Kinetically Limited Bulk Polymerization of Polymer Thin Films by Initiated Chemical Vapor Deposition.

An experimental study and kinetic model analysis of the initiated chemical vapor deposition (iCVD) of polymer thin films have been performed at saturated monomer vapor conditions. Previous iCVD kinetic studies have focused on subsaturated monomer conditions where polymer deposition kinetics is known to be limited by monomer adsorption. However, iCVD kinetics at saturated conditions have so far not been systematically investigated, and it remains unclear whether the adsorption-limited phenomenon would still apply at saturation, given the abundance of monomer for reaction. To probe this question, a series of depositions of poly(vinylpyrrolidone) (PVP) thin films as a model system were performed by iCVD at substrate temperatures from 10 to 25 °C at both fully saturated (100%) and subsaturated (50%) conditions. While the deposition rates at subsaturated conditions exhibit the expected adsorption-limited behavior, the deposition rates at saturated conditions unexpectedly show two distinct deposition regimes with reaction time: an initial adsorption-limited regime followed by a kinetically limited steady-state regime. In the steady-state regime, the deposition kinetics is found to be thermally activated by raising substrate temperature with an overall activation energy of +86 kJ/mol, which agrees reasonably well with the experimentally determined value of +89 kJ/mol in the literature for bulk PVP polymerization and a mechanistically derived value of +91 kJ/mol based on the bulk free radical polymerization mechanism of PVP. These findings open new operating windows for iCVD polymerization and thin-film growth in which fast polymer deposition can be achieved without substrate cooling that can greatly simplify the iCVD scale-up to roll-to-roll processing and enable iCVD polymerization of highly volatile monomers relevant for diverse applications in biomedicine, smart wearables, and renewable energy.

Conformal Growth of Ultrathin Hydrophilic Coatings on Hydrophobic Surfaces Using Initiated Chemical Vapor Deposition.

Hydrophilic poly(2-hydroxyethyl methacrylate) (PHEMA) was deposited onto hydrophobic polytetrafluoroethylene (PTFE) surfaces using initiated chemical vapor deposition. By tuning the reactor conditions, the reaction kinetics were varied to achieve a wide range of deposition rates that spanned over 2 orders of magnitude (∼0.1-10 nm/min). Depositions rates at >1 nm/min were successful in overcoming the interfacial energy and wettability barriers between the hydrophobic and hydrophilic polymers and were found to achieve both conformal and ultrathin coatings. PHEMA coatings as thin as ∼10 nm over PTFE were able to transform a hydrophobic surface with a water contact angle of ∼110° to a hydrophilic one with an angle of ∼20°.

Formation and Stability of Thin Condensing Films on Structured Amphiphilic Surfaces.

We present a microamphiphilic surface to promote the formation of a thin, stable liquid film during condensation. The surface consists of a hydrophilic micropillar array with hydrophobic pillar tips and was made using photolithography, deep reactive ion etching, and liftoff. The hydrophobic tips prevent the liquid film from growing thick, thereby keeping the thermal resistance low without the cyclical growth and shedding process of dropwise condensation. The wetting behavior was modeled analytically, and the parameters required for film formation were determined and verified with ESEM experiments. When a surface filled with condensate and lacked a low-pressure zone for the water to leave, a rupture event occurred, and a large Wenzel droplet emerged to flood the surface irreversibly. A number of strategies were found to combat rupture events. Tilting the surface vertically and dipping in a liquid pool gave the condensate a low-pressure region and prevented rupture. Irreversible flooding can also be avoided by ensuring that the emerged droplet was a nonwetting, highly mobile Cassie droplet. Parameters for Cassie-stable amphiphilic surfaces were determined analytically, but the high aspect ratios required prevented the manufacture of these surfaces for this study. Instead a hierarchical design was presented that demonstrated emerged Cassie droplets without challenging the manufacturing limits of the microfabrication procedure. This design avoided Wenzel droplet flooding without the need for a designated low-pressure zone. Additionally, sites for Cassie emergence could be engineered by removing a single pillar from the array at a designated location.

