Plasma-polymerized Fluorocarbon Research Articles

Analogous Design of a Microlayered Silicon Oxide-Based Electrode to the General Electrode Structure for Thin-Film Lithium-Ion Batteries.

Development of miniaturized thin-film lithium-ion batteries (TF-LIBs) using vacuum deposition techniques is crucial for low-scale applications, but addressing low energy density remains a challenge. In this work, structures analogous to SiOx-based thin-film electrodes are designed with close resemblance to traditional LIB slurry formulations including active material, conductive agent, and binder. The thin-film is produced using mid-frequency sputtering with a single hybrid target consisting of SiOx nanoparticles, carbon nanotubes, and polytetrafluoroethylene. The thin-film SiOx/PPFC (plasma-polymerized fluorocarbon) involves a combination of SiOx and conductive carbon within the PPFC matrix. This results in enhanced electronic conductivity and superior elasticity and hardness in comparison to a conventional pure SiOx-based thin-film. The electrochemical performance of the half-cell consisting of thin-film SiOx/PPFC demonstrates remarkable cycling stability, with a capacity retention of 74.8% up to the 1000th cycle at 0.5 C. In addition, a full cell using the LiNi0.6Co0.2Mn0.2O2 thin-film as the cathode material exhibits an exceptional initial capacity of ≈120 mAh g-1 at 0.1 C and cycle performance, marked by a capacity retention of 90.8% from the first cycle to the 500th cycle at a 1 C rate. This work will be a stepping stone for the AM/CB/B composite electrodes in TF-LIBs.

Flexible BioMEMS devices enabled by micromachining of plasma-polymerized fluorocarbon

Flexible BioMEMS devices enabled by micromachining of plasma-polymerized fluorocarbon

Investigation of thermal property of plasma‐polymerized fluorocarbon thin films

AbstractThe physical property changes in the plasma‐polymerized fluorocarbon (PPFC) thin films near the melting temperature (Tm) were investigated through chemical structure analysis. The PPFC thin films, produced by semi‐crystalline polytetrafluoroethylene (PTFE)‐based polymer sputtering target, form amorphous polymers with outstanding properties, such as high water repellency and high optical transmittance, electrical insulation, and chemical resistance. Interestingly, in‐situ X‐ray photoelectron spectroscopy analysis revealed that the PPFC thin films maintained their physical properties at temperatures above the Tm in vacuum and exhibited properties similar to those of bulk PTFE while maintaining amorphous structure. Therefore, this thin film can be applied to various devices and surface coatings manufactured at high temperatures.

Thermal reflow of plasma-polymerized fluorocarbon for nanochannels and particle encapsulation

Thermal reflow is an important property for thermoplastic polymers, which has been studied extensively especially for photoresists and electron beam resists in semiconductor industries. While the surface smoothening effect is beneficial to reduce the roughness of micro- and nanostructures, the drastic morphology change has been tested to be efficient to fabricate optical devices like microlens arrays. Plasma-polymerized fluorocarbon (PPFC) is a feasible polymer material, which can be achieved conveniently with standard plasma etching systems, however, there have been limited studies regarding its properties and applications apart from its usage as a passivation layer during reactive ion etching. In this study, the thermal reflow behavior of PPFC on various substrates will be presented, including planar surfaces, gratings and trenches. Importantly, the formation of buried micro- and nanochannels has been demonstrated, when PPFC is heated above its glass transition temperature on trench structures. This encapsulation dynamics is analyzed with regard to various parameters like temperature and duration of thermal treatment, trench widths and initial thickness of PPFC film. As a proof of concept, silicon nanorods have been encapsulated in the microchannels by the reflowed PPFC. The results have demonstrated strong potentials of PPFC for applications like micro- and nanofluidics, microcontainers and drug delivery. Because of its good chemical stability and biocompatibility, PPFC can also be expected to be used for various biological devices like brain-machine interfaces, neural probes, epidermal devices and biological implants.

Nanostructured Plasma Polymerized Fluorocarbon Films for Drop Coating Deposition Raman Spectroscopy (DCDRS) of Liposomes.

