Charge‐Tunable Directed Self‐Assembly for High‐Resolution Stretchable Metal Nanowire Conductors

ABSTRACT Directed self‐assembly (DSA) using wettability contrast guides functional inks into hydrophilic regions through interfacial tension. Herein, we report a charge‐tunable DSA strategy using parallel‐beam vacuum ultraviolet (PVUV) irradiation and alkaline activation to selectively modulate the dispersive ( σ _s ^D ) and polar ( σ _s ^P ) fractions of the surface free energy (SFE) of polymer substrates. σ _s ^D ‐rich regions repel polar inks, while σ _s ^P ‐rich regions attract them, enabling a controllable transition between attractive and repulsive patterning. In polydimethylsiloxane (PDMS), short PVUV exposure induces a higher negative surface charge, leading to electrostatic repulsion that expels ink from the modified regions. In contrast, prolonged PVUV exposure reduces the surface charge density while increasing the polarity, enabling van der Waals attraction to dominate and promote ink deposition. The mechanism is elucidated using a modified Derjaguin–Landau–Verwey–Overbeek framework. Utilizing this platform, silver nanowire (AgNW) inks are patterned into stretchable conductive networks with resolutions down to 50 µm. The resulting AgNW traces exhibit low resistivity (8.19 × 10 ⁻⁸ Ω m) and reliable electromechanical responses under 60% tensile strain. This lithography‐free, charge‐tunable DSA approach provides a scalable route for fabricating high‐resolution stretchable electronics with potential for use in wearable sensors and electrotactile haptic interfaces.