Deposition Behavior of Polyaniline on Carbon Nanofibers by Oxidative Chemical Vapor Deposition.

Oxidative chemical vapor deposition (oCVD) offers unique advantages as a liquid-free processing technique in synthesizing and integrating conducting polymers, including polyaniline (PANI), by enabling conformal coatings onto nanostructured substrates, like carbon nanofibers. With relatively thick nanofiber mats, the challenge is to ensure uniform coating thickness through the porous substrates. Here, the substrate temperature during oCVD is found to be a primary factor influencing PANI coating uniformity. Coating uniformity is enhanced by operating at a higher substrate temperature, where monomer adsorption is believed to be limiting relative to intrinsic reaction kinetics. Also, a higher substrate temperature leads to significantly less PANI oligomers and more PANI in the emeraldine oxidation state. A systematic study of oCVD kinetics with substrate temperature shows a reaction-limited regime at lower substrate temperatures with an activation energy of 12.0 kJ/mol, which is believed to be controlled by the self-catalyzed PANI polymerization reaction that transitions at higher substrate temperatures above 90 °C to an adsorption-limited regime as indicated by a negative activation energy of -18.8 kJ/mol. Overall, by operating within an adsorption-limited oCVD regime, more uniform oCVD PANI coatings on electrospun carbon nanofiber mats have been achieved.

Reduced cell attachment to poly(2-hydroxyethyl methacrylate)-coated ventricular catheters in vitro.

The majority of patients with hydrocephalus are dependent on ventriculoperitoneal shunts for diversion of excess cerebrospinal fluid. Unfortunately, these shunts are failure-prone and over half of all life-threatening pediatric failures are caused by obstruction of the ventricular catheter by the brain's resident immune cells, reactive microglia and astrocytes. Poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels are widely used for biomedical implants. The extreme hydrophilicity of PHEMA confers resistance to protein fouling, making it a strong candidate coating for ventricular catheters. With the advent of initiated chemical vapor deposition (iCVD), a solvent-free coating technology that creates a polymer in thin film form on a substrate surface by introducing gaseous reactant species into a vacuum reactor, it is now possible to apply uniform polymer coatings on complex three-dimensional substrate surfaces. iCVD was utilized to coat commercially available ventricular catheters with PHEMA. The chemical structure was confirmed on catheter surfaces using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. PHEMA coating morphology was characterized by scanning electron microscopy. Testing PHEMA-coated catheters against uncoated clinical-grade catheters in an in vitro hydrocephalus catheter bioreactor containing co-cultured astrocytes and microglia revealed significant reductions in cell attachment to PHEMA-coated catheters at both 17-day and 6-week time points. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1268-1279, 2018.

Oxidative chemical vapor deposition of polyaniline thin films.

Polyaniline (PANI) is synthesized via oxidative chemical vapor deposition (oCVD) using aniline as monomer and antimony pentachloride as oxidant. Microscopy and spectroscopy indicate that oCVD processing conditions influence the PANI film chemistry, oxidation, and doping level. Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) indicate that a substrate temperature of 90 °C is needed to minimize the formation of oligomers during polymerization. Lower substrate temperatures, such as 25 °C, lead to a film that mostly includes oligomers. Increasing the oxidant flowrate to nearly match the monomer flowrate favors the deposition of PANI in the emeraldine state, and varying the oxidant flowrate can directly influence the oxidation state of PANI. Changing the reactor pressure from 700 to 35 mTorr does not have a significant effect on the deposited film chemistry, indicating that the oCVD PANI process is not concentration dependent. This work shows that oCVD can be used for depositing PANI and for effectively controlling the chemical state of PANI.

Suitability of N-propanoic acid spiropyrans and spirooxazines for use as sensitizing dyes in dye-sensitized solar cells.

