Oxygen Plasma Exposure Research Articles

Piezoelectric energy harvesting from the atomic oxygen hypervelocity impact in low Earth orbit

Atomic oxygen (AO) in low Earth orbit (LEO) can cause severe progressive damage to spacecraft orbiting at hypervelocities over 7 km/s; therefore, all space-graded materials need to be qualified for protection against these high energy impacts. Instead of treating AO as a threat, can we use these atomic impacts, which have enough energy to cause material failure, to generate power? Despite its potential, no attempt has yet been made to utilize the hypervelocity impact energy of AO. Thus, we propose a piezoelectric energy harvesting method through the hypervelocity AO impact in LEO. In this study, energy harvesting with various configurations was experimentally demonstrated using a conventional lead zirconate titanate (PZT) ceramic plate under oxygen plasma exposure to simulate AO impact. The average output power density was 4 W/m2 under 1.43 × 1016 atoms/cm2s effective AO flux conditions. Our study provides a new method for generating energy in a space environment with limited energy sources.

Imaging the magnetic nanowire cross section and magnetic ordering within a suspended 3D artificial spin-ice

Artificial spin-ice systems are patterned arrays of magnetic nanoislands arranged into frustrated geometries and provide insight into the physics of ordering and emergence. The majority of these systems have been realized in two-dimensions, mainly due to the ease of fabrication, but with recent developments in advanced nanolithography, three-dimensional artificial spin ice (ASI) structures have become possible, providing a new paradigm in their study. Such artificially engineered 3D systems provide new opportunities in realizing tunable ground states, new domain wall topologies, monopole propagation, and advanced device concepts, such as magnetic racetrack memory. Direct imaging of 3DASI structures with magnetic force microscopy has thus far been key to probing the physics of these systems but is limited in both the depth of measurement and resolution, ultimately restricting measurement to the uppermost layers of the system. In this work, a method is developed to fabricate 3DASI lattices over an aperture using two-photon lithography, thermal evaporation, and oxygen plasma exposure, allowing the probe of element-specific structural and magnetic information using soft x-ray microscopy with x-ray magnetic circular dichroism (XMCD) as magnetic contrast. The suspended polymer–permalloy lattices are found to be stable under repeated soft x-ray exposure. Analysis of the x-ray absorption signal allows the complex cross section of the magnetic nanowires to be reconstructed and demonstrates a crescent-shaped geometry. Measurement of the XMCD images after the application of an in-plane field suggests a decrease in magnetic moment on the lattice surface due to oxidation, while a measurable signal is retained on sub-lattices below the surface.

Single-Particle Spectroelectrochemistry: Promoting the Electrocatalytic Activity of Gold Nanorods via Oxygen Plasma Treatment without Structural Deformation.

Understanding of the electrocatalytic activity enhancement in gold nanoparticles is still limited. Herein, we present the effect of the oxygen plasma treatment on the electrochemical activity of gold nanorods (AuNRs). Oxygen plasma treatment resulted in the blueshift and line width narrowing of the localized surface plasmon resonance (LSPR) spectra obtained from individual AuNRs immobilized on an indium tin oxide (ITO) surface. These changes can be attributed to increases in the surface charges of the AuNRs. The formation of a Au-ITO heterojunction provided structural stability to the immobilized AuNRs regardless of the duration of oxygen plasma exposure. The electrocatalytic oxidation of hydrogen peroxide (H2O2) was induced by increases in the free-electron densities on the surfaces of these AuNRs owing to oxygen plasma treatment, and Au did not dissolve under the experimental conditions. However, the potential-dependent LSPR spectra of the individual AuNRs showed similar patterns of LSPR behavior, irrespective of the duration of oxygen plasma treatment and the concentration of H2O2. Therefore, this study based on single-particle spectroelectrochemistry and cyclic voltammetry improves the understanding of the role of oxygen plasma treatment in promoting the catalytic activity of structurally stable AuNRs immobilized on an ITO surface.

