Temperature
variation at the nanoscale is pivotal for the thermodynamics
and kinetics of small entities. Surface-enhanced Raman spectroscopy
(SERS) is a promising technique for monitoring temperature variations
at the nanoscale. A key but ambiguous topic is methods to design a
sensitive SERS thermometer. Here, we elucidate that the type of chemical
bond of molecular probes and the surface chemical bonding effect are
crucial for maximizing the sensitivity of the SERS thermometer, as
illustrated by the variable-temperature SERS measurements and quantum
chemistry calculations for the frequency–temperature functions
of a series of molecules. The sensitivity of the frequency–temperature
function follows the sequence of triple bond > double bond >
single
bond, which is available for both aliphatic and aromatic molecules.
The surface chemical bonding effect between the SERS substrate and
molecular probe substantially increases the sensitivity of the frequency–temperature
function. These results provide universally available guidelines for
the rational design of a sensitive SERS thermometer by examining the
functional groups of molecular probes.
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