This work deals with the fabrication and evaluation of color-changing dye-sensitized solar cells (DSSCs) that include N-propanoic acid-functionalized spiropyrans and spirooxazines as sensitizing dyes. We investigated the photophysical properties of these compounds in various solvents and pH conditions using UV-Vis spectroscopy, and their behavior on TiO2 photoanode surfaces using a combination of UV-Vis and FT-IR. Their performance as sensitizing dyes for DSSCs was also analyzed. This study revealed a number of unique properties for this class of compounds that affect their performance as both photochromic compounds and DSSC sensitizers, which allow for future creation of efficient photochromic DSSCs.

Polarization screening-induced magnetic phase gradients at complex oxide interfaces.

Thin-film oxide heterostructures show great potential for use in spintronic memories, where electronic charge and spin are coupled to transport information. Here we use a La0.7Sr0.3MnO3 (LSMO)/PbZr0.2Ti0.8O3 (PZT) model system to explore how local variations in electronic and magnetic phases mediate this coupling. We present direct, local measurements of valence, ferroelectric polarization and magnetization, from which we map the phases at the LSMO/PZT interface. We combine these experimental results with electronic structure calculations to elucidate the microscopic interactions governing the interfacial response of this system. We observe a magnetic asymmetry at the LSMO/PZT interface that depends on the local PZT polarization and gives rise to gradients in local magnetic moments; this is associated with a metal-insulator transition at the interface, which results in significantly different charge-transfer screening lengths. This study establishes a framework to understand the fundamental asymmetries of magnetoelectric coupling in oxide heterostructures.

Full-field dynamic characterization of superhydrophobic condensation on biotemplated nanostructured surfaces.

While superhydrophobic nanostructured surfaces have been shown to promote condensation heat transfer, the successful implementation of these coatings relies on the development of scalable manufacturing strategies as well as continued research into the fundamental physical mechanisms of enhancement. This work demonstrates the fabrication and characterization of superhydrophobic coatings using a simple scalable nanofabrication technique based on self-assembly of the Tobacco mosaic virus (TMV) combined with initiated chemical vapor deposition. TMV biotemplating is compatible with a wide range of surface materials and applicable over large areas and complex geometries without the use of any power or heat. The virus-structured coatings fabricated here are macroscopically superhydrophobic (contact angle >170°) and have been characterized using environmental electron scanning microscopy showing sustained and robust coalescence-induced ejection of condensate droplets. Additionally, full-field dynamic characterization of these surfaces during condensation in the presence of noncondensable gases is reported. This technique uses optical microscopy combined with image processing algorithms to track the wetting and growth dynamics of 100s to 1000s of microscale condensate droplets simultaneously. Using this approach, over 3 million independent measurements of droplet size have been used to characterize global heat transfer performance as a function of nucleation site density, coalescence length, and the apparent wetted surface area during dynamic loading. Additionally, the history and behavior of individual nucleation sites, including coalescence events, has been characterized. This work elucidates the nature of superhydrophobic condensation and its enhancement, including the role of nucleation site density during transient operation.

Enhanced charge storage of ultrathin polythiophene films within porous nanostructures.

In a single step polymerization and coating, oxidative chemical vapor deposition (oCVD) has been used to synthesize unsubstituted polythiophene. Coatings have been conformally coated within porous nanostructures of anodized aluminum oxide, titanium dioxide, and activated carbon. Significant enhancement in charge capacity has been found with ultrathin polythiophene coatings that preserve the surface area and pore space of the nanostructures. Pseudocapacitors consisting of ultrathin polythiophene coated within activated carbon yielded increases of 50 and 250% in specific and volumetric capacitance compared with bare activated carbon. Devices were stable up to the 5000 cycles tested with only a 10% decrease in capacitance.

Thickness-dependent crossover from charge- to strain-mediated magnetoelectric coupling in ferromagnetic/piezoelectric oxide heterostructures.