Irreversible Bonding of Polydimethylsiloxane-Lithium Niobate using Oxygen Plasma Modification for Surface Acoustic Wave based Microfluidic Application: Theory and Experiment.

Acoustic microfluidic chips, fabricated by combining lithium niobate (LiNbO3) with polydimethylsiloxane (PDMS), practically find applications in biomedicine. However, high-strength direct bonding of LiNbO3 substrate with PDMS microchannel remains a challenge due to the large mismatching of thermal expansion coefficient at the interface and the lack of bonding theory. This paper elaborately reveals the bonding mechanisms of PDMS and LiNbO3, demonstrating an irreversible bonding method for PDMS-LiNbO3 heterostructures using oxygen plasma modification. An in-situ monitoring strategy by using resonant devices is proposed for oxygen plasma, including quartz crystal microbalance (QCM) covered with PDMS and surface acoustic wave (SAW) fabricated by LiNbO3. When oxygen plasma exposure occurs, surfaces are cleaned, oxygen ions are implanted, and hydroxyl groups (-OH) are formed. Upon interfaces bonding, the interface will form niobium-oxygen-silicon covalent bonds to realize an irreversible connection. A champion bonding strength is obtained of 1.1 MPa, and the PDMS-LiNbO3 acoustic microfluidic chip excels in leakage tests, withstanding pressures exceeding 60 psi, outperforming many previously reported devices. This work addresses the gap in PDMS-LiNbO3 bonding theory and advances its practical application in the acoustic microfluidic field.

Glucose Oxidase Loading in Ordered Porous Aluminosilicates: Exploring the Potential of Surface Modification for Electrochemical Glucose Sensing.

Enzymatic electrochemical sensors have become the leading glucose detection technology due to their rapid response, affordability, portability, selectivity, and sensitivity. However, the performance of these sensors is highly dependent on the surface properties of the electrode material used to store glucose oxidase and its ability to retain enzymatic activity under variable environmental conditions. Mesoporous thin films have recently attracted considerable attention as promising candidates for enzyme storage and activity preservation due to their well-defined nanoarchitecture and tunable surface properties. Herein, we systematically compare pathways for the immobilization of glucose oxidase (GOx) and their effectiveness in electrochemical glucose sensing, following modification protocols that lead to the electrostatic attraction (amino functionalization), covalent bonding (aldehyde functionalization), and electrostatic repulsion (oxygen plasma treatment) of the ordered porous aluminosilicate-coated electrodes. By direct comparison using a quartz crystal microbalance, we demonstrate that glucose oxidase can be loaded in a nanoarchitecture with a pore size of ∼50 nm and pore interconnections of ∼35 nm using the native aluminosilicate surface, as well as after amino or aldehyde surface modification, while oxygen plasma exposure of the native surface inhibits glucose oxidase loading. Despite a variety of routes for enzyme loading, quantitative electrochemical glucose sensing between 0 and 20 mM was only possible when the porous surface was functionalized with amino groups, which we relate to the role of surface chemistry in accessing the underlying substrate. Our results highlight the impact of rational surface modification on electrochemical biosensing performance and demonstrate the potential of tailoring porous nanoarchitecture surfaces for biosensing applications.

Easy cleaning plus stable activation of glassy carbon electrode surface by oxygen plasma

Glassy carbon (GC) electrodes are widely used in electroanalytical applications especially in bioelectrochemistry. Their use starts with an efficient surface cleaning and activation protocol, mostly based on surface polishing steps. We studied the use of an oxygen plasma exposure of GC electrodes to replace common polishing procedures. The cyclic voltammetry (CV) responses of ferrocyanide and ferrocene-dimethanol were used to compare brand new, surface-polished and plasma-treated GC electrodes. Plasma treatment induces CV responses with improved features, close to theoretical values, as compared to other methods. The plasma effects were quasi-stable over a week when electrodes were stored in water, this being explained by increased surface energy and hydrophilicity. Furthermore, when electroreduction of diazonium was performed on GC electrodes, the surface blockade could be removed by the plasma. Thus, a short oxygen plasma treatment is prone to replace polishing protocols, that display person-dependent efficiency, in most of the experiments with GC electrodes.

