Anna Maria Coclite

Global and local planarization of surface roughness by chemical vapor deposition of organosilicon polymer for barrier applications

Particulates and asperities on the surface of plastic substrates limit the performance of the current protective barrier coatings for flexible electronics. By applying a smoothing layer to the substrate, prior to barrier deposition, permeation is reduced. While application of smoothing layers from the liquid-phase application and curing of acrylate monomers is well known, reports of planarization achieved by vapor deposition are quite limited. In the current work, the chemical vapor deposition (CVD) of a flexible smoothing layer, requiring no curing, is implemented in the same reactor chamber and from the same organosilicon monomer used for depositing the multilayer barrier stack. The process similarity between the smoothing and barrier layer deposition steps has the potential to lower the overall cost of the process and to improve interfacial properties, such as adhesion between the smoothing layer and the barrier stack. The current methods adapts and combines features of two well established methods for...

Polymer Encapsulation of an Amorphous Pharmaceutical by initiated Chemical Vapor Deposition for Enhanced Stability

The usage of amorphous solids in practical applications, such as in medication, is commonly limited by the poor long-term stability of this state, because unwanted crystalline transitions occur. In this study, three different polymeric coatings are investigated for their ability to stabilize amorphous films of the model drug clotrimazole and to protect against thermally induced transitions. For this, drop cast films of clotrimazole are encapsulated by initiated chemical vapor deposition (iCVD), using perfluorodecyl acrylate (PFDA), hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA). The iCVD technique operates under solvent-free conditions at low temperatures, thus leaving the solid state of the encapsulated layer unaffected. Optical microscopy and X-ray diffraction data reveal that at ambient conditions of about 22 °C, any of these iCVD layers extends the lifetime of the amorphous state significantly. At higher temperatures (50 or 70 °C), the p-PFDA coating is unable to provide protection, while the p-HEMA and p-MAA strongly reduce the crystallization rate. Furthermore, p-HEMA and p-MAA selectively facilitate a preferential alignment of clotrimazole and, interestingly, even suppress crystallization upon a temporary, rapid temperature increase (3 °C/min, up to 150 °C). The results of this study demonstrate how a polymeric coating, synthesized directly on top of an amorphous phase, can act as a stabilizing agent against crystalline transitions, which makes this approach interesting for a variety of applications.

Mechanically robust silica-like coatings deposited by microwave plasmas for barrier applications

Dense and flexible silicon dioxide-like barrier coatings were deposited by microwave postdischarge (downstream plasma). The optical transparency, recyclability, and compatibility with microwave usage are some of the advantages of SiOx offers as compared to thin metallic coatings. Generally, porous silicon dioxide coatings with poor barrier properties are obtained by microwave downstream plasmas, because of limited ion bombardment. Here, we demonstrate that by using very high powers, mechanically robust, barrier coatings deposit both by pulsed and continuous microwave downstream discharges. These SiOx coatings exhibit hardness comparable to Al2O3, but have higher elasticity. Thus, the SiOx have superior cohesion and the ability to recover after cracking. The high critical tensile and compression strain for crack formation demonstrates that these coatings are very resistant and flexible. Correspondingly, a two orders of magnitude barrier improvement is obtained with 100-nm-thick-coating deposited by continu...

Super-Hydrophobic and Oloephobic Crystalline Coatings by Initiated Chemical Vapor Deposition

Preferred crystallographic orientation (texture) in thin films frequently has a strong effect on the properties of the materials and it is important for stable surface properties. Organized molecular films of poly-perfluorodecylacrylate p(PFDA) were deposited by initiated Chemical Vapor Deposition (iCVD). The high tendency of p(PFDA) to crystallize has been fully retained in the polymers prepared by iCVD. The degree of crystallinity and the preferred orientation of the perfluoro side chains, either parallel or perpendicular to the surface, were controlled by tuning the CVD process parameters (i.e. initiator to monomer flow rate ratio, filament temperature, and substrate temperature). Superhydrophobicity (advancing water contact angle, WCA, of 160°, low hysteresis of 5°), and oleophobicity (advancing CA with mineral oil of 120°) were achieved. Low hysteresis was associated with high crystallinity, particularly when the orientation of the crystallites resulted in the perfluoro side groups being oriented parallel to the surface. The latter texture resulted in smoother film (RMS roughness < 30 nm) than the texture with the chains oriented perpendicularly to the surface. This can be very advantageous for applications that require smooth but still crystalline films.

Surface-Induced Phase of Tyrian Purple (6,6′-Dibromoindigo): Thin Film Formation and Stability

The appearance of surface-induced phases of molecular crystals is a frequently observed phenomenon in organic electronics. However, despite their fundamental importance, the origin of such phases is not yet fully resolved. The organic molecule 6,6′-dibromoindigo (Tyrian purple) forms two polymorphs within thin films. At growth temperatures of 150 °C, the well-known bulk structure forms, while at a substrate temperature of 50 °C, a surface-induced phase is observed instead. In the present work, the crystal structure of the surface-induced polymorph is solved by a combined experimental and theoretical approach using grazing incidence X-ray diffraction and molecular dynamics simulations. A comparison of both phases reveals that π–π stacking and hydrogen bonds are common motifs for the intermolecular packing. In-situ temperature studies reveal a phase transition from the surface-induced phase to the bulk phase at a temperature of 210 °C; the irreversibility of the transition indicates that the surface-induced phase is metastable. The crystallization behavior is investigated ex-situ starting from the sub-monolayer regime up to a nominal thickness of 9 nm using two different silicon oxide surfaces; island formation is observed together with a slight variation of the crystal structure. This work shows that surface-induced phases not only appear for compounds with weak, isotropic van der Waals bonds, but also for molecules exhibiting strong and highly directional hydrogen bonds.

