The Photoluminescence Mechanism in Carbon Dots (Graphene Quantum Dots, Carbon Nanodots, and Polymer Dots) : Current State and Future Perspective

Nano Research 2015, 8(2): 355–381
DOI 10.1007/s12274-014-0644-3
The photoluminescence mechanism in carbon dots

(graphene quantum dots, carbon nanodots, and polymer
dots): Current state and future perspective
Shoujun Zhu, Yubin Song, Xiaohuan Zhao, Jieren Shao, Junhu Zhang, and Bai Yang ()
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China
Received: 9 September 2014 ABSTRACT

Revised: 10 November 2014 At present, the actual mechanism of the photoluminescence (PL) of fluorescent
Accepted: 14 November 2014 carbon dots (CDs) is still an open debate among researchers. Because of the variety
of CDs, it is highly important to summarize the PL mechanism for these kinds
© Tsinghua University Press of carbon materials; doing so can guide the development of effective synthesis
and Springer-Verlag Berlin routes and novel applications. This review will focus on the PL mechanism of
Heidelberg 2014 CDs. Three types of fluorescent CDs were involved: graphene quantum dots
(GQDs), carbon nanodots (CNDs), and polymer dots (PDs). Four reasonable PL
KEYWORDS mechanisms have been confirmed: the quantum confinement effect or conjugated
carbon dots, π-domains, which are determined by the carbon core; the surface state, which is
graphene quantum dots, determined by hybridization of the carbon backbone and the connected chemical
carbon nanodots, groups; the molecule state, which is determined solely by the fluorescent
polymer dots, molecules connected on the surface or interior of the CDs; and the crosslink-
photoluminescence enhanced emission (CEE) effect. To give a thorough summary, the category and
mechanism synthesis routes, as well as the chemical/physical properties for the CDs, are
briefly introduced in advance.
1 Introduction fluorescent carbon-based nanomaterials have been

synthesized, including carbon nanodots (CNDs) [1, 2],
Carbon materials, which include graphite, diamond, fluorescent carbon nanotubes (CNTs) [3], graphene
fullerenes, carbon nanotubes (CNTs), and graphene, oxide (GO) [4, 5], graphene quantum dots (GQDs)
have been well known for many years. To make these [6–12], polymer dots (PDs) [13–15], nanodiamonds
materials fluorescent, their size and surface chemical [16, 17], and so on. In this review, carbon dots (CDs)—
groups should be carefully modulated. As-prepared which include GQDs, CNDs, and PDs—prepared by
fluorescent carbon materials always consist of sp2/sp3 chemical synthetic strategies are discussed. These three
carbon, oxygen/nitrogen-based groups, and post- types of CDs possess similar photoluminescence (PL),
modified chemical groups. Up to now, many kinds of although they are distinguished by their intrinsic
Address correspondence to [email protected]

356 Nano Res. 2015, 8(2): 355–381
inner structure and surface chemical groups. The mined solely by the fluorescent molecules connected
synthesis of CDs can be divided into top-down nano- on the surface or interior of the CDs; and the
cutting methods and bottom-up organic approaches. crosslink-enhanced emission (CEE) effect. To give a
Top-down nano-cutting generally includes cutting thorough summary, the category, synthesis routes,
different carbon resources such as GO, carbon fiber, and chemical/physical properties for CDs are briefly
CNTs, fullerenes, and graphite electrodes. Bottom- introduced in advance. Owing to the number of
up organic approaches include carbonization of reports about CDs, we apologize to researchers whose
carbohydrates, self-assembly of polycyclic aromatic important publications may be left out.
hydrocarbons (PAHs), and organic synthesis from
small molecules.
2 Category and synthesis routes
At present, the actual mechanism of CD photo-
luminescence is still an open debate among researchers 2.1 Classification of reported CDs
[18]. Because of the variety of CDs, it is highly
important to summarize the PL mechanism for these “CDs” is a comprehensive term for various nanosized
types of carbon materials; doing so can guide the carbon materials. In a broad sense, all nanosized
development of effective synthesis routes and novel materials that are composed mainly of carbon can be
applications. This review will therefore focus on the called CDs. CDs always possess at least one dimension
PL mechanism of CDs. Three types of fluorescent less than 10 nm in size and fluorescence as their
CDs are discussed: graphene quantum dots (GQDs), instinct properties. The structure of CDs consists of
carbon nanodots (CNDs), and polymer dots (PDs) sp2/sp3 carbon and oxygen/nitrogen-based groups or
(Fig. 1) [19]. Four respectable PL mechanisms have polymeric aggregations. CDs mainly include GQDs,
been confirmed: the quantum confinement effect or CNDs, and PDs (Fig. 1). GQDs possess one or a few
conjugated π-domains, which are determined by the layers of graphene and connected chemical groups on
carbon core; the surface state, which is determined by the edges. They are anisotropic with lateral dimensions
hybridization of the carbon backbone and connected larger than their height. CNDs are always spherical
chemical groups; the molecule state, which is deter- and they are divided into carbon nanoparticles, which
Figure 1 Three types of fluorescent CDs are discussed in this review: graphene quantum dots (GQDs), carbon nanodots (CNDs), and
polymer dots (PDs).