Robust formation of ferroelectric HfO2 films by Y2O3 sub-monolayer lamination

Process robustness of ferroelectric HfO2 films formed by dopant-laminated structure is investigated. Ferroelectric hysteresis obtained by the sub-monolayer Y2O3 laminated structure confirms that entire doping to the HfO2 films is not indispensable to stabilizing the ferroelectric phase. The Y-laminated HfO2 capacitors show robustness against the oxygen plasma exposure time, in contrast to the positive hysteresis shift for uniformly doped HfO2 ones. The number of switching cycles was increased, presumably owing to the reduction of oxygen vacancies associated with the incorporated dopants. Moreover, the leakage current showed a reduction with a higher breakdown voltage.

Oxidation Resistance Improvement of Graphene-Oxide-Semiconductor Planar-Type Electron Sources Using h-BN as an Oxygen-Resistant, Electron-Transmissive Coating.

Graphene–oxide–semiconductor (GOS) planar-type electron emission devices with a hexagonal boron nitride (h-BN) protective layer have demonstrated improved oxidation resistance while maintaining their emission performance. The devices with a monolayer or a multilayer (13 nm in thickness) h-BN protective layer can emit electrons even after oxygen plasma exposure (ashing). Remarkably, the device with a monolayer h-BN was able to emit electrons with a maximum efficiency of 11% after a 4-min ashing, showing that a thin h-BN protection layer can provide oxygen tolerance to GOS devices without a significant emission loss. The thicker multilayer h-BN imparted higher oxidation resistance to the device but with decreased emission efficiency compared with the device with monolayer h-BN. Thus, the use of h-BN necessitates a trade-off between the device’s emission performance and its oxidation resistance. In addition, the etching rate of h-BN by the oxygen plasma treatment was found to increase by exposure to air after the first plasma treatment, which indicates that the adherence of H2O to the surface of h-BN is one probable cause of h-BN etching during the ashing process.

Designing Multifunctional Cobalt Oxide Layers for Efficient and Stable Electrochemical Oxygen Evolution

AbstractDisordered and porous metal oxides are promising earth‐abundant and cost‐effective alternatives to noble‐metal electrocatalysts. Herein, nonsaturated oxidation in plasma‐enhanced atomic layer deposition is leveraged to tune the structural, mechanical, and optical properties of biphasic cobalt hydroxide films, thereby tailoring their catalytic activities and chemical stabilities. Short oxygen plasma exposure times and low plasma powers incompletely oxidize the cobaltocene precursor to Co(OH)2 and result in carbon impurity incorporation. These Co(OH)2 films are highly porous and catalytically active, but their electrochemical stability is impacted by poor substrate adhesion. In contrast, long exposure times and high powers completely oxidize the precursor to Co3O4, reduce the carbon incorporation, and improve the crystallinity. While the Co3O4 films have high electrochemical stability, they are characterized by low oxygen evolution reaction activity. To overcome these competing properties, the established relation between deposition parameters and functional film properties is applied to design bilayer films exhibiting simultaneously improved electrochemical performance and chemical stability. The bilayer films combine a highly active Co(OH)2 surface with a stable Co3O4 interface layer. These coatings exhibit minimal light absorption, thus making them suitable as protective catalytic layers on semiconductor light absorbers for application in photoelectrochemical devices.

Scalable production of single 2D van der Waals layers through atomic layer deposition: bilayer silica on metal foils and films

The self-limiting nature of atomic layer deposition (ALD) makes it an appealing option for growing single layers of two-dimensional van der Waals (2D-VDW) materials. In this paper it is demonstrated that a single layer of a 2D-VDW form of SiO2 can be grown by ALD on Au and Pd polycrystalline foils and epitaxial films. The silica was deposited by two cycles of bis(diethylamino) silane and oxygen plasma exposure at 525 K. Initial deposition produced a three-dimensionally disordered silica layer; however, subsequent annealing above 950 K drove a structural rearrangement resulting in 2D-VDW. The annealing could be performed at ambient pressure. Surface spectra recorded after annealing indicated that the two ALD cycles yielded close to the silica coverage obtained for 2D-VDW silica prepared by precision SiO deposition in ultra-high vacuum (UHV). Analysis of ALD-grown 2D-VDW silica on a Pd(111) film revealed the co-existence of amorphous and incommensurate crystalline 2D phases. In contrast, ALD growth on Au(111) films produced predominantly the amorphous phase while SiO deposition in UHV led to only the crystalline phase, suggesting that the choice of Si source can enable phase control.