Novel Light-Responsive Biocompatible Hydrogels Produced by Initiated Chemical Vapor Deposition

A novel multiresponsive hydrogel has been synthesized by initiated chemical vapor deposition (iCVD). Hydrogels are known for their dynamic swelling response to aqueous environments. A chemical functionalization of the hydrogel surface was performed to add other stimuli-responsive functionalities and obtain a smart material that responds to two stimuli: light irradiation and exposure to aqueous environment. Modifying the hydrogel surface with solution-based methods is often problematic because of the damages caused by the permeation of solvents in the hydrogel. This issue is completely bypassed by the use of solvent-free techniques. Cross-linked polymers of 2-hydroxyethyl methacrylate (HEMA) were functionalized with azobenzene groups, as confirmed by IR spectroscopy and X-ray photoelectron spectroscopy (XPS). Through photoisomerization of the azobenzene, the polarity within the hydrogel is modified and as a consequence the affinity to water. Light irradiation modifies the degree of swelling within thin hydrogel films from 13% before exposure to UV light to 25% after exposure. The possibility of controlling the degree and rate of swelling by light irradiation was never reported before on these time scales and can have exceptional implications for light-induced drug delivery or light-controlled microfluidic systems. The light-responsive hydrogels showed also biocompatibility, which makes them suitable for a great variety of applications as biomaterials.

Dry Polymerization of Functional Thin Films and Multilayers by Chemical Vapor Deposition

Responsive polymers with electronic and photonic properties have recently gained a widespread interest because of their versatility and cheapness. Chemical vapor deposition (CVD) offers a method to combine the large portfolio of conventional organic polymerization with the advantages of easy thin film processing, uniformity and scalability. CVD polymerization takes place in a mild vacuum environment, the substrate is kept near room temperature and in the complete absence of solvent. This allows to deposit polymers on unconventional delicate and flexible substrates, such as paper or plastic, with control over thickness on large areas. High reflectance distributed Bragg reflectors are based on multilayer structures whose growth can be facilitated by the absence of solvent, hence without risk of swelling or dissolving the underlying material. The conformal coverage of three-dimensional feature is also a unique characteristic of CVD polymers. In this chapter, fundamental background together with successful applications of CVD polymers will be reviewed. New techniques, as initiated CVD and oxidative CVD, will be introduced and it will be emphasized how they allow to obtain polymers with high chemical specificity (i.e., large retention of chemical functionality) at elevated speed. The accent will be on the applications where all-dry-processing is critical, such as deposition of insoluble polymers (e.g., highly cross-linked) for reactive and responsive surfaces, molecular crystals of fluoropolymers, conjugated polymers, composite and multilayer structures.

Controlling Indomethacin Release through Vapor-Phase Deposited Hydrogel Films by Adjusting the Cross-linker Density

Vapor-phase deposited polymer coatings are applied on thin indomethacin films to modify the drug release. Hydrogel-forming co-polymers of 2-hydroxyethyl methacrylate and ethylene glycol dimethacrylate were prepared directly on top of solution cast indomethacin thin films by initiated Chemical Vapor Deposition (iCVD). This technique allows for solvent-free processing under mild conditions, thus minimizing a potential impact on the pharmaceutical. The drug release behavior, among other properties, was evaluated for polymers of different compositions and at different temperatures. The data show that the release kinetics can be tuned by several orders of magnitude as the cross-linker fraction is varied in the polymer coating. While uncoated indomethacin films were fully released within an hour, polymer coatings showed gradual liberation over several hours to days. Additional insight is gained from evaluating the experimental dissolution data in the framework of diffusive transport. The results of this study show that the iCVD technique has some promises for pharmaceutical technology, potentially allowing for tailored release behavior also for other drug systems.

Growth Regimes of Poly(perfluorodecyl acrylate) Thin Films by Initiated Chemical Vapor Deposition

Control over thin film growth (e.g., crystallographic orientation and morphology) is of high technological interest as it affects several physicochemical material properties, such as chemical affinity, mechanical stability, and surface morphology. The effect of process parameters on the molecular organization of perfluorinated polymers deposited via initiated chemical vapor deposition (iCVD) has been previously reported. We showed that the tendency of poly(1H,1H,2H,2H-perfluorodecyl acrylate) (pPFDA) to organize in an ordered lamellar structure is a function of the filament and substrate temperatures adopted during the iCVD process. In this contribution, a more thorough investigation of the effect of such parameters is presented, using synchrotron radiation grazing incidence and specular X-ray diffraction (GIXD and XRD) and atomic force microscopy (AFM). The parameters influencing the amorphization, mosaicity, and preferential orientation are addressed. Different growth regimes were witnessed, characterized by a different surface structuring and by the presence of particular crystallographic textures. The combination of morphological and crystallographic analyses allowed the identification of pPFDA growth possibilities between island or columnar growth.

Tuning of material properties of ZnO thin films grown by plasma-enhanced atomic layer deposition at room temperature

The ability to grow inorganic thin films with highly controllable structural and optical properties at low substrate temperature enables the manufacturing of functional devices on thermo-sensitive substrates without the need of material postprocessing. In this study, the authors report on the growth of zinc oxide films by direct plasma-enhanced atomic layer deposition at near room temperature. Diethyl zinc and oxygen plasma were used as the precursor and coreactant, respectively. The process was optimized with respect to the precursor and coreactant dosing as well as to the purging times, which ultimately resulted in saturated atomic layer deposition growth. The so-obtained films exhibit a polycrystalline pattern with a (100) texture and low amount of incorporated carbon. Furthermore, the possibility to tune crystallite size, refractive index, and bandgap of the films by adapting the plasma radio-frequency power is demonstrated.