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Nano Res. 2015, 8(2): 355–381 357
do not have a crystal lattice, and carbon quantum dots make these types of carbon sources photoluminescent,
(CQDs), which have an obvious crystal lattice. As a their size and surface chemistry must be carefully
result, the PL center is very different for the different modulated. The most common cutting method uses a
types of CNDs. PDs are aggregated or cross-linked concentrated oxidizing acid (HNO3 or an H2SO4/HNO3
polymers prepared from linear polymers or monomers. mixture) [29]. In this process, the bulk carbon materials
In addition, the carbon core and the connected poly- are cut into small pieces and the surfaces of the pieces
mer chains can self-assemble to form PDs. Owing to are modified by oxygen-based groups. The resulting
the diversity of CDs, there are many approaches to small carbon product is known as GQDs, CQDs, or
fabricating them, the most common of which are CNDs. It should be noted that two-step cutting routes
“top-down” cutting from different carbon sources and have always been used to prepare GQDs. The first step
“bottom-up” synthesis from organic molecules or is to convert a graphite-based material into GO sheets
polymers and modification of surface functionality or (usually using the modified Hummers method). The
passivation. We call the “top-down” and “bottom-up” second step is cutting the GO into GQDs using various
routes “nano-methods,” which are distinguished from methods [30, 31].
the exclusively organic routes [20, 21]. Other “top-down” cutting routes include electro-
chemistry [32, 33], hydrothermal/solvothermal/special
2.2 “Top-down” cutting from different carbon
oxidation [30, 34], metal–graphite intercalation [35],
sources
and strong physical routes, such as arc discharge [36],
Generally, CDs are obtained by oxide cutting carbon laser ablation [37], and nanolithography by reactive ion
resources such as graphite power [22], carbon rods [23], etching (RIE) [38, 39]. In the electrochemistry method,
carbon fibers [24], carbon nanotubes [25, 26], carbon the graphite rod electrode is broken up during the
black [27], and even candle soot [28] (Fig. 2). These electrochemical cutting process to form CQDs or GQDs.
carbon materials possess a perfect sp2 carbon structure The applied electrolyte contains ethanol [23], an ionic
and lack an efficient band gap to give fluorescence. To liquid [32], NaH 2 PO4 [40], tetrabutylammonium
Figure 2 The main approaches to fabricating CDs: “Top-down” cutting from different carbon sources and “bottom-up” synthesis from
organic molecules or polymers.
www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

358 Nano Res. 2015, 8(2): 355–381
perchlorate (TBAP) [41], phosphate buffered saline which can be modified by other chemical groups.
(PBS)/water [42, 43], etc. The electric field peels off Functionality and passivation can be used to enhance
nanosized carbon from the electrode through graphite the quantum yields (QYs) of CDs, change the PL
layer intercalation and/or a radical reaction. emission, and meet the requirements of special
In hydrothermal/solvothermal/special oxidation applications. The QYs of raw CDs used to be very low,
methods, some oxidized carbon resources such as GO making them difficult to use in applications; even
and oxidized CNTs that possess defect-based chemical detecting these CDs was difficult. Sun’s group
groups (oxygen-based groups) are cut into pieces at pioneered the use of NH2–polyethylene glycol (PEG)
high temperature and pressure [30, 34]. Some special passivation to elevate the PL QY of CNDs [53]. Zhu et
oxidation methods, such as a photo-Fenton reaction al. used a similar method to enhance the PL properties
of GO to GQDs [44], can also break up GO. GQDs of GQDs [54]. Yang’s group used the cross-linked
prepared by mask-assisted RIE in particular is an route to enhance the PL properties of PDs; bare
efficient approach for precisely controlling the size and polyethyleneimine (PEI) possessed little fluorescence,
surface chemistry of CDs [38], resulting in an ideal whereas cross-linked PDs had an elevated PL QY [55].
model system for clarifying the PL mechanism. Surface or edge modification has also been used to
tune the PL emission of CDs. For example, the green
2.3 “Bottom-up” synthesis from organic molecules emission can be changed to a blue emission by surface
or polymers reduction [56].
The “bottom-up” methods are efficient routes to
produce fluorescent CDs on a large scale (Fig. 2). For 3 Chemical and physical properties
example, small molecules and polymers may undergo
dehydration and further carbonization to form CNDs 3.1 Chemical structure
and PDs. The applied molecules always possess –OH,
As mentioned in the discussion of categories and
–COOH, –C=O, and –NH2 groups, which can dehydrate
synthesis routes, there are diversiform fluorescent CDs
at elevated temperatures. There are many approaches
and various synthesis routes to obtain these materials.
for carrying out the dehydration and carbonization
As a result, the chemical structures of CDs are diverse
processes, such as hydrothermal [45], microwave [46],
according to the different synthesis approaches. For
and combustion [47] methods, pyrolysis in con-
example, GQDs possess single or a few graphene
centrated acid [48], carbonization in a microreactor [49],
layers and connected chemical groups on the edges.
enhanced hydrothermal (microwave-hydrothermal [50]
They are anisotropic, with lateral dimensions larger
and plasma-hydrothermal [51]) methods, and so on.
