Achieving highly tunable and localized surface plasmon resonance up to near infrared (NIR) regions is a key target in nanoplasmonics. In particular, a self-assembly process capable of producing highly uniform and solution-processable nanomaterials with tailor-made plasmonic properties is lacking. We herein address this problem through a conjunctive use of wet Ag soldering and dry thermal sintering to produce nanodimer-derived structures with precisely engineered charge-transfer plasmon (CTP). The sintered dimers are water soluble, featuring gradually shifted CTP spanning an 800 nm wavelength range (up to NIR II). Upon silica removal, the products are grafted by DNA to offer surface functionality. This process is also adaptable to DNA-linked AuNP dimers toward plasmonic meta-materials via DNA-guided soldering and sintering.

Chemical modifiability is achieved for self-assembled plasmonic nanogaps to enable charge transfer plasmon resonance and unified plasmonic and catalytic functions.

The ability to re-engineer self-assembled functional structures with nanometer accuracy through solution-processing techniques represents a big challenge in nanotechnology. Herein we demonstrate that Ag+-soldered nanodimers with a steric confinement coating of silica can be harnessed to realize an in-solution nanosecond laser reshaping to form interparticle conductive pathway with finely controlled conductance. The high structural purity of the nanodimers, the rigid silica coating, and the uniform (but still adjustable) sub-1-nm interparticle gap together determine the success of the laser reshaping process. This method is applicable to DNA-assembled nanodimers, and thus promises DNA-based programming toward higher structural complexity. The resulting structures exhibit highly tunable charge transfer plasmons at visible and near-infrared frequencies dictated by the fluence of the laser pulses. Our work provides an in-solution, rapid, and nonperturbative route to realize charge transfer plasmonic coupling along prescribed paths defined by self-assembly, conferring great opportunities for functional metamaterials in the context of chemical, biological, and nanophotonic applications. The ability to continuously control a subnm interparticle gap and the nanomeric width of a conductive junction also provides a platform to investigate modern plasmonic theories involving quantum and nonlocal effects.