Wetting phenomena are ubiquitous in nature and technology. A solid substrate exposed to the environment is almost invariably covered by a layer of fluid material. In this review, the surface forces that lead to wetting are considered, and the equilibrium surface coverage of a substrate in contact with a drop of liquid. Depending on the nature of the surface forces involved, different scenarios for wetting phase transitions are possible; recent progress allows us to relate the critical exponents directly to the nature of the surface forces which lead to the different wetting scenarios. Thermal fluctuation effects, which can be greatly enhanced for wetting of geometrically or chemically structured substrates, and are much stronger in colloidal suspensions, modify the adsorption singularities. Macroscopic descriptions and microscopic theories have been developed to understand and predict wetting behavior relevant to microfluidics and nanofluidics applications. Then the dynamics of wetting is examined. A drop, placed on a substrate which it wets, spreads out to form a film. Conversely, a nonwetted substrate previously covered by a film dewets upon an appropriate change of system parameters. The hydrodynamics of both wetting and dewetting is influenced by the presence of the three-phase contact line separating "wet" regions from those that are either dry or covered by a microscopic film only. Recent theoretical, experimental, and numerical progress in the description of moving contact line dynamics are reviewed, and its relation to the thermodynamics of wetting is explored. In addition, recent progress on rough surfaces is surveyed. The anchoring of contact lines and contact angle hysteresis are explored resulting from surface inhomogeneities. Further, new ways to mold wetting characteristics according to technological constraints are discussed, for example, the use of patterned surfaces, surfactants, or complex fluids.

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Wetting and Spreading

In the 19th century, Oscar Wilde stated “We live, I regret to say, in an age of surfaces”. Today, we do so even more, and we do not regret it: key advances in the understanding and fabrication of surfaces with controlled wetting properties are about to make the dream of a contamination-free (or 'no-clean') surface come true. Two routes to self-cleaning are emerging, which work by the removal of dirt by either film or droplet flow. Although a detailed understanding of the mechanisms underlying the behaviour of liquids on such surfaces is still a basic research topic, the first commercial products in the household-commodity sector and for applications in biotechnology are coming within reach of the marketplace. This progress report describes the current status of understanding of the underlying mechanisms, the concepts for making such surfaces, and some of their first applications.

Self-cleaning surfaces - virtual realities

Within the field of nanotechnology, nanoparticles are one of the most prominent and promising candidates for technological applications. Self-assembly of nanoparticles has been identified as an important process where the building blocks spontaneously organize into ordered structures by thermodynamic and other constraints. However, in order to successfully exploit nanoparticle self-assembly in technological applications and to ensure efficient scale-up, a high level of direction and control is required. The present review critically investigates to what extent self-assembly can be directed, enhanced, or controlled by either changing the energy or entropy landscapes, using templates or applying external fields.

Directed Self-Assembly of Nanoparticles

2.3. Medical Devices and Sensors 9 2.4. Radio Frequency Applications 10 3. Materials 12 3.1. Organic Electronics Materials 12 3.2. Semiconducting Polymer Design 13 3.3. Poly(3-alkylthiophenes) 14 3.4. Poly(thieno(3,2-b)thiophenes 15 3.5. Benchmark Polymer Semiconductors 15 3.6. High Performance Polymer Semiconductors 15 4. Device Stability 16 4.1. Bias Stress in Organic Transistors 17 4.1.1. Bias Stress Characterization 17 4.1.2. Bias Stress Mechanism 18 4.2. Short Channel Effects in Organic Transistors 19 5. Materials Patterning and Integration 20 6. Conclusions 22 7. Acknowledgments 22 8. References 22

Materials and applications for large area electronics: solution-based approaches.

Inkjet printing is viewed as a versatile manufacturing tool for applications in materials fabrication in addition to its traditional role in graphics output and marking. The unifying feature in all these applications is the dispensing and precise positioning of very small volumes of fluid (1–100 picoliters) on a substrate before transformation to a solid. The application of inkjet printing to the fabrication of structures for structural or functional materials applications requires an understanding as to how the physical processes that operate during inkjet printing interact with the properties of the fluid precursors used. Here we review the current state of understanding of the mechanisms of drop formation and how this defines the fluid properties that are required for a given liquid to be printable. The interactions between individual drops and the substrate as well as between adjacent drops are important in defining the resolution and accuracy of printed objects. Pattern resolution is limited by the extent to which a liquid drop spreads on a substrate and how spreading changes with the overlap of adjacent drops to form continuous features. There are clearly defined upper and lower bounds to the width of a printed continuous line, which can be defined in terms of materials and process variables. Finer-resolution features can be achieved through appropriate patterning and structuring of the substrate prior to printing, which is essential if polymeric semiconducting devices are to be fabricated. Low advancing and receding contact angles promote printed line stability but are also more prone to solute segregation or “coffee staining” on drying.