than the height. Owing to the existence of a carbon
It is difficult to control these formation processes,
core, GQDs possess certain crystallinity, with an
resulting in CDs with polydispersity. However, using
average lattice parameter of 0.24 nm (Fig. 3(a)), which
designed precursors may allow us to accurately obtain
corresponds to (100) spacing of single graphene dots
GQDs with the desired molecular weight and size,
on lacey support films [35]. CNDs are always spherical,
such as intramolecular oxidative polycyclic aromatic
and they are divided into carbon nanoparticles without
hydrocarbons (PAHs). Although organic-synthesized
a crystal lattice and CQDs with an obvious crystal
GQDs are the perfect model for understanding the
lattice [57]. The typical interlayer distance of CQDs
PL mechanism of fluorescent carbon materials, the
is ca. 0.34 nm, which corresponds to (002) spacing
complicated synthesis method and variations in
of the crystalline graphite (Fig. 3(b)). PDs are an
fluorescence as compared with common fluorescent aggregation/assembly or cross-linked polymers from
CDs reduce their usefulness [52]. linear non-conjugated polymers. In addition, the
2.4 Surface functionality or passivation carbon core and grafted polymer chains can also form
PDs. All of the CDs possess connected or modified
Prepared CDs always possess many reactive groups, chemical groups on the surface, such as oxygen-based,
Nano Res. 2015, 8(2): 355–381 359
Figure 3 Selected typical structures of CDs. (a) Anisotropic GQDs with a single-layer carbon structure, with a height less than 1 nm
and a lattice spacing of 0.24 nm. Reproduced by permission of Royal Society of Chemistry from Ref. [35]. (b) High-resolution TEM
images of the CNDs. Reproduced by permission of American Chemical Society from Ref. [57]. (c) Possible stable structure for each
molecular structure of the GQDs that corresponds to the observed MALDI-TOF mass pattern Reproduced by permission of Wiley-VCH
from Ref. [58].
amino-based groups, polymer chains, etc. The direct 3.2 Optical properties
characterization methods for the carbon core include
high-resolution TEM (HRTEM), Raman spectroscopy, Despite the diversity of the structures, CDs possess
and X-ray diffraction (XRD). To evaluate the grafting some similar optical properties in terms of their
of chemical groups, Fourier transform infrared (FTIR), absorption and fluorescence. Herein, we will just
X-ray photoelectron spectroscopy (XPS), nuclear summarize the common optical properties rather than
magnetic resonance (NMR), matrix-assisted laser consider specific examples. CDs typically show strong
desorption ionization time-of-flight (MALDI-TOF) optical absorption in the UV region (230–320 nm),
(Fig. 3(c)), and element analysis are used to determine with a tail extending into the visible range. For the
the general structure [58]. As a result, these types of carbon core, a maximum peak at ca. 230 nm is ascribed
fluorescent CDs are not “pure” carbon materials. The to the π–π* transition of aromatic C–C bonds, whereas
hybridization and coefficient between the carbon a shoulder at 300 nm is attributed to the n–π*
core and surrounding chemical groups play a leading transition of C=O bonds or other connected groups
role in the PL behavior of these CDs. [59]. In addition, the connected chemical groups may

360 Nano Res. 2015, 8(2): 355–381
contribute to the absorption at the UV–visible regions. blinking nor meaningful reductions in PL intensity
The observed deviations in absorption spectra data, are observed in such CDs after continuous exposure
at least to some extent, indicate differences in the to excitation (Fig. 4(a)) [37]. However, for CDs with
compositions or structures of different hybridization molecule-state emission, the PL intensity decreases
derivatives. dramatically after high-power UV exposure [65]. Some
The PL properties of CDs are the most important special luminescence behaviors of CDs can be observed
issue in terms of investigating the PL mechanism and in some situations, such as with electrochemical
adapting CDs for novel applications. Generally, the luminescence (ECL, Fig. 4(b)) [33]. The ECL mechanism
emission spectra of CDs are roughly symmetrical on of CDs is suggested to involve the formation of
the wavelength scale. The emission peaks of CDs are excited-state CDs via electron-transfer annihilation
usually wide, with large Stokes shifts as compared of negatively charged and positively charged CDs.
with the emission of organic dyes. The emission peak Although up-conversion PL (two-photon absorption
position is always related to the excitation wavelength, and anti-Stokes PL) has been reported [23, 54], it is
which is known as wavelength-dependent behavior. quite important to establish a proper characterization
This behavior may result from the wide distribution of system in order to investigate these types of properties
differently sized dots and surface chemistry, different because some so-called “up-conversion PL” in CDs
emissive traps (salvation effect), or a mechanism could be due to the excitation of second-order diffrac-
currently unresolved [60]. Fortunately, the excitation- tion light (wavelength λ/2) from the monochromators in
dependent PL behaviors can be applied in multicolor the fluorescence spectrophotometer [66, 67]. Amplified
imaging applications [61, 62]. spontaneous green emission and lasing emission has
The PL of CDs is a property similar to that of also been observed from CNDs (Fig. 4(c)) [68], and the
semiconductor quantum dots (QDs), but fluorescent high PL quantum yield and small overlap between
nanoparticles possess many differences. First, it is the absorption and emission of CDs in an ethanol
inefficient to tune the PL color by controlling the size solution were the key factors in achieving lasing
of CDs. In most situations, the PL color of CDs is emission. These special optical properties may lead
relative to the surface groups rather than the size. to novel application of different types of CDs.
