Atomically precise graphene quantum dots synthesized by bottom-up chemistry are promising versatile single emitters with potential applications for quantum photonic technologies. Toward a better understanding and control of graphene quantum dot (GQD) optical properties, we report on single-molecule spectroscopy at cryogenic temperature. We investigate the effect of temperature on the GQDs’ spectral linewidth and vibronic replica, which we interpret building on density functional theory calculations. Finally, we highlight that the vibronic signatures are specific to the GQD geometry and can be used as a fingerprint for identification purposes.
REFERENCES
1.
R.
Rieger
and K.
Müllen
, “Forever young: Polycyclic aromatic hydrocarbons as model cases for structural and optical studies
,” J. Phys. Org. Chem.
23
, 315
–325
(2010
).2.
K.
Müllen
, “Evolution of graphene molecules: Structural and functional complexity as driving forces behind nanoscience
,” ACS Nano
8
, 6531
–6541
(2014
).3.
X.
Yan
, X.
Cui
, and L.-S.
Li
, “Synthesis of large, stable colloidal graphene quantum dots with tunable size
,” J. Am. Chem. Soc.
132
, 5944
–5945
(2010
).4.
X.-Y.
Wang
, X.
Yao
, and K.
Müllen
, “Polycyclic aromatic hydrocarbons in the graphene era
,” Sci. China: Chem.
62
, 1099
(2019
).5.
Z.
Qiu
, S.
Asako
, Y.
Hu
, C.-W.
Ju
, T.
Liu
, L.
Rondin
, D.
Schollmeyer
, J.-S.
Lauret
, K.
Müllen
, and A.
Narita
, “Negatively curved nanographene with heptagonal and [5]helicene units
,” J. Am. Chem. Soc.
142
, 14814
–14819
(2020
).6.
J.
Liu
and X.
Feng
, “Synthetic tailoring of graphene nanostructures with zigzag-edged topologies: Progress and perspectives
,” Angew. Chem., Int. Ed.
59
, 23386
–23401
(2020
).7.
M.
Grzybowski
, B.
Sadowski
, H.
Butenschön
, and D. T.
Gryko
, “Synthetic applications of oxidative aromatic coupling—From biphenols to nanographenes
,” Angew. Chem., Int. Ed.
59
, 2998
–3027
(2020
).8.
Z.
Liu
, H.
Qiu
, S.
Fu
, C.
Wang
, X.
Yao
, A. G.
Dixon
, S.
Campidelli
, E.
Pavlica
, G.
Bratina
, S.
Zhao
, L.
Rondin
, J.-S.
Lauret
, A.
Narita
, M.
Bonn
, K.
Müllen
, A.
Ciesielski
, H. I.
Wang
, and P.
Samorì
, “Solution-processed graphene–nanographene van der Waals heterostructures for photodetectors with efficient and ultralong charge separation
,” J. Am. Chem. Soc.
143
, 17109
–17116
(2021
).9.
Y.-Z.
Tan
, B.
Yang
, K.
Parvez
, A.
Narita
, S.
Osella
, D.
Beljonne
, X.
Feng
, and K.
Müllen
, “Atomically precise edge chlorination of nanographenes and its application in graphene nanoribbons
,” Nat. Commun.
4
, 2646
(2013
).10.
S.
Zhao
, J.
Lavie
, L.
Rondin
, L.
Orcin-Chaix
, C.
Diederichs
, P.
Roussignol
, Y.
Chassagneux
, C.
Voisin
, K.
Müllen
, A.
Narita
, S.
Campidelli
, and J.-S.
Lauret
, “Single photon emission from graphene quantum dots at room temperature
,” Nat. Commun.
9
, 3470
(2018
).11.
T.
Liu
, C.
Tonnelé
, S.
Zhao
, L.
Rondin
, C.
Elias
, D.
Medina-Lopez
, H.
Okuno
, A.
Narita
, Y.
Chassagneux
, C.
Voisin
, S.
Campidelli
, D.
Beljonne
, and J.-S.
Lauret
, “Vibronic effect and influence of aggregation on the photophysics of graphene quantum dots
,” Nanoscale
(published online) (2022
).12.
Q.
Chen
, S.
Thoms
, S.
Stöttinger
, D.
Schollmeyer
, K.
Müllen
, A.
Narita
, and T.
Basché
, “Dibenzo[hi, st] ovalene as highly luminescent nanographene: Efficient synthesis via photochemical cyclodehydroiodination, optoelectronic properties, and single-molecule spectroscopy
,” J. Am. Chem. Soc.
141
, 16439
–16449
(2019
).13.
H.
Thyrrestrup
, G.
Kiršanskė
, H.
Le Jeannic
, T.
Pregnolato
, L.
Zhai
, L.
Raahauge
, L.
Midolo
, N.
Rotenberg
, A.
Javadi
, R.
Schott
, A. D.
Wieck
, A.
Ludwig
, M. C.
Löbl
, I.
Söllner
, R. J.
Warburton
, and P.
Lodahl
, “Quantum optics with near-lifetime-limited quantum-dot transitions in a nanophotonic waveguide
,” Nano Lett.
18
, 1801
–1806
(2018
).14.
B.
Kozankiewicz
, J.
Bernard
, and M.
