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Further decrease of the pinhole rate led to a more dramatic drop of 4-MBA signals, which is consistent with the previous results of acridine molecules, except the fact that 4-MBA could interact not only with Ag surface but also with Al2O3 shells [24 27].
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The pinhole rate ranges from ~18.0 to ~5.3%%, and further longer exposure time results in no obvious change of the pinhole rate.
The pinholes can be readily tuned by varying the exposure time of Al2O3 precursors during ALD coating, and the pinhole rate was estimated using the Raman signals of acridine molecules on uncoated Ag NRs and PC Ag@Al2O3 substrates.
Remarkably, we found that their melting point increase monotonously with the decrease of pinhole rate, starting from 257 °C with ~18.0 % pinholes and reaching a maximum at 277 °C when the pinhole rate was ~5.3%%.
It is observed that the substrates with less or smaller Al2O3 pinholes could keep better the nanorod shape and generate less fusion spots after annealing, indicating the pinhole rate's effect on the thermal and morphological stability of these substrates.
It is found that the melting point of PC Ag@Al2O3 raised along with the decrement of pinhole rate, and substrates with less pinholes exhibited better thermal stability but sacrificed SERS efficiency.
Due to the unique structures of these substrates, the melting point of PC Ag@Al2O3 increased along with the decline of the Al2O3 pinhole rate.
b The melting point of PC Ag@Al2O3 substrates as a function of their pinhole rate.
Furthermore, the melting point of various PC Ag@Al2O3 substrates as a function of their pinhole rate was quantitatively evaluated and depicted in Fig. 4.
In summary, we successfully synthesized PC Ag@Al2O3 nanostructures with controllable pinhole rate and investigated in detail the relationship between the melting behavior of PC substrates and Al2O3 pinhole rate.
Fig. 3 Experimental setup; the 3-pinhole aperture has 1.5 mm diameter pinholes (d) and 4 mm of the pinhole space (d').
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