The most common CDs have strong PL from blue to In addition to direct characterization, there are
green, and a few CDs possess optimal emission in several indirect approaches for studying PL mechanisms
long-wavelength regions [23, 28, 63]. Another main in CDs. pH-Dependent and solvent-dependent PL is
difference between CDs and QDs is that the PL very important for investigating the emission behaviors
bandwidth of CDs is much wider. This wide peak may of CDs (Figs. 4(d)–4(e)) [30, 34]. The molecule state is
result from the inhomogeneous chemical structure affected under both strongly acidic and strongly basic
and diverse PL centers. atmospheres, whereas the PL intensity of the carbon
QY is the number of emitted photons relative to the core–edge state may increase owing to protonation or
number of absorbed photons. CDs possessed rather deprotonation of the functional groups. The PL quench
low QYs (even lower than 1%) when they were first behaviors of CDs are another important tool for
discovered. After surface modification or passivation, understanding the PL mechanism (Fig. 4(f)) [69].
the QY can be dramatically increased. The enhanced
3.3 Biological toxicity
PL properties are attributed to the strongly PL centers
on the surface, the synergy between the carbon core The toxicity of CDs is of extraordinary concern because
and the chemical groups, or solely to the presence of of their potential for use in bio-based applications
fluorophores [64]. The QYs of CDs have continually [12, 19, 70, 71]. Bio-imaging-based applications in vitro/
improved year by year. Generally, QY depends on the in vivo must be non-toxic and biocompatible [72]. Over
synthesis route and the surface chemistry. the last several years, metal-based QD bio-imaging
Most CDs possess good photostability, which is methodologies have appeared, together with toxicity
the result of the carbon core-based PL center. Neither concerns because of the use of intrinsically toxic
Nano Res. 2015, 8(2): 355–381 361
Figure 4 Selected optical properties of CDs. (a) The photo-stability of CNDs. Reproduced by permission of American Chemical
Society from Ref. [37]. (b) ECL of CNDs in aqueous 0.1 M PBS solution in the presence and absence of 1 mM K2S2O8. Inset: ECL
responses of CNCs/S2O82– obtained during a continuous potential scan at 0.1 V·s–1. Reproduced by permission of American Chemical
Society from Ref. [33]. (c) Schematic diagram of experimental setup for optical pumping investigations of the CND-based laser device.
The images below show the operating CND-based laser device under 355 nm laser pumping at 30 kW·cm–2 and 90 kW·cm–2.
Reproduced by permission of Wiley-VCH from Ref. [68]. (d) The pH-dependent behavior of GQDs. Reproduced by permission of
Wiley-VCH from Ref. [34]. (e) The PL solvent-dependent behavior of GQDs. Reproduced by permission of Royal Society of Chemistry
from Ref. [30]. (f) Schematic of a Förster Resonance Energy Transfer (FRET)-based GQD sensor for detection of TNT: quenching
mechanism through (1) resonance energy transfer from the GQD donor to the TNT acceptor and (2) charge transfer from the excited
GQDs to TNT. Reproduced by permission of Elsevier from Ref. [69].
elements such as cadmium. As compared with metal- particles. All the evidence points to the great potential
based QDs, GQDs are composed of an intrinsically of CDs for in vitro and in vivo imaging studies.
non-toxic element, carbon, which makes them a
particularly useful and promising bio-analytical tool. 4 PL mechanism of GQDs
Toxicity studies have been conducted by various
research groups, and CDs appear to have low toxicity GQDs are the simplest CDs, with a single-layer carbon
in vitro and in vivo. So far, the inherent toxicities of core with connected chemical groups on the surface
CDs have been evaluated by the cell-viability assay. or edges. As a result, GQDs are the ideal model to
The results indicate that GQDs, CNDs, and PDs investigate the PL mechanism of CDs. To explain the PL
possess excellent biocompatibility and low cytotoxicity mechanism of GQDs, the PL behavior of chemically
[15, 29, 30, 53, 73–75]. Carboxylated GQDs did not derived GO is introduced first because GO is an
cause apparent toxicities in rats at different dosages important raw material for GQD preparation and thus
(5 and 10 mg·kg–1) over 22 days, as evidenced by GO and GQDs possess similar chemical structures.
blood biochemistry and hematological analysis [76]. GO contains oxygen-based functional groups, either
No severe symptoms of inflammation were observed on the basal plane or at the edges. Therefore, the
in the liver, kidney, spleen, heart, or lungs 22 days after 2–3 nm aromatic sp2 domains are surrounded by a
the administration of the carboxylated GQD nano- linearly aligned epoxy and hydroxyl-boned sp3 C–O

362 Nano Res. 2015, 8(2): 355–381
matrix [5, 77]. Because GO has such a structure, the Similar to GO, GQDs possess more defects, oxygen
fluorescent properties are determined by the π states groups, and functional groups on the surface. The
of the sp2 sites. The π and π* electronic levels of the fluorescence results obtained for GO can be used
sp2 clusters, which are influenced by the band gap to understand these emissions in GQDs. Excitons
of the σ and σ* states of the sp3 matrix, are strongly in graphene have an infinite Bohr diameter. Thus,
confined. Radiative recombination of electron–hole graphene fragments of any size will show quantum
(e–h) pairs in such sp2 clusters can facilitate fluorescence confinement effects. As a result, GQDs have a non-zero
[78]. Because of the existence of a wide size distri- band gap and PL on excitation. This band gap is
bution of sp2 domains in GO, the band gaps of different tunable by modifying the size and surface chemistry
sizes of sp2 cover a wide range, leading to a wide PL of the GQDs [6]. Considerable development in the
emission spectrum from visible to near infrared (Fig. 5). preparation of GQDs has been witnessed in the last
Many groups have investigated the fluorescence of five years, and researchers have discovered reasonable
GO and reduced GO (r-GO). For example, Luo et al. PL mechanisms: the surface/edge state and conjugated
proposed that bond distortions may contribute to π-domains.
the fluorescence of GO and r-GO [79]. Gokus et al.
