Gold nanoparticles (AuNPs) were the basis for the earliest research in the field of surface enhanced Raman scattering (SERS). Coupling of their surface plasmon resonances creates hot-spots of high electromagnetic intensities found to be very useful for sensing applications. However, chemically synthesized AuNPs in suspension are usually polydisperse and when arranged on a SERS substrate, lack periodic spatial organization. This leads to large variations in the enhancement factor (EF) which is detrimental to the sensing capabilities of the SERS substrate. Here, we showcase reproducible fabrication of an array of spherical AuNPs at the apices of shell isolated silicon nanocones with a homogeneous EF for SERS. The AuNPs are produced through discrete rotation glancing angle deposition of Au on shell isolated silicon nanocones (SI-SiNC) with square lattice periodicity and 250 nm pitch. By tuning the substrate tilt angle, substrate rotation angle and deposition thickness, the location and the size of the AuNPs formed can be controlled. Using this method, we successfully fabricated 60 nm AuNPs positioned at the apices of the nanocone array. Finite-Difference Time-Domain (FDTD) simulations were performed to visualize the electric field enhancement and verify conditions such as tip radius and oxide shell thickness to optimize the same. The EF was then experimentally calculated by performing SERS measurements on benzenethiol (BT) functionalized AuNPs at 400 unique points over the SI-SiNC substrate and compared to measurements of pure BT solution. A homogeneous substrate EF of (2.05 ± 0.05) ∙107 (99% confidence interval) at par with literature was calculated for the C-S in-plane deformation mode, δCS, of the BT molecule excited at 1077 cm-1. Our work highlights the advantages of nanofabrication for homogeneous SERS EF substrates.
Solution processed quantum dot (QD) lasers are one of the holy-grails of nanoscience. They are not yet commercialized because the lasing threshold is too high: one needs < 1 exciton per QD, which is hard to achieve due to fast non-radiative Auger recombination. The threshold can however be reduced by electronic doping of the QDs, which decreases the absorption near the band-edge, such that the stimulated emission (SE) can easily outcompete absorption. Here, we show that by electrochemically doping films of CdSe/CdS/ZnS QDs we achieve quantitative control over the gain threshold. We obtain stable and reversible doping more than two electrons per QD. We quantify the gain threshold and the charge carrier dynamics using ultrafast spectroelectrochemistry and achieve quantitative agreement between experiments and theory, including a vanishingly low gain threshold for doubly doped QDs. Over a range of wavelengths with appreciable gain coefficients, the gain thresholds reach record-low values of ~10-5 excitons per QD. These results demonstrate an unprecedented level of control over the gain threshold in doped QD solids, paving the way for the creation of cheap, solution-processable low-threshold QD-lasers.
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