Printed graphene and its composite with copper for electromagnetic interference shielding applications.

Advances in mobile electronics and telecommunication systems along with 5G technologies have been escalating the electromagnetic interference (EMI) problem in recent years. Graphene-based material systems such as pristine graphene, graphene-polymer composites and other graphene-containing candidates have been shown to provide adequate EMI shielding performance. Besides achieving the needed shielding effectiveness (SE), the method of applying the candidate shielding material onto the object in need of protection is of enormous importance due to considerations of ease of application, reduced logistics and infrastructure, rapid prototyping and throughput, versatility to handle both rigid and flexible substrates and cost. Printing readily meets all these criteria and here we demonstrate plasma jet printing of thin films of graphene and its composite with copper to meet the EMI shielding needs. SE over 30 dB is achieved, which represents blocking over 99.9% of the incoming radiation. Graphene and its composite with copper yield higher green index compared to pure copper shields, implying reduced reflection of incoming electromagnetic waves to help reduce secondary pollution.

Plasma Jet Printing and in Situ Reduction of Highly Acidic Graphene Oxide.

Miniaturization of electronic devices and the advancement of Internet of Things pose exciting challenges to develop technologies for patterned deposition of functional nanomaterials. Printed and flexible electronic devices and energy storage devices can be embedded onto clothing or other flexible surfaces. Graphene oxide (GO) has gained much attention in printed electronics due its solution processability, robustness, and high electrical conductivity in the reduced state. Here, we introduce an approach to print GO films from highly acidic suspensions with in situ reduction using an atmospheric pressure plasma jet. Low-temperature plasma of a He and H2 mixture was used successfully to reduce a highly acidic GO suspension (pH < 2) in situ during deposition. This technique overcomes the multiple intermediate steps required to increase the conductivity of deposited GO. X-ray spectroscopic studies confirmed that the reaction intermediates and the concentration of oxygen functionalities bonded to GO have been reduced significantly by this approach without any additional steps. Moreover, the reduced GO films showed enhanced conductivity. Hence, this technique has a strong potential for printing conducting patterns of GO for a range of large-scale applications.

Morphological and chemical changes of aerosolized E. coli treated with a dielectric barrier discharge.

This study presents the morphological and chemical modification of the cell structure of aerosolized Escherichia coli treated with a dielectric barrier discharge (DBD). Exposure to DBD results in severe oxidation of the bacteria, leading to the formation of hydroxyl groups and carbonyl groups and a significant reduction in amine functionalities and phosphate groups. Near edge x-ray absorption fine structure (NEXAFS) measurements confirm the presence of additional oxide bonds upon DBD treatment, suggesting oxidation of the outer layer of the cell wall. Electron microscopy images show that the bacteria undergo physical distortion to varying degrees, resulting in deformation of the bacterial structure. The electromagnetic field around the DBD coil causes severe damage to the cell structure, possibly resulting in leakage of vital cellular materials. The oxidation and chemical modification of the bacterial components are evident from the Fourier transform infrared spectroscopy and NEXAFS results. The bacterial reculture experiments confirm inactivation of airborne E. coli upon treating with DBD.

Plasma jet printing of electronic materials on flexible and nonconformal objects.

We present a novel approach for the room-temperature fabrication of conductive traces and their subsequent site-selective dielectric encapsulation for use in flexible electronics. We have developed an aerosol-assisted atmospheric pressure plasma-based deposition process for efficiently depositing materials on flexible substrates. Silver nanowire conductive traces and silicon dioxide dielectric coatings for encapsulation were deposited using this approach as a demonstration. The paper substrate with silver nanowires exhibited a very low change in resistance upon 50 cycles of systematic deformation, exhibiting high mechanical flexibility. The applicability of this process to print conductive traces on nonconformal 3D objects was also demonstrated through deposition on a 3D-printed thermoplastic object, indicating the potential to combine plasma printing with 3D printing technology. The role of plasma here includes activation of the material present in the aerosol for deposition, increasing the deposition rate, and plasma polymerization in the case of inorganic coatings. The demonstration here establishes a low-cost, high-throughput, and facile process for printing electronic components on nonconventional platforms.

Scalable low-cost fabrication of disposable paper sensors for DNA detection.

Controlled integration of features that enhance the analytical performance of a sensor chip is a challenging task in the development of paper sensors. A critical issue in the fabrication of low-cost biosensor chips is the activation of the device surface in a reliable and controllable manner compatible with large-scale production. Here, we report stable, well-adherent, and repeatable site-selective deposition of bioreactive amine functionalities and biorepellant polyethylene glycol-like (PEG) functionalities on paper sensors by aerosol-assisted, atmospheric-pressure, plasma-enhanced chemical vapor deposition. This approach requires only 20 s of deposition time, compared to previous reports on cellulose functionalization, which takes hours. A detailed analysis of the near-edge X-ray absorption fine structure (NEXAFS) and its sensitivity to the local electronic structure of the carbon and nitrogen functionalities. σ*, π*, and Rydberg transitions in C and N K-edges are presented. Application of the plasma-processed paper sensors in DNA detection is also demonstrated.