4.1 Surface/edge state in GQDs
observed visible luminescence in oxygen plasma-
treated graphene and attributed the emission to The surface/edge state contains triple carbene at the
CO-related localized electronic states at the oxidation zigzag edges, oxygen-based groups on the graphene
sites [4]. Furthermore, Galande et al. studied the core, and resonance of amine moieties and the
pH-dependent fluorescence of GO, and they suggested graphene core.
the emission of quasi-molecular fluorophores in such When graphene sheets are cut along different
types of materials [80]. They found that the excited crystallographic directions, diverse types of edges
state of the fluorophore species was protonated in (armchair and zigzag edges) can be obtained. The
acidic media, which makes the PL spectra different in edge type plays an important role in determining the
acidic and basic solutions. This kind of quasi-molecular electronic, magnetic, and optical properties of the GQD.
fluorophore is caused by carboxylic acid groups that Ritter et al. stated that predominantly zigzag-edge
are electronically coupled with the surrounding GQDs with average dimensions of 7–8 nm are metallic
graphene core sheets [81]. owing to the presence of zigzag-edge states and that
Figure 5 Proposed PL emission mechanisms of (a) the predominant "red emission" in GO from disorder-induced localized states and
(b) the predominant “blue emission” in reduced GO from confined cluster states. Reproduced with permission of Wiley-VCH from Ref. [78].
Nano Res. 2015, 8(2): 355–381 363
Graphene nanoribbons (GNRs) with a higher fraction approximately 20 nm by exfoliating and disintegrating
of zigzag edges exhibit a smaller energy gap than CNTs or graphite flakes [35]. The obvious single layer
those with a predominantly armchair-edge ribbon of and clear zigzag edge were confirmed using AFM
similar width [82]. Radovic and Bockrath reported that and bright-field high-resolution TEM. A newly opened
the zigzag sites are carbene-like, with a triplet ground band gap arose from the triple carbenes at the zigzag
state being the most common, whereas the armchair edges, corresponding to the transition from the highest
sites are carbyne-like, with a singlet ground state being occupied molecular orbital (HOMO) to σ and to the
the most common [83]. Pan et al. suggested that the π orbital of the lowest unoccupied molecular orbital
blue PL exhibited by hydrothermally cut GQDs might (LUMO) in the triple carbenes. These two types of
be attributed to free zigzag sites, with a carbine-like GQDs with sizes of 9.6 nm and 20 nm, respectively,
triplet ground state described as σ1π1 [34]. Under possessed similar absorption and emission behavior,
acidic conditions, the free zigzag sites of the GQDs which proved that the PL mechanism was determined
are protonated, forming a reversible complex between by the triple carbene at the zigzag edges instead of by
the zigzag site and H+ and leading to the breaking of the quantum confinement effects (Fig. 6(a)).
the emissive triple carbene state and PL quenching Pan et al. also used single-particle spectroscopic
(Fig. 4(b)). On the other hand, the PL recovers because measurements to investigate the PL behaviors of GQDs
the free zigzag sites are restored under alkaline [84]. As schematically shown in Fig. 6(b), photo-
conditions. Lin et al. prepared GQDs with a size of excited electrons through the π–π* transitions were
Figure 6 Surface/edge states in GQDs. (a) Free zigzag emission mechanism of the GQDs. Reproduced with permission of Royal
Society of Chemistry from Ref. [35]. (b) 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-lying defect states. Reproduced with permission of American
Chemical Society from Ref. [84]. (c) HOMO and LUMO energy levels of GQD–(NH2)n. Black and blue lines indicate HOMO and
LUMO levels, respectively. The dotted lines denote the HOMO and LUMO energy level of NH2. Reproduced with permission of
American Chemical Society from Ref. [85]. (d) The PL picture in green-fluorescence GQDs. (ABS: absorption; ESA: excited-state
absorption). Reproduced with permission of Wiley-VCH from Ref. [89].

364 Nano Res. 2015, 8(2): 355–381
proposed to relax into either the sp2 energy levels or the band gap gradually decreased with the increasing
the defect states (what we call the surface state), giving number of –NH2 groups (Fig. 6(c)). Kumar et al. also
rise to blue or long-wavelength PL, respectively. The investigated the PL behaviors of amino-functionalized
blue emission might bear discrete features owing to GQDs. First-principles calculations suggested that
the quantum confinement effect (QCE) of electrons primary amine-edge termination (NH2) resulted in
inside the sp2 carbon domains. The long-wavelength formation of an additional interband ca. 3.28 eV within
emission is related to the the hybrid structure com- the energy gap owing to p-orbital hybridization of
prising the oxygen functional groups (at the edges C–N atoms at the edge sites [86]. Feng and co-workers
and/or on the basal planes) and the graphene core. proved that 1,2-ethylenediamine functionalization on
Despite noticeable differences in the size and the the surface of GQDs can form a specific cyclic structure
number of layers from particle to particle, all of the that facilitates proton transfer from the ammonium
GQDs studied possessed almost the same spectral line moiety to the conjugated structure, thus leading to the
shapes and peak positions. This suggests that the PL largest enhancement of fluorescence in the serial of
of these GQDs was caused by their surface state. samples [87].
