ArXiv · 2026
We use temperature-dependent Raman spectroscopy to investigate five configurations of atomically precise 9-armchair graphene nanoribbons (9-AGNRs) differing in substrate, alignment, and coverage. Measurements from 70 to 300 K and full-window Lorentzian fits yield the positions and linewidths of the radial-breathing-like mode (RBLM), confinement-activated D, and G modes. The D and G modes soften on heating at configuration-dependent rates. For the same unaligned high-coverage film before and after polymer-free transfer, measured D- and G-mode redshift rates are smaller on the Raman-optimised substrate than on Au by factors of 4.7 and 5.6, respectively. We model the frequency shifts as thermoelastic contributions from substrate-ribbon thermal-expansion mismatch plus a Klemens-type anharmonic term. Between 80 and 290 K, the model gives D- and G-mode redshifts from 0.305 to 6.322 cm⁻¹, whereas the zero-K-referenced Klemens-type contribution remains below 0.050 cm⁻¹. Under the adopted assumptions, thermal-expansion mismatch therefore dominates these shifts. The modelled RBLM change remains below 1 cm⁻¹ and cannot be robustly separated into its two contributions. The dense aligned Au array additionally shows intermediate-temperature minima in the D- and G-mode linewidths, inconsistent with conventional monotonic anharmonic broadening and indicating an additional temperature-dependent broadening or line-shape contribution.
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