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Hierarchical micro-nanostructured surfaces are key components of ‘smart’ multifunctional materials, used to control wetting, adhesion, tactile, friction, optical, antifogging, antibacterial, and many more surface properties. Hierarchical surfaces comprise random or ordered structures ranked by their length scale spanning the range from a few nanometers to a few micrometers, with the larger microstructures typically embedding smaller nanostructures. Despite the importance of hierarchical surfaces, there have been few studies on their precise and controlled fabrication or their quantitative characterization, and they usually involve multiple and complex fabrication steps. Here, we present a new plasma nanotechnology, which we term ‘nanoinhibit’, and a new plasma reactor for producing in one facile process-step-controlled hierarchy at will on polymeric surfaces. We couple the new plasma nanotechnology with detailed computational nanometrology based on the analysis of scanning electron microscopy images and targeted to specific functionality. We showcase the potential of ‘nanoinhibit’ for functional surface fabrication by controlling the wetting and optical functionality of the fabricated hierarchical surfaces and showing its dependence on surface morphology metrics. Finally, we observe that ‘nanoinhibit’ produces a new class of ‘strong hierarchical’ surfaces exhibiting spatially separated periodic and fractal-like components.

Plasma treatment is an environmentally friendly solution for modifying or nanostructuring the surface of several materials including photoactive polymers. The detailed characterization of the effect of plasma treatment on chemical and optoelectronic properties of photoactive polymers is, therefore, of specific interest. Herein, the effect of the exposure of poly(3-hexylthiophene) (P3HT) thin films to plasma created in three different gases (oxygen, argon and hydrogen) was studied. A range of spectroscopic techniques, such as x-ray (XPS) and ultraviolet (UPS) photoelectron spectroscopy in conjunction with UV–vis absorption, Fourier transform infrared (FTIR) and photoluminescence (PL) spectroscopies, are employed to quantify the extent of chemical modification occurring in each particular case. It is shown that oxygen plasma treatment leads to the disruption of the π-conjugation via the direct oxidation of the sulfur atom of the thiophene ring while the aliphatic side chain remains nearly unaffected. An oxidation mechanism is proposed according to which the sulfur atom of the thiophene ring is oxidized into sulfoxides and sulfones, which subsequently degraded into sulfonates or sulfonic acids in a relatively small degree. For argon and hydrogen plasma treatments some oxidation products are detected only at the polymer surface. In all cases the polymer surface Fermi level is shifted closer to the highest occupied molecular orbital (HOMO) energy after plasma treatment indicating p-type doping arising from surface oxidation.

In this work, we present plasma etching alone as a directed assembly method to both create the nanodot pattern on an etched polymeric (PMMA) film and transfer it to a silicon substrate for the fabrication of silicon nanopillars or cone-like nanostructuring. By using a shield to control sputtering from inside the plasma reactor, the size and shape of the resulting nanodots can be better controlled by varying plasma parameters as the bias power. The effect of the shield on inhibitor deposition on the etched surfaces was investigated by time-of-flight secondary ion mass spectroscopy (ToF-SIMS) measurements. The fabrication of quasi-ordered PMMA nanodots of a diameter of 25 nm and period of 54 nm is demonstrated. Pattern transfer to the silicon substrate using the same plasma reactor was performed in two ways: (a) a mixed fluorine-fluorocarbon-oxygen nanoscale etch plasma process was employed to fabricate silicon nanopillars with a diameter of 25 nm and an aspect ratio of 5.6, which show the same periodicity as the nanodot pattern, and (b) high etch rate cryogenic plasma process was used for pattern transfer. The result is the nanostructuring of Si by high aspect ratio nanotip or nanocone-like features that show excellent antireflective properties.

Zinc oxide (ZnO) is an important material for polymer solar cells (PSCs) where the characteristics of the interface can dominate both the efficiency and lifetime of the device. In this work we study the effect of fluorine (SF6) plasma surface treatment of ZnO films on the performance of PSCs with an inverted structure. The interaction between fluorine species present in the SF6 plasma and the ZnO surface is also investigated in detail. We provide fundamental insights into the passivation effect of fluorine by analyzing our experimental results and theoretical calculations and we propose a mechanism according to which a fluorine atom substitutes an oxygen atom or occupies an oxygen vacancy site eliminating an electron trap while it may also attract hydrogen atoms thus favoring hydrogen doping. These multiple fluorine roles can reduce both the recombination losses and the electron extraction barrier at the ZnO/fullerene interface improving the selectivity of the cathode contact. Therefore, the fabricated devices using the fluorine plasma treated ZnO show high efficiency and stable characteristics, irrespective of the donor : acceptor combinations in the photoactive blend. Inverted polymer solar cells, consisting of the P3HT:PC71BM blend, exhibited increased lifetime and high power conversion efficiency (PCE) of 4.6%, while the ones with the PCDTBT:PC71BM blend exhibited a PCE of 6.9%. Our champion devices with the PTB7:PC71BM blends reached a high PCE of 8.0% and simultaneously showed exceptional environmental stability when using the fluorine passivated ZnO cathode interlayers.