In addition to oxygen-based groups, amine-based The mechanism of GQD emission was further
groups also contribute to the surface state in GQDs. investigated with femtosecond transient absorption
In the work of Tetsuka et al., the ammonia-assisted spectroscopy and femtosecond time-resolved
hydrothermal method was used to prepare GQDs. The fluorescence dynamics measured by a fluorescence
product was edge-terminated by a primary amine, upconversion technique and a nanosecond time-
allowing the electronic structure to be modified by correlated single-photon counting technique by Wang’s
the effective orbital resonance of the amine moieties and Yang’s groups [88, 89]. They found that two
and the graphene core [58]. For GQDs of the same size, independent molecule-like states and a dark intrinsic
the emission wavelength increased with increasing state existed in solvothermally synthesized GQDs, as
numbers of amine groups. Furthermore, the GQDs shown in Fig. 6(d). The intrinsic state is attributed to
possessed high QYs because of the reduction of car- the graphene core and its PL occurs at approximately
boxylic and epoxide groups, which act as non-radiative 470 nm, with a dominant short lifetime and low PL
electron–hole recombination centers. Combining the QY. Two additional irrelevant molecule-like states
experimental results and ab initio calculations, the at approximately 320 nm and 400 nm exhibited blue
primary amines at the edges of GQDs were shown to fluorescence, with a peak at ca. 430 nm, and green
have a higher HOMO than hydrogen-terminated fluorescence, with a peak at ca. 530 nm. The three
groups owing to the strong orbital interaction with types of emission states constitute the fascinating PL
the –NH2 groups. The resonance feature between the of green-fluorescence GQDs. In related work, Yang’s
delocalized π orbital and the molecule orbital in the group found that the PL of GQDs could be changed
–NH2 groups results in a narrowing of the optical from green emission to blue emission by tuning the
band gap. Such amino-containing GQDs have also surface chemistry [90]. Through modification of the
been reported by other groups. Jin et al. reported that GQDs, the connected alkylamines transferred the
functionalized GQDs exhibited a redshift in the PL –COOH and epoxy of GQDs into –CONHR and
emission spectrum as compared to non-functionalized –CNHR, both of which can reduce the non-radiative
GQDs (the PL emissions of the amine-functionalized recombination induced by the –COOH and epoxy
GQDs also shifted with changes of the pH owing to groups [91] and transfer GQDs from defect-state
the protonation and deprotonation of the functional emission into intrinsic-state emission. In the reduction
groups) [85]. Calculations from density functional method, the carbonyl, epoxy, and amino moieties
theory (DFT) illustrated that PL shifts resulted from were changed into –OH groups, which suppressed
charge transfers between the functional groups and the non-radiative process and further enhanced the
GQDs, which can tune the band gap of the GQDs. The integrity of the π-conjugated system (it also reduced
band gap of the GQDs decreased to 2.254 eV when the defects). As a result, intrinsic-state emission
they were functionalized by one amino group. Also, (containing both the intrinsic and blue molecule-like
Nano Res. 2015, 8(2): 355–381 365
state observed in transient absorption, TA) rather 4.2 Quantum confinement effect of conjugated
than defect-state emission plays a leading role. Blue π-domains in GQDs
and green emissions of GQDs and graphene oxide
quantum dots (GOQDs) were also reported by Seo et In the last section, the surface state rather than the
al. [92]. They revealed that the green luminescence of intrinsic graphene core state was shown to play a
GOQDs originates from defect states with oxygenous leading role in the PL behavior of related GQDs.
functional groups, whereas the blue luminescence of However, for GQDs with a perfect graphene core
GQDs is dominated by intrinsic states in the highly and fewer surface chemical groups, the band gap of
crystalline structure. conjugated π-domains is thought to be the true
The surface/edge state of PL in the GQDs has also intrinsic PL center. A major feature of QDs is the QCE,
been investigated by other groups [93–98]. For example, which occurs when quantum dots are smaller than
Lingam et al. found evidence for edge-state PL in their exciton Bohr radius [100]. DFT calculations have
solvothermally synthesized GQDs. If the edge of the shown that the band gap increases to approximately
GQDs was destroyed or disappeared, the PL intensity 2 eV in GQDs consisting of 20 aromatic rings and
decreased to the point that it vanished [99]. All similar 7 eV for benzene (Fig. 7(a)) [5]. In other words, the PL
work proved that the surface state (or edge state) was emission of the GQDs can be tuned by adjusting the
the key PL mechanism in these types of GQDs. In size of the conjugated π-domains. Typically, because
addition, for some types of GQDs, the functional sur- the particles are smaller, the luminescence energies
face state could be considered as special polyaromatic are blue-shifted to a higher energy.
fluorophores. First, GQDs prepared by the organic solution method
Figure 7 Quantum confinement effect of conjugated π-domains in GQDs. (a) Energy gap of π–π* transitions calculated based on DFT
as a function of the number of fused aromatic rings (N). The inset shows the structures of the graphene molecules used for the
calculation. Reproduced with permission of Wiley-VCH from Ref. [5]. (b) Solubilization strategy for colloidal GQDs. Reproduced with
permission of American Chemical Society from Ref. [101]. (c) The suggested energy levels of C42H18, C96H30, C132, C132H34, and
C222H42. The size-dependent energy levels in these H-passivated small GQDs are in agreement with the molecule orbital calculation. The
intrinsic state depends on size. The energy-level offset between the intrinsic state and the edge state determines its optical properties.
