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Photoluminescence mechanism in graphene quantum dots: Quantum

confinement effect and surface/edge state
Shoujun Zhu a,b , Yubin Song a , Joy Wang b , Hao Wan b , Yuan Zhang a , Yang Ning a,c ,
Bai Yang a,∗
a
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012, PR China
b
Department of Chemistry, Stanford University, Stanford, CA 94305, USA
c
College of Environment and Resources, Jilin University, Changchun 130012, PR China

a r t i c l e i n f o a b s t r a c t

Article history: As a new class of fluorescent carbon materials, graphene quantum dots (GQDs) have drawn increasing
Received 20 July 2016 attention due to their outstanding properties and potential applications. Herein, GQDs prepared by chem-
Received in revised form 21 October 2016 ical synthetic strategies, which mainly contain cutting different carbon resources and carbonization from
Accepted 6 December 2016
small molecules or polymers, are discussed. Although the photoluminescence (PL) mechanism of GQDs
Available online xxx
can be explained by the size of the GQDs, surface chemical groups, and doping atoms, there is no universal
agreement on the specific PL mechanism. The dominant PL mechanism of GQDs consists of the quantum
Keywords:
confinement effect of conjugated ␲-domains, the surface/edge state in GQDs, as well as the synergistic
Graphene quantum dots
Photoluminescence mechanism
effect of these two factors.
Quantum confinement effect
© 2016 Elsevier Ltd. All rights reserved.
Surface state
Carbon dots

Introduction Synthesis routes of GQDs

To make carbon materials fluorescent, the size and surface
chemistry are very important (they always consist of sp2 and sp3
carbons and post-modified chemical groups) [1]. Many kinds of
fluorescent carbon-based nanomaterials have been synthesized,
including carbon dots [2–5], fluorescent CNTs [6], graphene oxide
(GO) [7], graphene quantum dots (GQDs) [8–11] and so on [12,13].
GQDs prepared by chemical synthetic strategies are chosen as
the main subject to discuss. In detail, the synthesis of GQDs can
be divided into “top-down” splitting methods and “bottom-up”
organic approaches. Due to the special chemical composition of
GQDs, they possess abundant surface groups and strong photolu-
minescence (PL). However, the most controversial issue is the PL
mechanism. The dominant PL center of GQDs contains the quan-
tum confinement effect of conjugated ␲-domains, the surface/edge
state in GQDs, as well as the synergistic effect of these two factors
[1] (Table S1).
∗ Corresponding author.
E-mail address: byangchem@jlu.edu.cn (B. Yang).
The “top-down” splitting method is a direct and efficient route
to preparing GQDs. The most popular “top-down” splitting route is
acid assisted cutting from different carbon sources by H2 SO4 /HNO3 :
the carbon source (graphite power, carbon fiber, carbon nanotube
or even coal) is firstly exfoliated and oxidized, and then undergoes
splitting at the oxygen based defect position by a zipper mecha-
nism (Fig. 1) [1]. Generally, the quantum yields (QYs) of GQDs by the
acid assisted cutting routes are lower than 1% [14]. In an improved
method, hydrothermal [8], solvothermal [15] and photo-fenton
reactions [16] are applied to GO as the initial material, resulting
in GQDs with elevated QYs due to surface modification. There are
other “top-down” splitting routes, involving electrochemistry [9],
metal-graphite intercalation [17], and nanolithography by reactive
ion etching (RIE) [18].
The “bottom-up” methods are efficient routes to produce fluo-
rescent GQDs, including the carbohydrate dehydration and organic
synthesis approaches (Fig. 1). In the carbohydrate carbonization
method, the GQDs are obtained using suitable small molecules or
polymers for dehydration and further carbonization. Commonly
used materials are citric acid and glucose [19]. These forma-
tion processes are usually uncontrollable, resulting in GQDs with
polydispersity; however, the use of designed precursors, such as
intramolecular oxidative polycyclic aromatic hydrocarbons (PAHs),
may accurately obtain GQDs with the desired molecular weight and

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Please cite this article in press as: S. Zhu, et al., Photoluminescence mechanism in graphene quantum dots: Quantum confinement effect
and surface/edge state, Nano Today (2016), http://dx.doi.org/10.1016/j.nantod.2016.12.006
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Fig. 1. Two main approaches were adopted to prepare fluorescent GQDs: the “top-down” splitting route from different carbon sources and “bottom-up” method from small
molecules or polymers.

