PECVD of silicon and titanium based coatings to enhance the biocompatibility of blood contacting biomedical devices

The clinical success of a surgical implantation depends on various factors including the design and biocompatibility of the biomaterial, surgical procedure adopted, injuries made during implantation and health and condition of the patient. The success of a biomaterial depends on the interaction and the progressive reaction between the blood components and the surface of the implant. Proteins present in the blood will be the first components to become adsorbed on the surface of the biomaterial. Studies show that the protein fibrinogen present in the blood plasma is the major initiator of inflammatory reactions and involved in blood clotting. By minimizing the fibrinogen adsorption it is possible to reduce the contribution of the biomaterial surface characteristics to thrombosis and inflammatory reactions. In this work, silicon and titanium based thin film coatings with four different surface characteristics were deposited by PECVD on 316L stainless steel substrates. Polymer-like SiOxCyHz, silica-like SiOx, titanium oxide TiO, and silicon-titanium mixed oxide coatings were deposited by plasma decomposition of organic molecules. An extensive study was done on silicon based coatings deposited from hexamethyl disiloxane (HMDSO) to analyze the influence of plasma process parameters like RF power, precursor flow ratio and flow rate on the surface chemical and mechanical characteristics of the film. Titanium dioxide coatings deposited from titanium tetraisopropoxide (TIP) were also analyzed for the effect of plasma process parameters on their surface characteristics. Silicon - titanium mixed oxide coatings were deposited to obtain intermediate characteristics between silicon oxide and titanium oxide films and the process was optimized to get a hydrophilic surface with wettability lower than SiO, and a bandgap higher than that of titanium dioxide. It was concluded, from the fibrinogen adsorption studies, that both the film wettability and bandgap has to be optimized in order to minimize the fibrinogen adsorption

Wet Chemical Synthesis and Characterization of Nanomaterials for Solar Cell Applications

During long term space missions, it is necessary to have a reliable source of energy. Solar cells are an easy and reliable way to convert energy from the sun to electrical energy. NASA has used solar cells manufactured on Earth as an energy source for many of its missions. In order to develop technologies that will enable high efficiency solar cells, we are synthesizing nanostructured materials. A range of nanostructured materials, such as titanium dioxide nanowires, nickel nanoparticles, copper nanoparticles, and silver nanoparticles/nanowires, are synthesized. In this work, we are reporting on the synthesis of these nanomaterials and the electron microscopic characterizations. Nanomaterials were synthesized using well-known protocols, such as the polyol process for silver nanowires and the hydrothermal method to produce titanium dioxide nanowires. The nanomaterials were characterized using Scanning Electron Microscopy (SEM) at NASA Ames and X-ray Photoelectron Spectroscopy (XPS) from the Stanford Synchrotron Radiation Lightsource at SLAC National Acceleratory Laboratory. This study will bring understanding on the chemical structure and morphology of these nanomaterials that will potentially be used for high efficiency solar cells

Plasma engineering of graphene

Recently, there have been enormous efforts to tailor the properties of graphene. These improved properties extend the prospect of graphene for a broad range of applications. Plasmas find applications in various fields including materials science and have been emerging in the field of nanotechnology. This review focuses on different plasma functionalization processes of graphene and its oxide counterpart. The review aims at the advantages of plasma functionalization over the conventional doping techniques. Selectivity and controllability of the plasma techniques opens up future pathways for large scale, rapid functionalization of graphene for advanced applications. We also emphasize on atmospheric pressure plasma jet as the future prospect of plasma based functionalization processes

Thin film diffusion barrier formation in PDMS microcavities

We describe a method to form glass like thin film barrier in polydimethylsiloxane (PDMS) microcavities. The reactive fragments for the surface reaction were created from O2 and hexamethyldisiloxane (HMDS) in RF plasma environment. The reaction is based on migration of the reactive fragments into the microcavities by diffusion, to form a glass like thin film barrier to conceal the naked surface of PDMS. The barrier successfully blocked penetration of a fluorescent dye rhodamine B (RhB) into PDMS. The thickness of the barrier could be controlled by the time of reaction and the pressure inside the reaction chamber. There is a wide range of applications of such a technique in various fields, e.g. for coating the covered surfaces of microfluidic channels, tubes, capillaries, medical devices, catheters, as well as chip-integrated capillary electrophoresis and advanced electronic and opto-fluidic packaging