Raman spectroscopy is one of the most used biodetection techniques. However, its usability is hampered in the case of low concentrated substances because of the weak intensity of the Raman signal. To overcome this limitation, the use of drop coating deposition Raman spectroscopy (DCDRS), in which the liquid samples are allowed to dry into well-defined patterns where the non-volatile solutes are highly concentrated, is appropriate. This significantly improves the Raman sensitivity when compared to the conventional Raman signal from solution/suspension. As DCDRS performance strongly depends on the wetting properties of substrates, we demonstrate here that the smooth hydrophobic plasma polymerized fluorocarbon films prepared by magnetron sputtering (contact angle 108°) are well-suited for the DCDRS detection of liposomes. Furthermore, it was proved that even better improvement of the Raman signal might be achieved if the plasma polymer surfaces are roughened. In this case, 100% higher intensities of Raman signal are observed in comparison with smooth fluorocarbon films. As it is shown, this effect, which has no influence on the profile of Raman spectra, is connected with the increased hydrophobicity of nanostructured fluorocarbon films. This results in the formation of dried liposomal deposits with smaller diameters and higher preconcentration of liposomes.

Transparent, Water-Repellent, Antiviral, Antistatic, and Flexible Cu-Plasma-Polymerized Fluorocarbon Nanocomposite Thin Films.

Polymer thin films containing fluorine are attracting much attention in various high-tech industries owing to their transparency, flexibility, and excellent water repellency. However, the generation of static electricity due to high electrical resistance limits their application. In this study, highly transparent and flexible Cu-plasma-polymerized fluorocarbon (PPFC) nanocomposite thin films that exhibit hydrophobicity and antistatic properties are proposed. These films, obtained using the mid-range frequency sputtering, exhibited a light transmittance of 84.2%, a water contact angle of 94.6°, and a sheet resistance of 1.2 × 1012 Ω/□. Transmission electron microscopy and small angle X-ray scattering confirmed that Cu nanoparticles with an average size of 4-5 nm were distributed uniformly in the PPFC matrix. In repeated fatigue bending tests, the Cu-PPFC nanocomposite thin films exhibited excellent mechanical robustness and flexibility. Antiviral properties of the Cu-PPFC nanocomposite thin films were evaluated against influenza A virus, and the number decreased by 96.9% after 30 min. Carbon nanotube-Cu-polytetrafluoroethylene composite targets are advantageous for large-area coating and mass production because they can be applied in large-area sputtering and roll-to-roll processes. The transparency, charging characteristics, and water repellency can be easily controlled in Cu-PPFC nanocomposite thin films by controlling the sputtering power density according to the required product. Therefore, these films can be applied in various industries such as flexible displays, medical, automobiles, functional textiles, and aerospace.

Area-selective atomic layer deposition of noble metals: Polymerized fluorocarbon layers as effective growth inhibitors

The increasingly complex nanoscale three-dimensional and multilayered structures utilized in nanoelectronic, catalytic, and energy conversion/storage devices necessitate novel substrate-selective material deposition approaches featuring bottom-up and self-aligned precision processing. Here, we demonstrate the area-selective atomic layer deposition (AS-ALD) of two noble metals, Pt and Pd, by using a plasma-polymerized fluorocarbon layer as growth inhibition surfaces. The contact angle, x-ray photoelectron spectroscopy (XPS), and scanning electron microscopy measurements were performed to investigate the blocking ability of polymerized fluorocarbon (CFx) layers against ALD-grown metal films. Both Pt and Pd showed significant nucleation delays on fluorocarbon surfaces. Self-aligned film deposition is confirmed using this strategy by growing Pt and Pd on the microscale lithographically patterned CFx/Si samples. CFx blocking layer degradation during ozone exposure was analyzed using XPS measurements, which confirmed the oxygen physisorption as the main responsible surface reaction with further hydroxyl group formation on the CFx surface. Our work reveals that the CFx layer is compatible with an ozone coreactant until the blocking polymer cannot withstand oxygen physisorption. Our results could potentially be used to investigate and develop radical-assisted AS-ALD processes for a wider selection of materials.

Low-temperature plasma polymerized fluorocarbon coating promotes surface charge dissipation in polystyrene

Polystyrene (PS) is a common insulating material in pulsed power devices, which has excellent and reliable insulation properties. However, the charge accumulation on the insulator surface seriously threatens its surface insulation property. Surface modification has been verified as an effective way for inhibiting surface charge accumulation. In this paper, plasma polymerized fluorocarbon (PPFC) coating was prepared by low-temperature plasma polymerization in the mixture of methyl-methacrylate and dodecafluoroheptyl-methacrylate (DFHMA). Compared with the untreated PS, the surface charge dissipation rate of PPFC coating is increased by more than 6 times. The introduction of DFHMA makes the coating have no obvious ageing effect after the storage, and has good reusability after the surface flashover. This work provides a new method for modification of polymer dielectrics and a novel way for the preparation of high-charge-dissipation polymers in other related fields.