size [20,21]. The organic synthesis approach is precise but compli-
cated, needing many steps to obtain GQDs in the large dimension.
Optical properties of GQDs
The absorption of GQDs is focused on the UV region. The peak
at 230–270 nm is attributed to the ␲-␲* transition, while the peak
at ca. 320 nm belongs to the n-␲* transition. The absorption tail is
regarded as the surface state, which is related to the hybrid struc-
ture between the graphene core and connected chemical groups.
The most reported GQDs possess emission peaks in the blue to
green region of the spectrum after excitation by UV light. Further-
more, the PL of GQDs is excitation-, pH- and solvent-dependent.
The PL exhibits weak photo-bleaching and is highly stable under
UV light [22].
Photoluminescence mechanism of GQDs
 Domain controlled quantum size effect in GQDs
The GQDs possess a graphene core and attached “uncertain”
chemical groups. The PL is controlled by both the graphene core
and the surrounding chemical groups. Specifically, the graphene
core determines the intrinsic emission, while the attached chemical
groups control the surface state [22].
For the GQDs with a perfect graphene core and fewer sur-
face chemical groups, the bandgap of the conjugated ␲-domains is
thought to be the true intrinsic PL center. A major feature of quan-
tum dots is the quantum confinement effect (QCE), which occurs
when quantum dots are smaller than their exciton Bohr radius
[23,24]. First of all, the GQDs prepared by the organic synthesis
method should be introduced because they possess special elec-
tronic and optical properties that make them suitable models to
investigate the PL of QCE [25]. Recently, Li et al. reported the syn-
thesis of colloidal GQDs with a uniform and tunable size through
organic chemistry routes [26] (Fig. 2a). The GQDs consist of light
atoms and thus have a small dielectric constant and weak spin-
orbit coupling. These lead to strong carrier–carrier interactions and
electronic states with a well-defined spin multiplicity. As a result,
GQDs have a much larger energy band than other inorganic semi-
conductor QDs with similar sizes. That is why most GQDs possess
PL in the blue to green region of the spectrum. Yang et al. investi-
gated the photophysics of the organic synthesized GQDs, and found
that the intrinsic state depends on their size, while the energy level
offset between the intrinsic state and edge state determines their
optical properties (Fig. 2b) [27]. If the energy level offset between
the intrinsic state and edge state is large enough, the fluorescence
is dominant. If the energy level offset is small enough, the long car-
rier lifetime in the intrinsic state offers a possibility for intersystem
crossing from the singlet excited state to the triplet excited state of
edge state [26]. In cases of C132 H34 and C222 H42 , it is possible that
the intrinsic states decrease to a lower energy level than the edge
state, and as a result, lose the expected fluorescence.
Edge and chemical groups controlled surface state in GQDs
For most GQDs prepared from “top-down” routes, the PL center
of the GQDs was suggested to be the surface state, which is related
to the hybridization structure of the edge groups and the connected
graphene core (Fig. 3a). The efficient edge groups for green emis-
sion are mainly carboxyl and amide groups while hydroxyl groups
contribute to blue emission [14,28]. Zhu et al. proved the exis-
tence of the surface state of GQDs using the following three factors
[14]: (1) the PL of the GQDs is enhanced by UV exposure, during

Please cite this article in press as: S. Zhu, et al., Photoluminescence mechanism in graphene quantum dots: Quantum confinement effect
and surface/edge state, Nano Today (2016), http://dx.doi.org/10.1016/j.nantod.2016.12.006
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Fig. 2. Quantum confinement effect of conjugated ␲-domains in GQDs. (a) Energy gap of ␲–␲* transitions calculated based on DFT as a function of the number of fused
aromatic rings (N). Reproduced with permission of Wiley-VCH from Ref. [32]. (b) Solubilization strategy for colloidal GQDs. Reproduced with permission from the American
Chemical Society from Ref. [26]. (c) The suggested energy levels of C42 H18 , C96 H30 , C132, C132 H34 , and C222 H42 . The energy level of C132 was determined from the reported
paper [26]. Reproduced by permission of Elsevier from Ref. [27].

Fig. 3. Surface/edge states in GQDs. (a) The oxygen groups were formed at the edge of GQDs during the splitting process. (b) The PL picture in green-fluorescence GQDs. The
oxygen and amino groups on the edge determine the band gap of these GQDs. Reproduced with permission from the Royal Society of Chemistry from Ref. [14]. (c) Energy
level structures to explain the optical behaviors of photoexcited electrons in GQDs, including their radiative recombination from discrete sp2 -related states and continuous
defect states, thermally activated decay into non-radiative traps, and non-radiative relaxation from higher- to lower- defect states. Reproduced with permission from the
American Chemical Society from Ref. [29]. (d) HOMO and LUMO energy levels of GQD–(NH2 )n. Black and blue lines indicate HOMO and LUMO levels, respectively. Reproduced
with permission from the American Chemical Society from Ref. [31].

