We
report on light-controlled in situ bidirectional tuning of longitudinal
surface plasmon resonance (LSPR) of single gold nanorods via oxidative
etching with ferric chloride. By removing the surfactant layer from
the surface of a gold nanorod, we demonstrate that the etching happens
only in the presence of an excitation laser, and the etching rate
and directionality can be controlled by the intensity of excitation
light. At a low excitation power, a blue shift of a nanorod’s
LSPR of up to 50 nm was observed, which indicates preferential etching
from its tips. Whereas at a high power, we see a red shift of the
nanorod’s LSPR of up to 140 nm indicating etching from sides.
These results present a new approach for in situ finer adjustments
of a selected nanorod’s plasmon resonance.
We
show that many complex gold nanostructures such as the water
chestnut, dog bone, nanobar, and octahedron, which are not easily
accessible via a direct seed-growth synthesis approach, can be prepared
via overgrowth of the same gold nanorods by varying pH and Ag concentrations
in the growth solution. Overgrown nanostructures’ shapes were
determined by the rate of gold atom deposition, which is faster at
higher pH. In the presence of AgNO
3
, codeposition of gold
and silver atoms affects the shapes of overgrown nanostructures, particularly
at high pH.
End-to-end dimers of gold nanorods are predicted to be excellent substrates for surface-enhanced spectroscopy. However, the synthesis of solution-stable end-to-end dimers remains challenging. We exploit the pH-dependent configurational change of polyelectrolytes to initiate and terminate the gold nanorod assembly formation to produce endto-end linked dimers in high yield. The gold nanorods are first overcoated with a polyelectrolyte, and the end-to-end attachment is initiated by adding a thiol linker in acidic medium. The assembly formation is then terminated at the dimer stage by changing the pH of the medium by the addition of an appropriate amount of 1,4-diazabicyclo[2.2.2]octane (DABCO).The nanorod dimers synthesized here are stable in solution for a week without any additional surface encapsulation.
End-to-end assemblies of anisotropic plasmonic nanostructures with small nanogaps are of great interest as they create strong hot spots for enhancing weak fluorescence and/or scattering of molecules.
We demonstrate an easy and controllable method for light-induced active tuning of the longitudinal surface plasmon resonance (LSPR) of gold nanorods (AuNRs) over
∼
94
n
m
. The red-shift of the LSPR can be controlled by varying the time of exposure to a 532 nm laser. The tuning is achieved by photo-induced dissolution of individual AuNRs by sodium dodecyl sulfate (SDS) under continuous illumination. The dissolution of the AuNRs increases the aspect ratio, and consequently the LSPR exhibits a gradual but large redshift. A key feature is that it is possible to selectively tune the LSPR of a specific AuNR in a group while leaving the others totally unaffected. Such controllable, light-induced, post-synthesis fine-tuning of the LSPR is useful for tailoring the plasmonic response of individual AuNRs for a wide range of applications.
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