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Inkjet Printing of Functional and Structural Materials: Fluid Property Requirements, Feature Stability, and Resolution

When a spilled drop of coffee dries on a solid surface, it leaves a dense, ring-like deposit along the perimeter (Fig 1a) The coffee—initially dispersed over the entire drop—becomes concentrated into a tiny fraction of it Such ring deposits are common wherever drops containing dispersed solids evaporate on a surface, and they influence processes such as printing, washing and coating1,2,3,4,5 Ring deposits also provide a potential means to write or deposit a fine pattern onto a surface Here we ascribe the characteristic pattern of the deposition to a form of capillary flow in which pinning of the contact line of the drying drop ensures that liquid evaporating from the edge is replenished by liquid from the interior The resulting outward flow can carry virtually all the dispersed material to the edge This mechanism predicts a distinctive power-law growth of the ring mass with time—a law independent of the particular substrate, carrier fluid or deposited solids We have verified this law by microscopic observations of colloidal fluids

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Capillary flow as the cause of ring stains from dried liquid drops

Solids dispersed in a drying drop will migrate to the edge of the drop and form a solid ring. This phenomenon produces ringlike stains and occurs for a wide range of surfaces, solvents, and solutes. Here we show that the migration is caused by an outward flow within the drop that is driven by the loss of solvent by evaporation and geometrical constraint that the drop maintain an equilibrium droplet shape with a fixed boundary. We describe a theory that predicts the flow velocity, the rate of growth of the ring, and the distribution of solute within the drop. These predictions are compared with our experimental results.

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Contact line deposits in an evaporating drop

Ring formation in an evaporating sessile drop is a hydrodynamic process in which solids dispersed in the drop are advected to the contact line. After all the liquid evaporates, a ring-shaped deposit is left on the substrate that contains almost all the solute. Here I show that the drop itself can generate one of the essential conditions for ring formation to occur: contact line pinning. Furthermore, I show that when self-induced pinning is the only source of pinning an array of patterns---that include cellular and lamellar structures, sawtooth patterns, and Sierpinski gaskets---arises from the competition between dewetting and contact line pinning.

http://www-personal.umich.edu/~rddeegan/PDF/Coffee_Rings_2_PRE.pdf

Pattern formation in drying drops

We report an experimental study of liquid drops moving against gravity, when placed on a vertically vibrating inclined plate, which is partially wetted by the drop. The frequency of vibrations ranges from 30 to 200 Hz, and, above a threshold in vibration acceleration, drops experience an upward motion. We attribute this surprising motion to the deformations of the drop, as a consequence of an up or down symmetry breaking induced by the presence of the substrate. We relate the direction of motion to contact angle measurements. This phenomenon can be used to move a drop along an arbitrary path in a plane, without special surface treatments or localized forcing.

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Vibration-induced climbing of drops

The impact of a drop onto a liquid layer produces a splash that results from the ejection and dissolution of one or more liquid sheets, which expand radially from the point of impact. In the crown splash parameter regime, secondary droplets appear at fairly regularly spaced intervals along the rim of the sheet. By performing many experiments for the same parameter values, we measure the spectrum of small-amplitude perturbations growing on the rim. We show that for a range of parameters in the crown splash regime, the generation of secondary droplets results from a Rayleigh–Plateau instability of the rim, whose shape is almost cylindrical. In our theoretical calculation, we include the time dependence of the base state. The remaining irregularity of the pattern is explained by the finite width of the Rayleigh-Plateau dispersion relation. Alternative mechanisms, such as the Rayleigh–Taylor instability, can be excluded for the experimental parameters of our study.

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Robert D. Deegan

Papers

Capillary flow as the cause of ring stains from dried liquid drops

Contact line deposits in an evaporating drop

Pattern formation in drying drops

Vibration-induced climbing of drops

Wavelength selection in the crown splash