Natural evolution over 3.8 billion years has produced a huge diversity of hierarchical micro/nanostructures that have become a source of inspiration for scientists to design and develop the next generation of materials and devices. In this work, a combination of plasma etching techniques and the hydrothermal growth is employed to synthesize in a controllable way bio-inspired, three-dimensional nanoarchitectures of ZnO onto periodic arrays of Si nanowires. It is demonstrated that the proposed methodology offers the ability to tune the length, diameter and density of the ZnO nanostructures resulting in a wide range of nanoarchitectures from plant-like structures to complex three-dimensional interconnected networks.

Tuning the transition between stable hydrophilicity and high etching-rate and simultaneous hydrophilization of polymethylmethacrylate (PMMA) films was achieved in an open-air environment simply by adjusting the O2 content in He gas injection through the showerhead-type electrode of a novel atmospheric pressure dielectric barrier discharge source. A comparative study was performed for He and He-O2 plasma treatment of PMMA. Electrical and optical measurements indicated severe alteration of plasma characteristics when O2 is added in gas feed. The enhancement of oxygen emission band intensities indicates an enhanced concentration of atomic oxygen, resulting in very high PMMA etching rates of ∼320 nm/min, ∼four times higher compared to pure He. In contrast, the He plasma showed higher nitrogen emission band intensities, translated into a higher nitrogen content on the PMMA surface according to x-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. This enhanced nitrogen content du...

A printed-circuit-board (PCB) based atmospheric pressure dielectric barrier discharge (DBD) capable of uniform processing over a large area was constructed consisting of two parallel plates. The first perforated plate is comprised of four layers: a RF powered metal layer, a polymeric dielectric layer, a floating metal grid and another dielectric layer. The second, grounded, plate was fluorine doped tin oxide (FTO) glass plate with surface of 100 × 100 mm2 and thickness of 2 mm. The PCB based atmospheric pressure DBD was characterized by (a) measuring electrical characteristics of the device using derivative I–V probes, (b) ICCD imaging and (c) optical emission spectroscopy (OES). Optical and electrical characteristics, as well as plasma uniformity were measured by changing He flow rate and input power, while keeping the gap between the PCB and the FTO glass plate ground electrode constant at 2 mm. The plasma uniformity strongly depends on the applied power and on the flow rate of the buffer gas. When increasing the flow rate, the intensity of the nitrogen-dominated emission drops, while emission of helium and oxygen lines increases. The source allows low temperature, uniform plasma operation over a wide area of 100 × 100 mm2, which could be essential for numerous applications. Examples of etching rate and hydrophilization are demonstrated.

Room-temperature deep Si etching using time-multiplexed deep reactive ion etching (DRIE) processes is investigated to fabricate ultra-high aspect ratio Si nanowires (SiNWs) perpendicular to the silicon substrate. Nanopatterning is achieved using either top-down techniques (e.g. electron beam lithography) or colloidal polystyrene (PS) sphere self-assembly. The latter is a faster and more economical method if imperfections in diameter and position can be tolerated. We demonstrate wire radii from below 100 nm to several micrometers, and aspect ratios (ARs) above 100:1 with etching rates above 1 μm min(-1) using classical mass flow controllers with pulsing rise times of seconds. The mechanical stability of these nanowires is studied theoretically and experimentally against adhesion and capillary forces. It is shown that above ARs of the order of 50:1 for spacing 1 μm, SiNWs tend to bend due to adhesion forces between them. Such large adhesion forces are due to the high surface energy of silicon. Wetting the SiNWs with water and drying also gives rise to capillary forces. We find that capillary forces may be less important for SiNW collapse/bending compared to adhesion forces of dry SiNWs, contrary to what is observed for polymeric nanowires/nanopillars which have a much lower surface energy compared to silicon. Finally we show that SiNW arrays have oleophobic and superoleophobic properties, i.e. they exhibit excellent anti-wetting properties for a wide range of liquids and oils due to the re-entrant profile produced by the DRIE process and the well-designed spacing.

A new concept of radio frequency (rf) driven atmospheric pressure dielectric barrier discharge source based on printed circuit board (PCB) is proposed for efficient and uniform large area processing of polymeric surfaces. The source comprises a perforated PCB with a metal electrode and an optional metallic (Cu) grid on its two surfaces. The source was characterized using electromagnetic simulations and electrical measurements. Different source configurations were compared concerning the existence of a Cu grid into the PCB configuration and also the cases of grid being powered or floating. Electric field simulations showed enhanced electric field peak values with the grid addition, especially for the powered grid configuration, and also high electric field uniformity over the discharge area. The electrical measurements in helium plasma confirmed that the grid existence resulted in lower breakdown voltages and higher power dissipation. Etching rate and water contact angle measurements in plasma treated poly(methyl methacrylate)/PMMA films were performed to evaluate the source efficiency in polymer processing. The etching rate increased almost two times in the presence of a grid, reaching values around 65 nm min−1 in pure He. An optimum water contact angle of 27.4° was achieved after plasma treatment with the powered grid source and this value increased to 33° after four weeks of storage indicating the enhanced hydrophilization stability.