Excitons in linear carbon chains

We synthesise and deposit on a substrate monoatomic chains of carbon atoms stabilised by gold nanoparticles. Raman, absorption and photoluminescence (PL) spectra reveal resonant features of straight polyyne chains, that is significantly beyond the theoretical stability limit of 6 atoms for free-standing carbon chains. Polyyne is a direct band gap semiconductor whose lowest energy optical transition varies in the range between 2 and 5 eV depending on the number of atoms in the chain. Low temperature PL spectra reveal a characteristic triplet fine-structure that repeats itself for carbon chains of different lengths. The triplet is invariably composed by a sharp intense peak accompanied by two broader satellites shifted by about 15 and 25 meV to the lower energy side of the main peak. We interpret these features as an edge-state neutral exciton, positively and negatively charged trions, respectively. The localization of exciton wave-functions at the end of gold-stabilised carbon chains is confirmed by ab-initio calculations. The time-resolved PL shows that the radiative life time of the observed quasiparticles is about 1 ns that is consistent with the characteristic exciton lifetimes in carbon nanotubes (CNT). The radiative lifetime increases with the increase of the length of the chain. At high temperatures a non-radiative exciton decay channel appears due to the termal hopping of carriers between parallel carbon chains. In contrast to CNT excitons, the excitons in carbyne are characterised by lower binding energies (of the order of 15-20 meV), large oscillator strengths and extremely low inhomogeneous broadenings that allow for the detection of the fine structure of exciton and trion transitions. The observation of strong and narrow exciton resonances in PL spectra of monoatomic carbon chains paves the way to their applications in nano-lasers and single photon emitters.

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