Surface modification of high-surface area graphites by oxygen plasma treatments

Two types of high-surface area graphite having different specific surface areas (HSAG100 and HSAG300) were treated in a low-pressure microwave discharge oxygen plasma for 3 and 10 min. The physico-chemical properties at surface scale of the resulting materials were investigated by N2 physisorption, Raman spectroscopy, temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). For both materials, an increase of the degree of graphitic order was observed following the longer oxygen plasma exposure. Likewise, the 10-min plasma treatment gave place to surface-functionalized materials without compromising their thermal stability and aromatic network. Particularly, for HSAG100, the longer plasma exposure contributed to the development of an edge surface-functionalized graphite. In the case of as-received HSAG300, the presence of a mechanically damaged sub-surface ascribable to the milling process could be evidenced.

Effect of O2 plasma exposure time during atomic layer deposition of amorphous gallium oxide

Amorphous gallium oxide thin films were grown by plasma-enhanced atomic layer deposition on (100) silicon substrates from trimethylgallium Ga(CH3)3 precursor and oxygen plasma. At 200 °C, the growth per cycle is in the range of 0.65–0.70 Å for O2 plasma exposure times ranging from 3 up to 30 s during each cycle. The effect of O2 plasma exposure times on the interfacial SiOx regrowth and the electrical properties was investigated. In situ spectroscopic ellipsometry shows that the SiOx regrowth occurs during the first three cycles and is limited to 0.27 nm for plasma times as long as 30 s. Increasing the O2 plasma exposure during each ALD cycle leads to a drastic decrease in the leakage current density (more than 5 orders of magnitude for 30 nm films), which is linked to the suppression of oxygen vacancy states as evidenced by spectroscopic ellipsometry. Interestingly, an increase in the dielectric constant with increasing O2 plasma exposure time is observed, reaching a value of εr∼14.2, larger than that of single crystalline β-Ga2O3. This study highlights the crucial role of oxygen plasma exposure time in the control and tuning of the electrical properties of amorphous gallium oxide films.

Iso- and Anisotropic Etching of Micro Nanofibrillated Cellulose Films by Sequential Oxygen and Nitrogen Gas Plasma Exposure for Tunable Wettability on Crystalline and Amorphous Regions.

The surface of cellulose films, obtained from micro nanofibrillated cellulose produced with different enzymatic pretreatment digestion times of refined pulp, was exposed to gas plasma, resulting in a range of surface chemical and morphological changes affecting the mechanical and surface interactional properties. The action of separate and dual exposure to oxygen and nitrogen cold dielectric barrier discharge plasma was studied with respect to the generation of roughness (confocal laser and atomic force microscopy), nanostructural and chemical changes on the cellulose film surface, and their combined effect on wettability. Elemental analysis showed that with longer enzymatic pretreatment time the wetting response was sensitive to the chemical and morphological changes induced by both plasma gases, but distinctly oxygen plasma was seen to induce much greater morphological change while nitrogen plasma contributed more to chemical modification of the film surface. In this novel study, it is shown that exposure to oxygen plasma, subsequently followed by exposure to nitrogen plasma, leads first to an increase in wetting, and second to more hydrophobic behaviour, thus improving, for example, suitability for printing using polar functional inks or providing film barrier properties, respectively.

Oxygen Plasma Treated-Electrospun Polyhydroxyalkanoate Scaffolds for Hydrophilicity Improvement and Cell Adhesion.