The energy level of C132 was determined from the reported paper [21]. Reproduced by permission of Elsevier from Ref. [104].

366 Nano Res. 2015, 8(2): 355–381
are introduced because they possess special electronic activation condition, ca. kBT), the long carrier lifetime
and optical properties, making them suitable models in the intrinsic state could facilitate intersystem crossing
for investigating the PL of GQDs exhibiting the QCE. from a singlet-excited edge state to a triplet-excited
Recently, Li et al. reported the synthesis and optical edge state, such as for the abovementioned C132. In
characterization of colloidal GQDs with a uniform the cases of C132H34 and C222H42, the intrinsic state
and tunable size through organic chemistry routes [21]. possibly decreased and was lower than the edge state;
The prepared GQDs consisted of graphene moieties as a result, the GQDs lost the expected fluorescence.
containing 168, 132, and 170 conjugated carbon atoms The size-dependent PL of GQDs prepared by
(Fig. 7(b)) [101]. The synthesis was based on oxidative “nano-methods,” in which the PL is not controlled
condensation reactions developed by Scholl, Müllen, by the QCE, is now introduced. Peng et al. prepared
etc. [102]. GQDs consist of light atoms, and thus they three kinds of GQDs with sizes of 1–4 nm, 4–8 nm,
have a small dielectric constant and weak spin-orbit and 7–11 nm by varying the reaction temperatures.
coupling. These characteristics lead to strong carrier– These GQDs emitted PL ranging from blue and green
carrier interactions and electronic states with well- to yellow, as shown in Figs. 8(a)–8(b) [24]. GQDs
defined spin multiplicity. As a result, GQDs have prepared via acidic oxidation from carbon black
a much larger energy band than other inorganic showed PL transitions from green to yellow as their
semiconductor QDs of similar size. This is why most sizes increased from 15 to 18 nm. Kim et al. presented
GQDs possess PL in the range from blue to green. size-dependent shape/edge-state variations of GQDs
Furthermore, the size-dependent, discrete excitonic and visible PL showing anomalous size dependences
levels could significantly slow the relaxation of highly (Fig. 8(c)) [105]. Upon varying the average size of
excited states in GQDs owing to a phonon bottleneck. the GQDs from 5 to 35 nm, the peak energy of the
In addition, strong carrier–carrier interactions could absorption spectra monotonically decreased (Fig. 8(d)).
lead to the generation of more than one exciton with The peak energy and shape of the PL spectra are
one photon absorbed, a process particularly useful strongly dependent on the size of the GQDs. All PL
for improving the efficiency of photon-generated spectra show similar size-dependent peak shifts, almost
carriers [103]. The singlet–triplet splitting of GQDs irrespective of excitation wavelength except 470 nm.
was determined to be ca. 175 meV, and intersystem The PL peak energy decreases as the QD diameter
crossing was so efficient that it competed with internal increases up to ca. 17 nm, which is consistent with
conversion among states with the same multiplicity. the QCE. However, when the diameter is larger than
As a result, the GQDs emitted both fluorescence and ca. 17 nm, the PL peak energy increases with increasing
phosphorescence [101]. Since triplet states have a diameter; in other words, the QCE no longer holds.
significantly longer lifetime, they could profoundly These results originate from changes to the edges.
affect the chemical reactivity and processes such as For diameters <17 nm, the majority of GQDs have
charge transfer or exciton migration in the GQD-based a circular/elliptical shape, with mixed zigzag and
system. Yang et al. investigated the photophysics of armchair edges; however, for diameters >17 nm, the
organically synthesized GQDs (C42H18, C96H30, C132H34, edges exhibit a polygonal shape with mostly armchair
and C222H42), and they found that the intrinsic state edges. These changed edges disturb the evolution
depended on size, whereas the energy-level offset between the QCE and the size of the GQDs. As
between the intrinsic state and the edge state deter- mentioned above, the greater number of armchair
mined the optical properties of the GQDs (Fig. 7(c)) edges as compared with zigzag edges could result in
[104]. As a result, the green fluorescence of C42H18 and larger energy gaps for graphene materials [82].
C96H30 not only depended on the size, it also resulted Most of the reported GQDs possessed diameters
from the bright edge state. If the energy-level offset greater than 5 nm and strongly visible PL emission.
between the intrinsic state and the edge state is large However, based on DFT results, the band gap energies
enough, the fluorescence is dominant. If the energy- of GQDs with diameters greater than 5 nm are no
level offset is small enough (meeting the thermal higher than 1.0 eV [106]. The visible PL found in
Nano Res. 2015, 8(2): 355–381 367
Figure 8 (a) UV-vis spectra of GQDs A, B, and C, which correspond to synthesized reaction temperatures at 120, 100, and 80 °C,
respectively. Inset is a photograph of the corresponding GQDs under UV light with 365 nm excitation. (b) PL spectra of GQDs with
different emission colors excited at 318, 331, and 429 nm. Reproduced with permission of American Chemical Society from Ref. [24].
(c) HRTEM images of GQDs for their major shapes and corresponding populations (p) with increasing average size of GQDs. Here, the
dotted line indicates a GQD region and p is defined as the ratio of the number of GQDs with a major shape at each average size. (d)
Size-dependent PL spectra excited at 325 nm for GQDs with average sizes of 5–35 nm in deionized (DI) water. Also shown is the
dependence of PL peak shifts on the excitation wavelength from 300 to 470 nm for GQDs with average sizes of 5–35 nm. Reproduced
with permission of American Chemical Society from Ref. [105].