Low temperature growth technique for nanocrystalline cuprous oxide thin films using microwave plasma oxidation of copper

We report on the direct formation of phase pure nanocrystalline cuprous oxide (Cu2O) film with band gap ~ 2 eV by microwave plasma oxidation of pulsed dc magnetron sputtered Cu films and the highly controlled oxidation of Cu in to Cu2O and CuO phases by controlling the plasma exposure time. The structural, morphological and optoelectronic properties of the films were investigated. p-type Cu2O film with a grain size ~20-30 nm, resistivity of ~66 Ω cm and a hole concentration of ~2×1017 cm-3 is obtained for a plasma exposure time of 10 min without using any foreign dopants. The optical absorption coefficient (~105 cm-1) of the Cu2O film is also reported

Efficacy of atmospheric pressure dielectric barrier discharge for inactivating airborne pathogens

Atmospheric pressure plasmas have gained attention in recent years for several environmental applications. This technology could potentially be used to deactivate airborne microorganisms, surface-bound microorganisms, and biofilms. In this work, the authors explore the efficacy of the atmospheric pressure dielectric barrier discharge (DBD) to inactivate airborne Staphylococcus epidermidis and Aspergillus niger that are opportunistic pathogens associated with nosocomial infections. This technology uses air as the source of gas and does not require any process gas such as helium, argon, nitrogen, or hydrogen. The effect of DBD was studied on aerosolized S. epidermidis and aerosolized A. niger spores via scanning electron microscopy (SEM). The morphology observed on the SEM micrographs showed deformations in the cellular structure of both microor- ganisms. Cell structure damage upon interaction with the DBD suggests leakage of vital cellular materials, which is a key mechanism for microbial inactivation. The chemical structure of the cell surface of S. epidermidis was also analyzed by near edge x-ray absorption fine structure spectros- copy before and after DBD exposure. Results from surface analysis revealed that reactive oxygen species from the DBD discharge contributed to alterations on the chemistry of the cell membrane/ cell wall of S. epidermidis

Tetraethyl orthosilicate and acrylic acid forming robust carboxylic functionalities on plastic surfaces for biodiagnostics

Surface functionalisation and effects related to non-specific binding of the detection molecules are the key aspects to be considered for fluorescence-linked bioassays. Here, we present a deposition of polymeric structures with carboxylic acid functionalities by plasma enhanced chemical vapour deposition. We report on characterisation and some unique properties of the film formed as a result of sequential, plasma assisted fragmentation and deposition from vapours of acrylic acid (AA) and tetraethyl orthosilicate (TEOS). TEOS serves as an adhesion layer to the plastic substrate and also as a network building layer for further cross-linking with AA, the sequential plasma deposition resulting in a film of composition graded from inside to outside. The presence of silanols (Si-OH) can facilitate large uptake of water molecules and cause significant hydration of the layer, which in combination with high total negative charge lowers the non-specific binding of biomolecules. Furthermore, the specific combination of TEOS and AA significantly increased the proportion of carboxyl groups in the layer, above that found from deposition of AA alone. The availability and reactivity of the carboxyl functionalities for covalent attachment of specific bioreceptor molecules was confirmed by a total internal reflection ellipsometry technique in a reaction with amino terminated ssDNA. The combination of low non-specific binding and high specific binding amount gave a high signal/noise ratio. Ageing studies of the film showed long-term stability over 50 d. Carboxylic acid coatings have been deposited by PECVD onto cyclic olefin polymer substrates from an acrylic acid monomer. Carboxy properties are enhanced through the addition of TEOS as a base layer to the substrate, results are compared to coatings without this adhesion layer. A thorough analysis of the deposited surface and a comprehensive characterisation of the surface is investigated. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Plasma jet based <i>in situ</i> reduction of copper oxide in direct write printing

