Exploiting breath figure reversibility for in situ pattern modulation and hierarchical design.

The breath figure (BF) method employs condensation droplets as dynamic templates for patterning polymer films. In the classical approach, dropwise condensation and film solidification are simultaneously induced through solvent evaporation, leading to empirically derived patterns with limited predictability of the final design. Here we use the temporally arrested BF methodology, controlling condensation and polymerisation independently to create diverse BF patterns with varied pore size, arrangement and distribution. External temperature control enables us to further investigate and exploit the inherent reversibility of the phase change process that governs the pattern formation. We modulate the level of subcooling and superheating to achieve subsequent regimes of condensation and evaporation, permitting in situ regulation of the droplet growth and shrinkage kinetics. The full reversibility of the phase change processes joined with active photopolymerisation in the current approach thus allows arresting of predictable BF kinetics at intermediate stages, thereby accessing patterns with varied pore size and spacing for unchanged material properties and environmental conditions. This simultaneous active control over both the kinetics of phase change and polymer solidification offers affordable routes for the fabrication of diverse predictable porous surfaces; manufacture of monolithic hierarchical BF patterns are ultimately facilitated through the advanced control of the BF assembly using the method presented here.

Temporally Arrested Breath Figure.

Since its original conception as a tool for manufacturing porous materials, the breath figure method (BF) and its variations have been frequently used for the fabrication of numerous micro- and nanopatterned functional surfaces. In classical BF, reliable design of the final pattern has been hindered by the dual role of solvent evaporation to initiate/control the dropwise condensation and induce polymerization, alongside the complex effects of local humidity and temperature influence. Herein, we provide a deterministic method for reliable control of BF pore diameters over a wide range of length scales and environmental conditions. To this end, we employ an adapted methodology that decouples cooling from polymerization by using a combination of initiative cooling and quasi-instantaneous UV curing to deliberately arrest the desired BF patterns in time. Through in situ real-time optical microscopy analysis of the condensation kinetics, we demonstrate that an analytically predictable self-similar regime is the predominant arrangement from early to late times O(10-100 s), when high-density condensation nucleation is initially achieved on the polymer films. In this regime, the temporal growth of condensation droplets follows a unified power law of D ∝ t. Identification and quantitative characterization of the scale-invariant self-similar BF regime allow fabrication of programmed pore size, ranging from hundreds of nanometers to tens of micrometers, at high surface coverage of around 40%. Finally, we show that temporal arresting of BF patterns can be further extended for selective surface patterning and/or pore size modulation by spatially masking the UV curing illumination source. Our findings bridge the gap between fundamental knowledge of dropwise condensation and applied breath figure patterning techniques, thus enabling mechanistic design and fabrication of porous materials and interfaces.