Ion irradiation as a tool for modifying the surface and optical properties of plasma polymerised thin films

Radio frequency (R.F.) glow discharge polyterpenol thin films were prepared on silicon wafers and irradiated with I10+ ions to fluences of 1 × 1010 and 1 × 1012 ions/cm2. Post-irradiation characterisation of these films indicated the development of well-defined nano-scale ion entry tracks, highlighting prospective applications for ion irradiated polyterpenol thin films in a variety of membrane and nanotube-fabrication functions. Optical characterisation showed the films to be optically transparent within the visible spectrum and revealed an ability to selectively control the thin film refractive index as a function of fluence. This indicates that ion irradiation processing may be employed to produce plasma-polymer waveguides to accommodate a variety of wavelengths. XRR probing of the substrate-thin film interface revealed interfacial roughness values comparable to those obtained for the uncoated substrate's surface (i.e., both on the order of 5 Å), indicating minimal substrate etching during the plasma deposition process.

Structural characterization of γ-terpinene thin films using mass spectroscopy and X-Ray photoelectron spectroscopy

Understanding the polymerization mechanism of a precursor is indispensable to enhance the requisite material properties. In situ mass spectroscopy and X-ray photoelectron spectroscopy is used in this study to understand the RF plasma polymerization of γ-terpinene. High-resolution mass spectra positive ion mass spectrometry data of the plasma phase demonstrates the presence of oligomeric species of the type [M+H]+ and [2M+H]+, where M represents a unit of the starting material. In addition, there is abundant fragmented species, with most dominant being [M+] (136 m/z), C10H13+ (133 m/z), C9H11+ (119 m/z), and C7H9+ (93 m/z). The results reported in this manuscript enables to comprehend the relationship between the degree of incorporation of oxygen and the rate of deposition with the input RF power.

Polymer encapsulation of magnesium to control biodegradability and biocompatibility

Clinical utility of biodegradable magnesium implants is undermined by the untimely degradation of these materials in vivo. Their high corrosion rate leads to loss of mechanical integrity, peri–implant alkalization and localised accumulation of hydrogen gas. Biodegradable coatings were produced on pure magnesium using RF plasma polymerisation. A monoterpene alcohol with known anti-inflammatory and antibacterial properties was used as a polymer precursor. The addition of the polymeric layer was found to reduce the degradation rate of magnesium in simulated body fluid. The in vitro studies indicated good cytocompatibility of non-adherent THP–1 cells and mouse macrophage cells with the polymer, and the polymer coated sample. The viability of THP–1 cells was significantly improved when in contact with polymer encapsulated magnesium compared to unmodified samples. Collectively, these results suggest plasma enhanced polymer encapsulation of magnesium as a suitable method to control degradation kinetics of this biomaterial.

Optical and surface characterization of radio frequency plasma polymerized 1-isopropyl-4-methyl-1,4-cyclohexadiene thin films

Low pressure radio frequency plasma-assisted deposition of 1-isopropyl-4-methyl-1,4-cyclohexadiene thin films was investigated for different polymerization conditions. Transparent, environmentally stable and flexible, these organic films are promising candidates for organic photovoltaics (OPV) and flexible electronics applications, where they can be used as encapsulating coatings and insulating interlayers. The effect of deposition RF power on optical properties of the films was limited, with all films being optically transparent, with refractive indices in a range of 1.57–1.58 at 500 nm. The optical band gap (Eg) of ~3 eV fell into the insulating Eg region, decreasing for films fabricated at higher RF power. Independent of deposition conditions, the surfaces were smooth and defect-free, with uniformly distributed morphological features and average roughness between 0.30 nm (at 10 W) and 0.21 nm (at 75 W). Films fabricated at higher deposition power displayed enhanced resistance to delamination and wear, and improved hardness, from 0.40 GPa for 10 W to 0.58 GPa for 75 W at a load of 700 μN. From an application perspective, it is therefore possible to tune the mechanical and morphological properties of these films without compromising their optical transparency or insulating property.

RF plasma polymerised thin films from natural resources

Plasma polymerisation is an effective tool for fabrication of thin films from volatile organic monomers. RF plasma assisted deposition is used for one-step, chemical-free polymerisation of nonsynthetic materials derived directly from agricultural produces. By varying the deposition parameters, especially the input RF power, the film properties can be tailored for a range of uses, including electronics or biomedical applications. The fabricated thin films are optically transparent with refractive index close to that of glass. Given the diversity of essential oils, this paper compares the chemical and physical properties of thin films fabricated from several commercially exploited essential oils and their components. It is interesting to note that some of the properties can be tailored for various applications even though the chemical structure of the derived polymer is very similar. The obtained material properties also show that the synthesised materials are suitable as encapsulating layers for biodegradable implantable metals.