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which partial OH groups are converted to carboxyl groups; (2)
the PL properties of GQDs can be further improved by a one-step
solvothermal treatment, in which partial carboxyl groups are con-
verted to amide groups, forming modified-GQDs (m-GQDs) with
even stronger surface states; (3) reduced m-GQDs possess more
OH groups than reduced GQDs, resulting in a greater number of
blue PL centers. No matter which energy level of the LUMO band an
electron is excited to, it finally relaxes into the surface state energy
levels, which determine the PL properties of the GQDs (Fig. 3b).
The quantum yield of the GQDs can be improved by three factors:
enhancement of PL centers by edge modification, enrichment of
the ␲ structure electron density through reduction, and suppres-
sion of non-radiative recombination by removing the epoxy groups.
Pan et al. suggested that blue PL of GQDs might be attributed to
free zigzag sites with a carbene/carbyne-like triplet ground state
described as ␴1 ␲1 . With single-particle spectroscopic technology,
the defect state has also been proven to determine the PL of GQDs
(Fig. 3c) [29]. Tetsuka et al. prepared GQDs with edge-terminated
by a primary amine, modifying the electronic structure to yield
effective orbital resonance between the amine moieties and the
graphene core [30]. Jin et al. reported that the functionalized GQDs
exhibit a redshift in the PL emission compared to the pre-existing
GQDs, and the PL emissions of the amine-functionalized GQDs also
shift with changes in pH due to the protonation and deprotonation
of the functional groups (Fig. 3d) [31].
Outlook
Other standpoints, such as molecule state, surface passiva-
tion, heteroatom doping, are also notable for understanding the
PL mechanism of GQDs. A reasonable explanation of GQDs’ PL
mechanism will be monumental not only in guiding synthesis
of graphene materials with multi-colors, improving output, and
enhancing quantum yields, but also in expanding their potential
in nano-electronics, photovoltaic devices, bio-detection, as well as
disease diagnostics/therapeutics.
The size and connected groups on GQDs are polydisperse, which
make PL mechanism complicated. Fortunately, these inherent func-
tionalized groups provide opportunities for tailoring their chemical
structures as well as their optical and optoelectronic properties.
The widely observed PL emission in GQDs may be a result of the
quantum size effect and surface state. The surface state also con-
tains triplet carbenes at the zigzag edges, attached chemical groups,
surface defects, heteroatom doping in carbon lattice, and giant
red-edge effect [7]. The influence of single- or multi-layer(s) in
GQDs is another important issue in understanding the PL mech-
anism. Many reported GQDs are in fact not single-layered, so a
comparison between single-layered and multi-layered GQDs is
desired. The multi-layered GQDs should actually be carbon quan-
tum dots (CQDs), which means that researchers should examine
the PL mechanism of carbon-based materials and investigate it
synthetically.
Acknowledgements
This work was supported by the NSFC under Grant nos.
21504029, 51373065, the 973 Program under Grant no.
2012CB933800, and the International Postdoctoral Exchange
Fellowship Program (20150031).
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.nantod.2016.
12.006.
Please cite this article in press as: S. Zhu, et al., Photoluminescence mechanism in graphene quantum dots: Quantum confinement effect
and surface/edge state, Nano Today (2016), http://dx.doi.org/10.1016/j.nantod.2016.12.006
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Shoujun Zhu is a postdoctor researcher in Stanford Uni-
versity (Dai lab). He received his Ph.D. in polymer physics
and chemistry in 2014 under the supervision of Prof. Bai
Yang and Junhu Zhang. His research is centered on func-
tional/targeting fluorophores and bio-detection/imaging
applications.
Yubin Song is now a Ph. D student in the State Key Lab
of Supramolecular Structure and Materials, majoring in
polymer chemistry and physics. Under the supervision of
Prof. Bai Yang, he is working at the PL mechanism and
novel application of the carbon nanomaterials.
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Joy Wang is a senior at Stanford University, currently
majoring in chemistry. She has been working in Hongjie
Dai’s lab for the past two years. Her research interests
lie in immunohistochemistry and generating fluorophore-
protein conjugates for disease detection. In 2015, she was
awarded the Goldwater scholarship for academic merit in
a scientific field.
Hao Wan is a postdoctor researcher in Stanford University
(Dai lab). He received his Ph.D. in Dalian Institute of Chem-
ical Physics (DICP), Chinese Academy of Sciences (CAS). His
current research is centered on bio-detection/imaging.
Yuan Zhang is a senior at Jilin University, currently major-
ing in chemistry. She has been working in Bai Yang’s lab for
the past two years. Her research interests lie in graphene materials.
quantum dots and carbon dots.
Please cite this article in press as: S. Zhu, et al., Photoluminescence mechanism in graphene quantum dots: Quantum confinement effect
and surface/edge state, Nano Today (2016), http://dx.doi.org/10.1016/j.nantod.2016.12.006
5
Yang Ning, Ph.D., a professor at College of Environment
and Resources, Jilin University. She received her Ph.D. in
polymer physics and chemistry in 2011 under the super-
vision of Prof. Bai Yang. Her current research interests are
focused on preparation and application of environment-
friendly functional materials.
Bai Yang, Ph.D., a professor at the State Key Lab of
Supramolecular Structure and Materials, Jilin Univer-
sity. His research work was awarded the Second Prize
of the State Natural Science Award of China. He is the
Cheung Kong Scholar of the Chinese Ministry of Edu-
cation and the Recipient of the National Science Fund
for Distinguished Young Scholars at the National Science
Foundation of China. His current research interests are
focused on polymeric carbon nanodots, polymeric nano-
hybridization and photoelectric materials and devices via
aqueous approaches, high performance polymeric hybrid
optical materials and ordered fabrication of polymeric
microstructures with multi-scale and photonic responsive