One-Pot but Two-Step Vapor-Based Amine- and Fluorine-Bearing Dual-Layer Coating for Improving Anticorrosion and Biocompatibility of Magnesium Alloy.

Hydrophobic coating is of great interest to enhance the corrosion resistance of magnesium alloy implants, which always suffer from rapid corrosion that leads to the failing application under physiological conditions. Plasma-polymerized fluorocarbon (C-F) coating has been widely studied as a substrate protection layer; however, the precise control of the deposition rate of C-F coating with fluorinated alkanes has been a challenge. In this study, a thin, uniform, pinhole-free, polymerlike, and hydrophobic C-F coating was successfully prepared using acetylene (C2H2) as a cross-linking agent, which endows the coating with tunable properties of deposition rate by incorporation of unsaturated bonds. Electrochemical corrosion and in vitro immersion test demonstrated that the C-F coating significantly slows down the corrosion rate of MgZnMn in phosphate-buffered saline solution at 37 °C. Furthermore, an additional layer of PPAam was deposited on the C-F coating to eliminate the adverse effect of C-F surface on cytocompatibility. Thus, such a stacked coating imparts MgZnMn with a significantly improved corrosion resistance and promotes cell adhesion and viability. Therefore, the strategy of acetylene-mediated C-F-based coating shows a great potential for tailoring ideal surface functionalities of magnesium-based medical devices.

Antireflective, self-cleaning and protective film by continuous sputtering of a plasma polymer on inorganic multilayer for perovskite solar cells application

Optical films with antireflective and self-cleaning surfaces have much potential for applications in solar cells, architectural glasses, and outdoor displays. Here we demonstrate the fabrication of novel self-cleaning antireflection (AR) thin films by depositing plasma-polymerized fluorocarbon (PPFC) which is fluorinated polymer consisting carbon and fluorine formed under plasma environment on Nb2O5/SiO2/Nb2O5 (NSN) trilayers using mid-range frequency power source in a continuous roll-to-roll sputtering system. The reflectance of PPFC/NSN films with a PPFC thickness of 70 nm was 1.71% at a wavelength of 528 nm, and the PPFC/NSN films showed low reflectance in a wide range in the visible region. The PPFC/NSN AR films exhibited a water-repelling surface with water contact angle of 105° after the application of a top fluorocarbon layer with low surface energy. We tested and confirmed the AR and self-cleaning functions of the PPFC/NSN films through the incorporation to perovskite solar cells (PSC). The short-circuit current density and power conversion efficiency of PPFC/NSN/HC-PET/PSC were 20.6 mA cm−2 and 17%. By attaching a self-cleaning AR films to both side of PSC, photocurrent collection of the device was improved and applicability of protective films to PSC was demonstrated.

Advances and challenges in the field of plasma polymer nanoparticles.

This contribution reviews plasma polymer nanoparticles produced by gas aggregation cluster sources either via plasma polymerization of volatile monomers or via radio frequency (RF) magnetron sputtering of conventional polymers. The formation of hydrocarbon, fluorocarbon, silicon- and nitrogen-containing plasma polymer nanoparticles as well as core@shell nanoparticles based on plasma polymers is discussed with a focus on the development of novel nanostructured surfaces.

Flexible Polymer/Metal/Polymer and Polymer/Metal/Inorganic Trilayer Transparent Conducting Thin Film Heaters with Highly Hydrophobic Surface.

Polymer/metal/polymer and polymer/metal/inorganic trilayer-structured transparent electrodes with fluorocarbon plasma polymer thin film heaters have been proposed. The polymer/metal/polymer and polymer/metal/inorganic transparent conducting thin films fabricated on a large-area flexible polymer substrate using a continuous roll-to-roll sputtering process show excellent electrical properties and visible-light transmittance. They also exhibit water-repelling surfaces to prevent wetting and to remove contamination. In addition, the adoption of a fluorocarbon/metal/fluorocarbon film permits an outer bending radius as small as 3 mm. These films have a sheet resistance of less than 5 Ω sq-1, sufficient to drive light-emitting diode circuits. The thin film heater with the fluorocarbon/Ag/SiNx structure exhibits excellent heating characteristics, with a temperature reaching 180 °C under the driving voltage of 13 V. Therefore, the proposed polymer/metal/polymer and polymer/metal/inorganic transparent conducting electrodes using polymer thin films can be applied in flexible and rollable displays as well as automobile window heaters and other devices.