Wetting, solubility and chemical characteristics of plasma-polymerized 1-isopropyl-4-methyl-1,4-cyclohexadiene thin films

Investigations on the wetting, solubility and chemical composition of plasma polymer thin films provide an insight into the feasibility of implementing these polymeric materials in organic electronics, particularly where wet solution processing is involved. In this study, thin films were prepared from 1-isopropyl-4-methyl-1,4-cyclohexadiene (γ-Terpinene) using radio frequency (RF) plasma polymerization. FTIR showed the polymers to be structurally dissimilar to the original monomer and highly cross-linked, where the loss of original functional groups and the degree of cross-linking increased with deposition power. The polymer surfaces were hydrocarbon-rich, with oxygen present in the form of O–H and C=O functional groups. The oxygen content decreased with deposition power, with films becoming more hydrophobic and, thus, less wettable. The advancing and receding contact angles were investigated, and the water advancing contact angle was found to increase from 63.14° to 73.53° for thin films prepared with an RF power of 10 W to 75 W. The wetting envelopes for the surfaces were constructed to enable the prediction of the surfaces’ wettability for other solvents. The effect of roughness on the wetting behaviour of the films was insignificant. The polymers were determined to resist solubilization in solvents commonly used in the deposition of organic semiconducting layers, including chloroform and chlorobenzene, with higher stability observed in films fabricated at higher RF power.

Plasma polymerised thin films for flexible electronic applications

The significant advancement and growth of organic and flexible electronic applications demand materials with enhanced properties. This paper reports the fabrication of a nonsynthetic polymer thin film using radio frequency plasma polymerisation of 3,7-dimethyl-1,6-octadien-3-ol. The fabricated optically transparent thin film exhibited refractive index of approximately 1.55 at 500 nm and rate of deposition was estimated to be 40 nm/min. The surface morphology and chemical properties of the thin films were also reported in this paper. The optical band gap of the material is around 2.8 eV. The force of adhesion and Young's modulus of the linalool polymer thin films were measured using force-displacement curves obtained from a scanning probe microscope. The friction coefficient of linalool polymer thin films was measured using the nanoscratch test. The calculated Young's modulus increased linearly with increase in input power while the friction coefficient decreased.

Materials and methods for encapsulation of OPV: A review

Amongst alternative energy sources, photovoltaics hold a considerable promise for it is a plentiful, easily accessible and renewable source of power. Yet, the overall cost of generating electricity using the most advanced silicon based solar cells remains high compared to both traditional and other renewable power generation approaches. Organic thin film photovoltaics are an emerging economically competitive photovoltaic technology that combines manufacturing adaptability, low-cost processing and a lightweight, flexible device end-product. At present, however, commercial use of organic photovoltaics is hindered by low conversion efficiency and poor overall stability of the devices. Encapsulation with high barrier performance materials and structures is one of the key ways to address these issues and improve device lifetime. This paper will briefly outline the current understanding of the major degradation mechanisms, their interrelation and the internal and external factors that initiate these processes. Then, the paper will provide an overview of currently available encapsulant materials, their utility in limiting chemical (water vapor and oxygen penetration) and mechanical degradation within individual layers and device as a whole, and potential drawbacks to their application in organic photovoltaic devices.

New encapsulating materials for implantable devices

Synthetic, natural, or composite, biomaterials occupy a key position in the management of disease and support continuous advancement of health care. Clinical utility of many permanent and biodegradable implants can be significantly improved via surface modification. Here, we discuss a novel polymer material developed from essential oil-based monoterpene alcohol using plasma polymerisation. The developed coatings are cytocompatible and limit adhesion and proliferation of a variety of pathogens. The coating can also be used to control degradation behaviour of resorbable materials, such as magnesium.

Analyzing hysteresis behavior of capacitance-voltage characteristics of IZO/C₆₀/pentacene/Au diodes with a hole-transport electron-blocking polyterpenol layer by electric-field-induced optical second-harmonic generation measurement

By using electric-field-induced optical second-harmonic generation (EFISHG) measurement, we analyzed hysteresis behavior of capacitance-voltage (C-V) characteristics of IZO/polyterpenol (PT)/C₆₀/pentacene/Au diodes, where PT layer is actively working as a hole-transport electron-blocking layer. The EFISHG measurement verified the presence of interface accumulated charges in the diodes, and showed that a space charge electric field from accumulated excess electrons (holes) that remain at the PT/C₆₀ (C₆₀/pentacene) interface is responsible for the hysteresis loop observed in the C-V characteristics.