X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites.

The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp2-derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.

Label-free detection of cardiac troponin-I using carbon nanofiber based nanoelectrode arrays.

A label-free biosensor is presented using carbon nanofiber (CNF) nanoelectrode arrays for the detection of cardiac troponin-I in the early diagnosis of myocardial infarction. Immobilization of anti-cTnI Ab on CNFs and the detection of human-cTnI were examined using electrochemical impedance spectroscopy and cyclic voltammetry techniques. Each step of the modification process was monitored, and the results show changes in electrical capacitance or resistance to charge transfer due to the specificity of corresponding adsorption of Ab-Ag interaction. The immunosensor demonstrates a good selectivity and high sensitivity against human-cTnI analytes and is capable of detecting cTnI at concentrations as low as ∼0.2 ng/mL, which is 25 times lower than that possible by conventional methods. Analysis of the electrode at various stages using atomic force microscopy and X-ray reflectivity provides information on the surface roughness and orientation of the antibody.

Reactive deposition of nano-films in deep polymeric microcavities.

We report the controlled diffusion of gas-phase high-reactivity chemical species into long polymeric microcavities to form glass-like, low-permeability barrier films on the interior surfaces of the microcavities. Reactive species created from fragmentation of O(2) and hexamethyldisiloxane (HMDSO) in a radio-frequency (RF) plasma environment are allowed to diffuse into the microcavities of polydimethylsiloxane (PDMS), where surface reactions lead to the formation of an effective, glass-like thin-film barrier. Reactive species including silicon radicals and elemental oxygen maintain their reactivity for sufficient times (up to 7000 s) and survive the random diffusional walk through the microcavities to form glass barriers as much as 65 mm from the cavity entrance. The barrier thickness and the growth length can be controlled by the reaction time and chamber operating pressure. Increasing the cross sectional area of the cavity inlet and/or decreasing the mean free path was found to increase the thickness of the barrier film. Optical emission spectroscopic analysis was used to characterize the reactive fragments formed from HMDSO, and energy-dispersive X-ray analysis revealed that the barrier composition is consistent with oxides of silicon (SiO(x)). Formed inside PDMS microcavities, the glass barrier blocks the penetration or absorption of small molecules such as rhodamine B (RhB) and biotin, and also resists permeation of organic solvents such as toluene, preventing the PDMS microfluidic structures from swelling and deforming. Moreover, formation of glass-like thin films in PDMS microcavities enhances the stability of electroosmotic flow (EOF) relative to uncoated PDMS devices, in which EOF instabilities are significant; this enables separation by electrophoresis with reproducibility (relative standard deviation 3%, n = 5) and baseline peak resolution (R:1.3) comparable to that obtained in conventional fused-silica capillaries.

Multi-layered plasma-polymerized chips for SPR-based detection.

The surface functionalization of a noble metal is crucial in a surface plasmon resonance-based biomolecular detection system because the interfacial coating must retain the activity of immobilized biomolecules while enhancing the optimal loading. We present here a one-step, room-temperature, high-speed, gas-phase plasma polymerization process for functionalizing gold substrates using siloxane as an adhesion layer and acrylic acid as a functional layer. Siloxane- and thiol-based coatings were compared for their performance as adhesion and the interfacial layer for subsequent functionalization. An in situ sequential deposition of siloxane and acrylic acid resulted in a 7-fold increase in carboxylic functionality surfacial content compared to films deposited with thiol-containing precursors. Grading of the layer composition achieved as a consequence of ion-induced mixing on the surface coating under the application of the plasma is confirmed through secondary ion mass spectroscopic studies. DNA hybridization assays were demonstrated on gold/glass substrates using surface plasmon enhanced ellipsometry and the applicability of this coating for protein immunoassays were demonstrated with plasma functionalized gold/plastic substrates in Biacore 3000 SPR instrument.

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.

Total internal reflection ellipsometry as a label-free assessment method for optimization of the reactive surface of bioassay devices based on a functionalized cycloolefin polymer.

We report a label-free optical detection technique, called total internal reflection ellipsometry (TIRE), which can be applied to study the interactions between biomolecules and a functionalized polymer surface. Zeonor (ZR), a cycloolefin polymer with low autofluorescence, high optical transmittance and excellent chemical resistance, is a highly suitable material for optical biosensor platforms owing to the ease of fabrication. It can also be modified with a range of reactive chemical groups for surface functionalization. We demonstrate the applications of TIRE in monitoring DNA hybridization assays and human chorionic gonadotrophin sandwich immunoassays on the ZR surface functionalized with carboxyl groups. The Ψ and Δ spectra obtained after the binding of each layer of analyte have been fitted to a four-layer ellipsometric model to quantitatively determine the amount of analytes bound specifically to the functionalized ZR surface. Our proposed TIRE technique with its very low analyte consumption and its microfluidic array format could be a useful tool for evaluating several crucial parameters in immunoassays, DNA interactions, adsorption of biomolecules to solid surfaces, or assessment of the reactivity of a functionalized polymer surface towards a specific analyte.