RMS roughness-independent tuning of surface wettability by tailoring silver nanoparticles with a fluorocarbon plasma polymer.

A layer of 14 nm-sized Ag nanoparticles undergoes complex transformation when overcoated by thin films of a fluorocarbon plasma polymer. Two regimes of surface evolution are identified, both with invariable RMS roughness. In the early regime, the plasma polymer penetrates between and beneath the nanoparticles, raising them above the substrate and maintaining the multivalued character of the surface roughness. The growth (β) and the dynamic (1/z) exponents are close to zero and the interface bears the features of self-affinity. The presence of inter-particle voids leads to heterogeneous wetting with an apparent water contact angle θa = 135°. The multivalued nanotopography results in two possible positions for the water droplet meniscus, yet strong water adhesion indicates that the meniscus is located at the lower part of the spherical nanofeatures. In the late regime, the inter-particle voids become filled and the interface acquires a single valued character. The plasma polymer proceeds to grow on the thus-roughened surface whereas the nanoparticles keep emerging away from the substrate. The RMS roughness remains invariable and lateral correlations propagate with 1/z = 0.27. The surface features multiaffinity which is given by different evolution of length scales associated with the nanoparticles and with the plasma polymer. The wettability turns to the homogeneous wetting state.

Area-Selective Atomic Layer Deposition Using an Inductively Coupled Plasma Polymerized Fluorocarbon Layer: A Case Study for Metal Oxides

Area-selective atomic layer deposition (AS-ALD) has attracted immense attention in recent years for self-aligned accurate pattern placement with subnanometer thickness control. Here, we demonstrate a methodology to achieve AS-ALD by using inductively couple plasma (ICP) grown fluorocarbon polymer film as hydrophobic blocking layer for selective deposition. Our approach has been tested for metal-oxide materials including ZnO, Al2O3, and HfO2. Contact angle, X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometer, and scanning electron microscopy (SEM) measurements were performed to investigate the blocking ability of plasma polymerized fluorocarbon layers against ALD-grown metal-oxide films. A considerable growth inhibition for ZnO has been observed on fluorocarbon coated Si(100) surfaces, while the same polymerized surface caused a relatively slow nucleation for HfO2 films. No growth selectivity was obtained for Al2O3 films, displaying almost the same nucleation behavior on Si and fluorocarbon ...

One-step fabrication of nickel nanocones by electrodeposition using CaCl2·2H2O as capping reagent

In this research, a method for the fabrication of nickel nanocones through the addition of CaCl2·2H2O to an electrodeposition solution was proposed. When electrodeposition was performed after CaCl2·2H2O addition, precipitation of the Ni ions onto the (200) crystal face was suppressed and anisotropic growth of the nickel electrodeposited structures was promoted. Sharper nanocones were produced with increasing concentration of CaCl2·2H2O added to the solution. Moreover, when temperature of the electrodeposition solutions approached 60°C, the apex angle of the nanostructures decreased. In addition, the nanocones produced were applied to superhydrophobic surface modification using a plasma-polymerized fluorocarbon (PPFC) coating. When the solution temperature was maintained at 60°C and the concentration of the added CaCl2·2H2O was 1.2M or higher, the fabricated samples showed superhydrophobic surface properties. The proposed nickel nanocone formation method can be applied to various industrial fields that require metal nanocones, including superhydrophobic surface modification.

Long-range surface plasmon resonance sensors fabricated with plasma polymerized fluorocarbon thin films

A rapid and simple approach to prepare the dielectric buffer layers is of crucial importance for the development of long-range surface plasmon resonance (LRSPR) sensors. In this regard, we describe for the first time the use of plasma polymerized fluorocarbon thin films as the dielectric buffer layers for the construction of LRSPR sensors. The fluorocarbon films were achieved by radio frequency plasma polymerization of perfluorooctyl ethylene (PFOE) at continuous wave mode with an input power of 60 Watts. The resulting ppPFOE exhibited good adhesion with both the glass substrate and the gold superstrate, and also remained relatively stable in aqueous solutions as seen by optical waveguide spectroscopy (OWS). The obtained LRSPR sensor consisting of a SF11-ppPFOE-Au structure was employed for the detection of both the bulk refractive index variation and the protein adsorption.