Orrit
, “Single molecule lines and spectral hole burning of terrylene in different matrices
,” J. Chem. Phys.
101
, 9377
–9383
(1994
).15.
M.
Orrit
and J.
Bernard
, “Single pentacene molecules detected by fluorescence excitation in a p-terphenyl crystal
,” Phys. Rev. Lett.
65
, 2716
–2719
(1990
).16.
C.
Raynaud
, T.
Claude
, A.
Borel
, M. R.
Amara
, A.
Graf
, J.
Zaumseil
, J.-S.
Lauret
, Y.
Chassagneux
, and C.
Voisin
, “Superlocalization of excitons in carbon nanotubes at cryogenic temperature
,” Nano Lett.
19
, 7210
–7216
(2019
).17.
A. B.
Myers
, P.
Tchenio
, M. Z.
Zgierski
, and W. E.
Moerner
, “Vibronic spectroscopy of individual molecules in solids
,” J. Phys. Chem.
98
, 10377
–10390
(1994
).18.
C.
Castiglioni
, C.
Mapelli
, F.
Negri
, and G.
Zerbi
, “Origin of the D line in the Raman spectrum of graphite: A study based on Raman frequencies and intensities of polycyclic aromatic hydrocarbon molecules
,” J. Chem. Phys.
114
, 963
(2001
).19.
R.
Gillen
, M.
Mohr
, and J.
Maultzsch
, “Symmetry properties of vibrational modes in graphene nanoribbons
,” Phys. Rev. B
81
, 205426
(2010
);arXiv:1003.0328.20.
D.
Liu
, C.
Daniels
, V.
Meunier
, A. G.
Every
, and D.
Tománek
, “In-plane breathing and shear modes in low-dimensional nanostructures
,” Carbon
157
, 364
–370
(2020
).21.
M. J.
Frisch
, G. W.
Trucks
, H. B.
Schlegel
, G. E.
Scuseria
, M. A.
Robb
, J. R.
Cheeseman
, G.
Scalmani
, V.
Barone
, G. A.
Petersson
, H.
Nakatsuji
, X.
Li
, M.
Caricato
, A. V.
Marenich
, J.
Bloino
, B. G.
Janesko
, R.
Gomperts
, B.
Mennucci
, H. P.
Hratchian
, J. V.
Ortiz
, A. F.
Izmaylov
, J. L.
Sonnenberg
, D.
Williams-Young
, F.
Ding
, F.
Lipparini
, F.
Egidi
, J.
Goings
, B.
Peng
, A.
Petrone
, T.
Henderson
, D.
Ranasinghe
, V. G.
Zakrzewski
, J.
Gao
, N.
Rega
, G.
Zheng
, W.
Liang
, M.
Hada
, M.
Ehara
, K.
Toyota
, R.
Fukuda
, J.
Hasegawa
, M.
Ishida
, T.
Nakajima
, Y.
Honda
, O.
Kitao
, H.
Nakai
, T.
Vreven
, K.
Throssell
, J. A.
Montgomery
, Jr., J. E.
Peralta
, F.
Ogliaro
, M. J.
Bearpark
, J. J.
Heyd
, E. N.
Brothers
, K. N.
Kudin
, V. N.
Staroverov
, T. A.
Keith
, R.
Kobayashi
, J.
Normand
, K.
Raghavachari
, A. P.
Rendell
, J. C.
Burant
, S. S.
Iyengar
, J.
Tomasi
, M.
Cossi
, J. M.
Millam
, M.
Klene
, C.
Adamo
, R.
Cammi
, J. W.
Ochterski
, R. L.
Martin
, K.
Morokuma
, O.
Farkas
, J. B.
Foresman
, and D. J.
Fox
, gaussian 16, Revision B.01, 2016
.22.
J. G.
Müller
, M.
Anni
, U.
Scherf
, J. M.
Lupton
, and J.
Feldmann
, “Vibrational fluorescence spectroscopy of single conjugated polymer molecules
,” Phys. Rev. B
70
, 035205
(2004
).23.
A.
Neumann
, J.
Lindlau
, S.
Thoms
, T.
Basché
, and A.
Högele
, “Accidental contamination of substrates and polymer films by organic quantum emitters
,” Nano Lett.
19
, 3207
–3213
(2019
).24.
L.
Fleury
, P.
Tamarat
, B.
Kozankiewicz
, M.
Orrit
, R.
Lapouyade
, and J.
Bernard
, “Single molecule spectra of an impurity found in N-hexadecane and polyethylene
,” Mol. Cryst. Liq. Cryst. Sci. Technol., Sect. A
283
, 81
–87
(1996
).25.
A.
Reigue
, R.
Hostein
, and V.
Voliotis
, “Resonance fluorescence of a single semiconductor quantum dot: The impact of a fluctuating electrostatic environment
,” Semicond. Sci. Technol.
34
, 113001
(2019
).26.
V. S.
Iyer
, M.
Wehmeier
, J. D.
Brand
, M. A.
Keegstra
, and K.
Müllen
, “From hexa-peri-hexabenzocoronene to ‘superacenes
,’” Angew. Chem., Int. Ed. Engl.
36
, 1604
–1607
(1997
).© 2022 Author(s). Published under an exclusive license by AIP Publishing.
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