Poly(hydroxyalkanoates) (PHAs) with differing material properties, namely, the homopolymer poly(3-hydroxybutyrate), P(3HB), the copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate), P(3HB-co-3HV), with a 3HV content of 25 wt.% and a medium chain length PHA, and mcl-PHA, mainly composed of 3-hydroxydecanoate, were studied as scaffolding material for cell culture. P(3HB) and P(3HB-co-3HV) were individually spun into fibers, as well as blends of the mcl-PHA with each of the scl-PHAs. An overall biopolymer concentration of 4 wt.% was used to prepare the electrospinning solutions, using chloroform as the solvent. A stable electrospinning process and good quality fibers were obtained for a solution flow rate of 0.5 mL h−1, a needle tip collector distance of 20 cm and a voltage of 12 kV for P(3HB) and P(3HB-co-3HV) solutions, while for the mcl-PHA the distance was increased to 25 cm and the voltage to 15 kV. The scaffolds’ hydrophilicity was significantly increased under exposure to oxygen plasma as a surface treatment. Complete wetting was obtained for the oxygen plasma treated scaffolds and the water uptake degree increased in all treated scaffolds. The biopolymers crystallinity was not affected by the electrospinning process, while their treatment with oxygen plasma decreased their crystalline fraction. Human dermal fibroblasts were able to adhere and proliferate within the electrospun PHA-based scaffolds. The P(3HB-co-3HV): mcl-PHA oxygen plasma treated scaffold highlighted the most promising results with a cell adhesion rate of 40 ± 8%, compared to 14 ± 4% for the commercial oxygen plasma treated polystyrene scaffold AlvetexTM. Scaffolds based on P(3HB-co-3HV): mcl-PHA blends produced by electrospinning and submitted to oxygen plasma exposure are therefore promising biomaterials for the development of scaffolds for tissue engineering.

Plasma augmented structural and electrical properties of half doped neodymium strontium manganites

The reduction in resistivity and modification of the thermoelectric power of perovskite oxides is in continuous demand because of its large scale industrial applications. Currently, electron or ion beam irradiations are the most preferred methods employed to improve its properties. The quantum of improvement achieved with these methods is appreciable, however, it involves intriguing technicalities in the production of the beams. Plasma is a natural medium with the presence of both electrons and ions that can be easily produced using the glow discharge technique. In this work, the effect of oxygen plasma exposure on the structural properties, electrical resistivity, and thermopower of Nd0.5Sr0.5MnO3 manganites is investigated. Powdered Nd0.5Sr0.5MnO3 manganites samples are prepared using the solid-state reaction method. It is found that plasma exposure has changed the lattice parameters thereby varying the cell volume, which are not normally seen in the case of electron beam exposure. Further, the electrical resistivity is observed to decrease significantly after plasma exposure that changed the transport properties. It is also observed that plasma exposure decreases the absolute value of thermopower at low temperatures but increases it at high temperatures.

Preparation of clean MgO surface by oxygen plasma: Comparison with standard substrate cleaning procedures

Different surface preparation methods for cleaning MgO, a widely used substrate in oxide epitaxy, are summarized and compared. We find that in situ surface preparation methods are preferable to ex situ preparation methods. We show that the complete removal of hydroxide, carbonate, and adventitious carbon from the MgO surface can be achieved via oxygen plasma exposure at 200 °C without high temperature annealing. Using this process, an atomically flat surface with root mean square roughness values of ∼0.1 nm is demonstrated. Surfaces treated thus also exhibit sharp RHEED streaks indicating good crystalline order of the surface. We also show that high temperature annealing of MgO, either by itself or following other ex situ cleaning methods, such as solvent cleaning, is a reasonably effective method for the removal of surface contaminants, enabling one to achieve a surface roughness of ∼0.2 nm. We show that wet etching or other ex situ cleaning methods alone without annealing cannot eliminate all surface contaminants and may even worsen the surface roughness significantly.