Influence of open area ratio on microstructure shape in Cu–Ni alloy electrodeposition

This research experimentally analyzed the influence of the open area ratio (OAR) on the formation and growth of the microstructure in Cu–Ni alloy electrodeposition. The OAR was controlled by changing the pitch of circular patterns with a diameter of 20 µm. For an OAR higher than 20 %, the electrodeposited structures grew vertically in pillar-like formations. As the OAR was decreased from 100 to 20 %, the density, height, and width of the structures increased. In addition, in this OAR range, the structures formed along the edge area of the circular patterns. In contrast, for an OAR lower than 10 %, dendrite structures were generated. The electrodeposited structures were coated with a hydrophobic plasma-polymerized fluorocarbon (PPFC) layer. In the electrodeposited sample without circular patterns (OAR = 100 %) with an OAR smaller than 1.25 %, the measured contact angles were almost the same as the contact angle (107°) measured from the flat surface without electrodeposition. In contrast, the samples with an OAR range of 2.5–50 % were modified to be superhydrophobic, and they demonstrated an excellent self-cleaning ability.

Poly(tetrafluoroethylene) sputtering in a gas aggregation source for fabrication of nano-structured deposits

R. f. magnetron sputtering of poly(tetrafluoroethylene) in configuration of a gas aggregation source is shown to produce super-hydrophobic nano-structured coatings in which cross-linked nano-particles of fluorocarbon plasma polymer are embedded in an uncross-linked continuous (CF2)x matrix. The 20–30nm nano-particles appear in proximity of the magnetron and have cross-linked structure as a result of fast random radical recombination in the plasma. The continuous phase is formed at remote distances from the magnetron as a result of slower step-growth gas phase polymerization of CF2 bi-radicals. The matrix has highly crystalline structure in which the CF2 groups tend to adopt a 15/7 helical configuration. At least part of the macromolecules constituting the polymeric phase are oligomers with the molar mass below 1400g/mol.

Deposition of fluorocarbon film with 1,1,1,2-tetrafluoroethane pulsed plasma polymerization

The fluorocarbon films were synthesized by radio frequency pulsed 1, 1, 1, 2-tetrafluoroethane plasma polymerization using various duty cycles. The deposition rates and water contact angles were examined for radio frequency pulsed plasma polymerized fluorocarbon films. The film surface properties were also determined by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy. For varying duty cycle from 100% to 10% in pulsed plasma process, the plasma polymerized film drastically changed the surface property. Specifically, it has been observed that modulated plasmas with the proper duty cycle of 10% lead to the formation of the super-hydrophobic film by static water contact angle value of 150°. The surface properties of fluorocarbon films were determined as the Cassie state. In the transmittance, UV–VIS transmission spectra showed that these radio frequency pulsed plasma polymerized coatings were transparent in visible light region. By adjusting duty cycles in relation to radio frequency pulsed plasma polymerization, the hydrophobicity of the resulting thin fluorocarbon films could be tuned.

Effect of the diffusion rate of the copper ions on the co-electrodeposition of copper and nickel

This study experimentally analyzed the influence of the diffusion rate of Cu ions on the growth of microstrucutres during the coelectrodeposition of copper and nickel. To change the diffusion rate of the Cu ions resolved in the electrodeposition solution, electrodeposition was performed under three different stirring conditions (0, 150, 300 rpm). The microstructure grew in an orientation vertical to the microstructure, similar to a probe without stirring, while a popcorn-shaped cluster with electrodeposition particles at the upper part of the microstructure was found under the stirring condition. Forced circulation of the electrodeposition solution by stirring drastically enhanced the movement of the Cu ions, and popcorn shaped clusters are formed. The average height and width of the structure electrodeposited for 20 minutes through stirring at 300 rpm were 1.5 and 4.3 times greater, respectively, than those of the structure electrodeposited without stirring. The substrate surfaces covered with electrodeposited microstructures were modified to be superhydrophobic by coating them with hydrophobic plasma polymerized fluorocarbon (PPFC).