduction of reflectance in the near-infrared region. Mechanistically, P(4-VP/S) chains that bear a short end-segment with rich 4-VP units constitute tiny hydrophilic cores because of entrapment of moisture during drying, surrounding which the long PS tails thus undergo chain coiling to form nanoparticles. They then aggregate to form submicron grains in rosette and the partial coalescence of adjacent grains results in micron lumps. Such hierarchical evolution finally constructs a matrix exhibiting an enhanced solar reflectance.

Thermally amendable and thermally stable thin film of POSS tethered Poly(methyl methacrylate) (PMMA) synthesized by ATRP

In this article we report the stability, dewetting suppression and scratch mending of thin film of POSS tethered PMMA hybrid material having thickness in the range of 100–300nm. The POSS–PMMA hybrid material was synthesized via thermal thiol-ene modification of allyl-POSS followed by O-acylation reaction and atom transfer radical polymerization (ATRP). The polymerization reaction was carried out using CuBr as catalyst in combination with N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) as ligand, and POSS–Br as initiator. NMR, FT-IR, WAXD and FE-SEM analyses were used to study the structure and morphology of the hybrid materials. FE-SEM analysis showed interesting honeycomb architecture in the hybrid material. Subsequently we investigated the thermal stability and scratch mending (SM) of spin cast thin films of the synthesized POSS–PMMA hybrid material. The as cast film had a holey, Swiss cheese morphology when dispersed from a rapidly evaporating solvent THF. The film, upon thermal annealing flattened out in favor of a smooth, featureless film that did not dewet with time even upon prolonged annealing. Further, scratches made on the film surface using a scalpel were seen to mend completely upon prolonged thermal annealing at temperatures above Tg of the polymer. The film could mend repeated scratches at the same location with complete recovery of mechanical strength, which was verified by nano-indentation measurement. The mending is entirely due to wetting of the polymer film in presence of low surface energy POSS. The scratch mending was slow, but was observed during repeated mending cycles. The films also exhibited improved hydrophobicity which remains un-altered even upon repeated mending cycles indicating presence of POSS moieties in the film surface. Importantly, when scratches made on the pristine PMMA film surface using a scalpel, the film was found to be ruptured during annealing due to strong influence of the dispersion forces across the low thickness zone and consequently, the film dewetted and the scratch width gradually increased with time.

Contribution of Aggregate States and Energetic Disorder to a Squaraine System Targeted for Organic Photovoltaic Devices

Squaraine dyes have significant potential for use in organic photovoltaic devices because their chemical and packing structure tunability leads to a broad solid state panchromaticity. Nevertheless, broadening of the spectrum does not always give rise to increasing power conversion efficiencies. Furthermore, the same processing strategy used to make devices from different squaraines does not lead to the same optimized performance. In this work, by varying the environmental conditions of a set of anilinic squaraines, we demonstrate that spin-cast thin films are made up of a complex set of states, with each state contributing differently to the overall device efficiency. We demonstrate crystallochromy in that small changes in the packing structure give rise to dramatically different absorption spectra. Through a remarkable comparison between squaraines in poly(methyl methacrylate) solid solution and squaraine:PC60BM blends, we also show long-range and orientational disorder broadening, which distorts the ability to correlate qualitative spectroscopic assessment with an understanding of the device mechanism. We conclude that a full quantitative assessment of the populations of each excited state must be carried out in order to make progress toward an improved understanding of each state's contribution to charge transfer at the bulk heterojunction interface.