Printing of nanostructured films with tailored oxidation state and electronic structure can have far reaching applications in several areas including printable electronics, optoelectronics, solar cells, catalytic conversion, and others. Widely used inkjet/aerosol/screen printing techniques require pre- and postprocessing for enhanced adhesion and tailoring of the chemical state of the thin film. Herein, we demonstrate atmospheric pressure plasma jet printing with unique capability to print and tune in situ the electronic properties and surface morphology of nanomaterials. Plasma printing of copper thin films with tailored oxidation state from an inexpensive copper oxide precursor is demonstrated and characterized using x-ray absorption spectroscopy, Raman spectroscopy, and electrical measurements

Evaluation of different nonspecific binding blocking agents deposited inside poly(methyl methacrylate) microfluidic flow-cells

Poly(methyl methacrylate) (PMMA) flow-cells containing microwells were deposited with different nonspecific binding blocking agents, namely, bovine serum albumin (BSA), cationic lipid (DOTAP:DOPE) and diethylene glycol dimethyl ether (DEGDME). Water contact angle (WCA) and atomic force microscope (AFM) measurements were carried out to confirm the successful depositions of BSA, DOTAP, and DEGDME onto the PMMA surfaces. Fluorescent intensity measurements were performed to evaluate the degree of nonspecific adsorption of Cy5-labeled anti-IgG proteins onto plain and oxygen plasma-treated (PT) PMMA flow-cells as well as PMMA flow-cells deposited with different above-mentioned blocking agents. We then employed a label-free detection method called total internal reflection ellipsometry (TIRE) to evaluate the stability of the deposited blocking agents inside the PMMA flow-cells. It was found that, while DOTAP:DOPE was the best agent for blocking the nonspecific adsorption, it could be removed from the PMMA surfaces of the flow-cells upon rinsing with phosphate buffered saline (PBS) and later deposited back onto the Au-coated glass sensing substrate of the TIRE. The removal of the blocking agents from PMMA surfaces and their deposition onto the sensing substrate were further manifested by measuring the kinetics and the amount of adsorbed anti-α-hCG proteins. Overall, the dry DEGDME coating by plasma-enhanced chemical vapor deposition (PECVD) showed very good blocking and excellent stability for subsequent assay inside the microwells. Our results could be useful when one considers what blocking agents should be used for PMMA-based microfluidic immunosensor or biosensor devices by looking at both the blocking efficiency and the stability of the blocking agent. © 2011 American Chemical Society

Functionalization of cyclo-olefin polymer substrates by plasma oxidation: Stable film containing carboxylic acid groups for capturing biorecognition elements

Many current designs in biomedical diagnostics devices are based on the use of low cost, disposable, easy-to-fabricate chips made of plastic material, typically a cyclo-olefin polymer (COP). Low autofluorescence properties of such material, among others, make it ideal substrate for fluorescence-based applications. Functionalization of this plastic substrate for biomolecule attachment is therefore of great importance and the quality of films produced on such surface have often a significant influence on the performance of the device. In this communication we discuss the surface chemistry and some other characteristics of hydrophilic films, containing carboxylic acid functional groups, formed by plasma oxidation of COP and also films containing cross-linked, polymerized acryclic acid produced by sequential deposition of tetraorthosilicate and acrylic acid by plasma enhanced chemical vapor deposition (PECVD). Immobilization of labeled, single stranded DNA revealed high binding capacity for both coatings. To our best knowledge, this is the first example of direct immobilization of biomolecules on just plasma oxidized COP. Furthermore, more sophisticated treatment of the oxidized plastic substrate by PECVD with other organic precursors increased the binding capacity by some 40% than that of just plasma oxidized COP. The carboxy functionalized surfaces, due to the negative charge of the carboxy groups, showed very positive trends towards increasing the signal to noise ratio when charged biomolecules such as DNA, are used. © 2010 Elsevier B.V