Implantable devices: issues and challenges

Ageing population and a multitude of neurological and cardiovascular illnesses that cannot be mitigated by medication alone have resulted in a significant growth in the number of patients that require implantable electronic devices. These range from sensors, gastric and cardiac pacemakers, cardioverter defibrillators, to deep brain, nerve, and bone stimulators. Long-term implants present specific engineering challenges, including low energy consumption and stable performance. Resorbable electronics may offer excellent short-term performance without the need for surgical removal. However, most electronic materials have poor bio- and cytocompatibility, resulting in immune reactions and infections. This paper reviews the current situation and highlights challenges for future advancements.

Solubility and surface interactions of RF plasma polymerized polyterpenol thin films

Organic thin films have myriad of applications in biological interfaces, micro-electromechanical systems and organic electronics. Polyterpenol thin films fabricated via RF plasma polymerization have been substantiated as a promising gate insulating and encapsulating layer for organic optoelectronics, sacrificial place-holders for air gap fabrication as well as antibacterial coatings for medical implants. This study aims to understand the wettability and solubility behavior of the nonsynthetic polymer thin film, polyterpenol. Polyterpenol exhibited monopolar behavior, manifesting mostly electron donor properties, and was not water soluble due to the extensive intermolecular and intramolecular hydrogen bonds present. Hydrophobicity of polyterpenol surfaces increased for films fabricated at higher RF power attributed to reduction in oxygen containing functional groups and increased cross linking. The studies carried out under various deposition conditions vindicate that we could tailor the properties of the polyterpenol thin film for a given application.

Efficient surface modification of biomaterial to prevent biofilm formation and the attachment of microorganisms

Biomaterials play a fundamental role in disease management and the improvement of health care. In recent years, there has been a significant growth in the diversity, function, and number of biomaterials used worldwide. Yet, attachment of pathogenic microorganisms onto biomaterial surfaces remains a significant challenge that substantially undermines their clinical applicability, limiting the advancement of these systems. The emergence and escalating pervasiveness of antibiotic-resistant bacterial strains makes the management of biomaterial-associated nosocomial infections increasingly difficult. The conventional post-operative treatment of implant-caused infections using systemic antibiotics is often marginally effective, further accelerating the extent of antimicrobial resistance. Methods by which the initial stages of bacterial attachment and biofilm formation can be restricted or prevented are therefore sought. The surface modification of biomaterials has the potential to alleviate pathogenic biofouling, therefore preventing the need for conventional antibiotics to be applied.

Electron-blocking hole-transport polyterpenol thin films

The carrier blocking property of polyterpenol thin films derived from non-synthetic precursor is studied using Electric Field Induced Optical Second Harmonic Generation (EFISHG) technique that can directly probe carrier motion in organic materials. A properly biased double-layer MIM device with a structure of indium zinc oxide (IZO)/polyterpenol/C₆₀/Al shows that by incorporating the polyterpenol thin film, the electron transport can be blocked while the hole transport is allowed. The inherent electron blocking hole transport property is verified using Al/C₆₀/Alq3/polyterpenol/IZO and Al/Alq3/polyterpenol/IZO structures. The rectifying property of polyterpenol is very promising and can be utilized in the fabrication of many organic devices.

Plasma assisted surface modification of organic biopolymers to prevent bacterial attachment

Despite many synthetic biomaterials having physical properties that are comparable or even superior to those of natural body tissues, they frequently fail due to the adverse physiological reactions they cause within the human body, such as infection and inflammation. The surface modification of biomaterials is an economical and effective method by which biocompatibility and biofunctionality can be achieved while preserving the favorable bulk characteristics of the biomaterial, such as strength and inertness. Amongst the numerous surface modification techniques available, plasma surface modification affords device manufacturers a flexible and environmentally friendly process that enables tailoring of the surface morphology, structure, composition, and properties of the material to a specific need. There are a vast range of possible applications of plasma modification in biomaterial applications, however, the focus of this review paper is on processes that can be used to develop surface morphologies and chemical structures for the prevention of adhesion and proliferation of pathogenic bacteria on the surfaces of in-dwelling medical devices. As such, the fundamental principles of bacterial cell attachment and biofilm formation are also discussed. Functional organic plasma polymerised coatings are also discussed for their potential as biosensitive interfaces, connecting inorganic/metallic electronic devices with their physiological environments.