Magnetoelectric oxide heterostructures are proposed active layers for spintronic memory and logic devices, where information is conveyed through spin transport in the solid state. Incomplete theories of the coupling between local strain, charge, and magnetic order have limited their deployment into new information and communication technologies. In this study, we report direct, local measurements of strain- and charge-mediated magnetization changes in the La0.7Sr0.3MnO3/PbZr0.2Ti0.8O3 system using spatially resolved characterization techniques in both real and reciprocal space. Polarized neutron reflectometry reveals a graded magnetization that results from both local structural distortions and interfacial screening of bound surface charge from the adjacent ferroelectric. Density functional theory calculations support the experimental observation that strain locally suppresses the magnetization through a change in the Mn-eg orbital polarization. We suggest that this local coupling and magnetization suppression may be tuned by controlling the manganite and ferroelectric layer thicknesses, with direct implications for device applications.

Electric field-induced, reversible lotus-to-rose transition in nanohybrid shish kebab paper with hierarchical roughness.

Nature uses a variety of strategies to tune wetting behavior for biological applications. By artificially mimicking these strategies, a variety of different wetting conditions can be achieved. Numerous examples exist of designed surfaces that can mimic the wetting behavior of lotus leaves or rose petals, but few surfaces that may reversibly transition between the two have been reported. In this paper, a combination of topological control over conductive, carbon-based nanomaterials and low surface energy coating was used to tune the wetting properties between "lotus" and "rose." The topological control was imparted by a hierarchical "nanohybrid shish kebab" structure, which uses solution-grown polymer single crystals on carbon nanotubes to tune the surface roughness of the latter. The low surface energy polytetrafluoroethylene (PTFE) coating was deposited by the initiated chemical vapor deposition technique. Application of electric potential on these unique nanostructures allows the surfaces to reversibly transition between "lotus" and "rose" behavior. A further irreversible transition between "rose" and the fully wetted Wenzel wetting state was also predicted and shown. These materials show remarkable promise for lab-on-a-chip devices and surface passivation for biological studies.

Carbon nanotube-directed polytetrafluoroethylene crystal growth via initiated chemical vapor deposition.

Initiated chemical vapor deposition (iCVD) has been shown to be suitable for blanketing surfaces with thin polymer coatings of ≈1-2 nm and greater. In this work, iCVD coatings of polytetrafluoroethylene (PTFE) deposited on carbon nanotube (CNT)-based surfaces show CNT-templated PTFE single crystal growth. While the coating forms disoriented agglomerates when deposited on an amorphous carbon background, "shish-kebab" structures are observed when grown on single-walled carbon nanotubes (SWCNT) as well as CNT buckypaper. It is shown that the shish-kebab structure is composed of PTFE lamellae arranged with the chain backbones running parallel to the SWCNT axis. This result allows one to control not only the surface chemistry using PTFE but also the coating surface topology.

Microencapsulation of a crop protection compound by initiated chemical vapor deposition.

In this work, initiated chemical vapor deposition (iCVD) has been employed as a one-step liquid-free process combining polymerization and coating for the encapsulation of 3D non-planar substrates. Coatings have been applied using iCVD specifically to encapsulate microparticles of a highly water-soluble crop protection compound (CPC) for controlled release. Release behavior has been compared among different coatings synthesized using different iCVD processing conditions, including varying degrees of polymer hydrophobicity, continuous and pulsed deposition, and crosslinking. iCVD has been found to provide tunable synthesis of hydrophobic, crosslinked polymers with control over mass diffusivity, and coating thickness for enhancing barrier properties.

Chemical vapor deposition synthesis of tunable unsubstituted polythiophene.

