Large-Area Nanosphere Self-Assembly Monolayers for Periodic Surface Nanostructures with Ultrasensitive and Spatially Uniform SERS Sensing.

Colloidal lithography provides a rapid and low-cost approach to construct 2D periodic surface nanostructures. However, an impressive demonstration to prepare large-area colloidal template is still missing. Here, a high-efficient and flexible technique is proposed to fabricate self-assembly monolayers consisting of orderly-packed polystyrene spheres at air/water interface via ultrasonic spray. This "non-contact" technique exhibits great advantages in terms of scalability and adaptability due to its renitent interface dynamic balance. More importantly, this technique is not only competent for self-assembly of single-sized polystyrene spheres, but also for binary polystyrene spheres, completely reversing the current hard situation of preparing large-area self-assembly monolayers. As a representative application, hexagonal-packed silver-coated silicon nanorods array (Si-NRs@Ag) is developed as an ultrasensitive surface-enhanced Raman scattering (SERS) substrate with very low limit-of-detection for selective detection of explosive 2,4,6-trinitrotoluene down to femtomolar (10-14 m) range. The periodicity and orderliness of the array allow hot spots to be designed and constructed in a homogeneous fashion, resulting in an incomparable uniformity and reproducibility of Raman signals. All these excellent properties come from the Si-NRs@Ag substrate based on the ordered structure, open surface, and wide-range electric field, providing a robust, consistent, and tunable platform for molecule trapping and SERS sensing for a wide range of organic molecules.