Programmable Wrinkling of Self-Assembled Nanoparticle Films on Shape Memory Polymers

Hierarchically structured materials, inspired by sophisticated structures found in nature, are finding increasing applications in a variety of fields. Here, we describe the fabrication of wrinkled gold nanoparticle films, which leverage the structural tunability of gold nanoparticles to program the wavelength and amplitude of gold wrinkles. We have carefully examined the structural evolution and tuning of these wrinkled surfaces through varying nanoparticle parameters (diameter, number of layers, density) and substrate parameters (number of axes constrained during wrinkling) through scanning electron microscopy and cross-sectional transmission electron microscopy. It is found that nanoparticle layers of sufficient density are required to obtain periodical wrinkled structures. It was also found that tuning the nanoparticle diameter and number of layers can be used to program the wrinkle wavelength and amplitude by changing the film thickness and mechanical properties. This dual degree of tunability, not previously seen with continuous films, allows us to develop one of the smallest wrinkles developed to date with tunability in the sub-100 nm regime. The effect of the induced structural tunability on the enhancement of the intensity of the 4-mercaptopyridine Raman spectra is also studied through the application of these devices as substrates for surface-enhanced Raman spectroscopy (SERS), where wrinkling proves to be an effective method for enhancing the SERS signal in cases where there is an inherently low density of gold nanoparticles.