Despite having exceptional electroactive properties, applications of unsubstituted polythiophene (PTh) have been limited due to its insolubility. To overcome this challenge, we have employed oxidative chemical vapor deposition (oCVD) as a unique liquid-free technique to enable the oxidative polymerization of PTh using thiophene as the starting monomer and vanadium oxytrichloride as an effective vaporizable oxidant initiator. Vibrational and phototelectron spectroscopy indicated the formation of unsubstituted polythiophene. Cyclic voltammetry revealed its electrochromic behavior in solution. Significantly, polymer conjugation length and electrical conductivity can be tuned by controlling oCVD process variables. Polymerization is found to be adsorption-limited, so by providing sufficient monomer and limiting the amount of initiator at the growth surface, PTh is believed to be formed through α-α thiophene linkages.

Photon to thermal response of a single patterned gold nanorod cluster under near-infrared laser irradiation.

The potential applications of the photon to thermal conversion technique by gold nanorods has attracted attention for biomedical applications since they show an intense absorption spectrum in the near-infrared region, and therefore, penetrate more deeply into biological tissues. The goal in this study is to assess a local heating phenomenon with a single patterned cluster of gold nanorods that are prepared as a wet chemically synthesized gold nanorod solution and mixed with aqueous 1% alginate and 0.1 M calcium chloride. In particular, we utilized the initiated chemical vapor deposition method to coat the cluster with poly(2-hydroxyethyl methacrylate) to enhance its high temperature resistance in the solution. The influence of the thermal energy on the surroundings is studied by measuring the surface temperature of the single patterned gold nanorod cluster as a function of laser irradiation time. The experimental results were compared with numerical simulation results. The results showed that the irradiated gold nanorods could rapidly heat to maximum surface temperatures of over 60 °C within 120 s. Furthermore, the temperature remained almost constant (i.e. reached a steady state) under continuous laser irradiation and rapidly cooled to the initial temperature within 90 s when the laser was turned off.

Pore filling of nanostructured electrodes in dye sensitized solar cells by initiated chemical vapor deposition.

The dye sensitized solar cell (DSSC) operation depends on a liquid electrolyte. To achieve better performance, the liquid should be replaced with a solid or gel electrolyte, e.g., polymers. Here, we demonstrate initiated chemical vapor deposition as an effective liquid-free means for in situ polymerization and pore filling. We achieve complete pore filling of 12 µm thick titania resulting in enhanced cell performance that is attributed to reduced charge recombination at the electrolyte-electrode interface.

Mechanical properties of ultrahigh molecular weight PHEMA hydrogels synthesized using initiated chemical vapor deposition.

In this work, poly(2-hydroxyethyl methacrylate) (PHEMA), a widely used hydrogel, is synthesized using initiated chemical vapor deposition (iCVD), a one-step surface polymerization that does not use any solvents. iCVD synthesis is capable of producing linear stoichiometric polymers that are free from entrained unreacted monomer or solvent and, thus, do not require additional purification steps. The resulting films, therefore, are found to be noncytotoxic and also have low nonspecific protein adsorption. The kinetics of iCVD polymerization are tuned so as to achieve rapid deposition rates ( approximately 1.5 microm/min), which in turn yield ultrahigh molecular weight polymer films that are mechanically robust with good water transport and swellability. The films have an extremely high degree of physical chain entanglement giving rise to high tensile modulus and storage modulus without the need for chemical cross-linking that compromises hydrophilicity.

All-dry synthesis and coating of methacrylic acid copolymers for controlled release.

Initiated chemical vapor deposition (iCVD) is presented as an all-dry synthesis and coating method for applying methacrylic acid copolymers as pH-responsive controlled release layers. iCVD combines the strengths of liquid-phase chemical synthesis with a precision solvent-free chemical vapor deposition environment. Copolymers of methacrylic acid and ethyl acrylate were confirmed by a systematic shift in the carbonyl bond stretching mode with a shift in the comonomer ratio within the copolymer and by the ability to apply the Fineman-Ross copolymerization equation to describe copolymerization kinetics. Copolymers of methacrylic acid and ethylene dimethacrylate showed pH-dependent swelling behavior that was applied to the enteric release of fluorescein and ibuprofen.