Electrical properties tunability of large area MoS2 thin films by oxygen plasma treatment

MoS2 thin films prepared via sulfurization of molybdenum films have attracted great attention due to their advantage for scalable synthesis with a large area coverage. However, the MoS2 thin films are typically more resistive than their exfoliated and co-evaporation chemical vapor deposition based counterparts. The ability to modulate the electrical property of MoS2 thin films will have a significant impact on scalable device applications in electronics, sensors, and catalysis. Here, we report the tuning of electrical transport properties of large area MoS2 thin films with different oxygen plasma exposure times. The electrical transport measurements of the pristine and plasma treated samples reveal that with increasing oxygen plasma treatment, the resistance of the MoS2 thin films first decreases by almost an order of magnitude and then increases again. The x-ray photoelectron spectroscopy measurements show that the S:Mo ratio continuously decreases with increasing plasma exposure time. For a short plasma exposure time, the resistance decrease can be explained due to the creation of sulfur vacancies leaving unsaturated electrons with molybdenum (Mo) atoms which act as electron donors. With increasing plasma exposure, more sulfur vacancies and hence more Mo atoms are created, many of which get converted to insulating MoO3 resulting in an increase in the resistance of the MoS2 thin film. The results presented here are a major step forward in realizing the overreaching goals of MoS2 thin films for practical device applications.

Protective coatings for front surface silver mirrors by atomic layer deposition.

The problem of protection of the front surface silver mirrors is a very important one for a number of applications. The atomic layer deposition (ALD) technique provides an efficient way to form a coating, protecting the sensitive surface of silver from a corrosive and oxidizing environment. Moreover, the ALD layer provides extremely high conformality (even when deposited over high aspect ratio features) and has high integrity, efficiently blocking foreign species diffusion to the silver-overcoat interface. We tested the efficiency of the protection of silver mirrors against oxygen plasma exposure by the ALD-deposited Al2O3 layers by combining spectroscopic ellipsometry, reflection measurements and pulsed glow-discharge optical emission spectroscopy (GD-OES) profiling. We have found that for optimal protection, the thickness of the ALD deposited layer should exceed at least 15 nm (about 150 ALD cycles at 150°C). We have also demonstrated that the deposition of 15 nm of a protective ALD-deposited Al2O3 layer does not affect the absolute reflectivity of a silver mirror in the spectral range 320 -2500 nm.

Atomic layer deposition of Y2O3 thin films with a high growth per cycle by Ar multiple boost injection

Atomic layer deposition of Y2O3 thin films has been examined by multiple injections of tris-isopropylcyclopentadienyl yttrium [Y(iPrCp)3] precursors followed by remote oxygen plasma. By boosting or pressurizing the precursor cylinder higher than the chamber pressure, one can effectively deliver the precursor into the chamber. By increasing the number of shots before oxygen plasma exposure, the growth per cycle increases and shows saturation at 0.22 nm/cycle, close to the unit monolayer (ML) thickness of the Y2O3 film (0.23 nm). By selecting a proper number of shots, one can effectively utilize the precursor over other methods including bubbling delivery. A multiple boost injection method allows the utilization of low vapor pressure precursor to deposit films in a high-pressure environment.

Facile Synthesis of Co3O4-Incorporated Multichannel Carbon Nanofibers for Electrochemical Applications.

Considering their superior electrochemical performances, extensive studies have been carried out on composite nanomaterials based on porous carbon nanofibers. However, the introduction of inorganic components into a porous structure is complex and has a low yield. In this study, we propose a simple synthesis of cobalt-oxide-incorporated multichannel carbon nanofibers (P-Co-MCNFs) as electrode materials for electrochemical applications. The cobalt oxide component is directly formed in the carbon structure by a simple oxygen plasma exposure of the phase-separated polymer nanofibers. P-Co-MCNF displays high specific capacitance (815 F g-1 at 2.0 A g-1), rate capability (821 F g-1 at 1 A g-1 and 786 F g-1 at 20 A g-1), and cycle stability (92.1% for 5000 cycles) as a supercapacitor electrode. Moreover, excellent sensitivity (down to 1 nM) and selectivity to the glucose molecule is demonstrated for nonenzyme sensor applications.