GQDs could be explained by the minimization of variations of GQDs, the electronic transitions can be
thermalization owing to electron–phonon scattering modified in nanometer-sized GQDs to produce strong
or by formation of an excited-state relaxation channel, visible PL emissions in a controlled fashion. The high-
resulting in inelastic light scattering by electric energy PL of GQDs is especially efficient owing to the
doping [100, 107]. By size-dependent shape/edge-state unique properties of graphene: fast carrier–carrier

368 Nano Res. 2015, 8(2): 355–381
scattering dominates over electron–phonon scattering. 5 PL mechanism of CNDs

This facilitates direct recombination of excited e–h
pairs, producing high-energy PL before thermalization 5.1 Quantum size effect in carbon quantum dots
of the carriers with the lattice [108]. The high Coulomb
There are a few studies concerned with the quantum
scattering rate of graphene, which is attributed to the
size effect in CNDs. We would rather call these types
strongly reduced dielectric screening in the two-
of CNDs “CQDs.” Kang et al. developed a current
dimensional structure, is also essential for producing
density-controlled electrochemical method to prepare
high-density non-equilibrium carriers responsible for
CQDs. After further separation, CQDs 1.2–3.8 nm in
the strong e–h recombination. size were obtained [23]. The PL properties varied
Moreover, because the surface/edge state-derived sensitively with CQD size (Fig. 9(a)), with small CQDs
PL emissions are relatively brighter, there may be a (1.2 nm, center) giving UV light emission, medium-
general risk for their contaminating the observed band sized CQDs (1.5–3 nm) giving visible light emission
gap fluorescence in GQDs [86]. As a result, much of (400–700 nm), and large CQDs (3.8 nm, center) giving
the experimentally observed PL of GQDs was surface/ near-infrared emission (Figs. 9(b)–9(j)). To further
edge-state PL. For clear investigation on the QCE of confirm these results and explain why these strong
GQDs, organic synthesis and nanolithography-based emissions came from the quantum-sized graphite
routes for fabricating perfect sample will be highly fragments of CQDs, Kang et al. performed theoretical
desired in the near future. calculations to investigate the relationship between
Chromatographic separation is also a powerful PL and cluster size. Figure 9k shows the dependence
tool for investigating the PL mechanism of GQDs. of HOMO–LUMO gaps on the size of the graphene
For example, Zhu et al. pioneered the use of column fragments. As the size of the fragment increases, the
chromatography to separate GQDs with a tuned gap gradually decreases. The gap energy in the visible
oxidation degree; as a result, the separated GQDs spectral range was obtained from graphene fragments
possessed PL from blue to green [31]. Matsuda and with diameters of 1.4–2.2 nm, which agrees well with
co-workers developed size-exclusion high-performance the visible emission of CDs with diameters of <3 nm.
liquid chromatography (HPLC) to separate the pre- Thus, they deduced that the strong emission of CDs
pared GQDs [109]. Drastic changes in the PL spectra comes from the quantum-sized graphite structure.
of GQDs from UV to red are observed according to Lau and co-workers developed a novel method of
the difference in their overall sizes. Discrete changes preparing water-soluble monodispersed crystalline
in emission wavelength indicate that the PL change CQDs (which they called GQDs in their work) with
comes from differences in the number of small sp2 diameters ranging from 1.5 to 3.9 nm ± 0.55 nm [110].
fragments of various sizes or from shapes embedded They proved that the larger the diameter of the GQD,
in the GQDs. the shorter the average lifetime. Rhee and Kwon
It is also highly important to clarify the PL developed size-controlled synthesis of CNDs using
mechanism of GQDs by theoretical calculations. For a “water-in-oil” emulsion as a self-assembled soft
example, Alam Sk et al. systematically investigated the template [111, 112]. The micelles were micro-emulsions
PL properties of GQDs using DFT and time-dependent of water encapsulated by surfactant molecules in
density functional theory (TDDFT) calculations [106]. the immiscible oil; the size of the micelles could be
The results revealed that the emission of zigzag-edged regulated by the water–surfactant molar ratio. Thus,
GQDs can cover the entire visible light spectrum by this reaction can offer size tunability and a narrow size
varying the diameter from 0.89 to 1.80 nm. Armchair distribution. They found that different-sized CNDs
edges and pyrrolic N-doping induce a blue-shift, had different band gaps and hence exhibited diverse
whereas chemical functionalities and defects can cause PL behaviors. The PL peak position was blue-shifted
a red-shifted PL. Furthermore, the isolated inhomo- by approximately 25 nm upon increasing the size of
geneous sp2 domains can widen the PL peaks of GQDs. the CNDs from 1.5 to 3.5 nm. These results, which are
Nano Res. 2015, 8(2): 355–381 369
5.2 Surface state in CNDs
Functional groups have various energy levels, which

may result in a series of emissive traps. When the light
of a certain excitation wavelength illuminates the
CNDs, a surface state emissive trap will dominate the
emission. A higher degree of surface oxidation or other
effective modification can result in more surface
defects, resulting in a red-shifted emission. The surface
state does not consist of isolated chemical groups but
rather the hybridization of the carbon backbone and
connected chemical groups. From the first report of
CNDs [25], which were prepared via electrophoretic
analysis and purification of fluorescent CNT fragments
in 2004 (the CNDs were an oxidation-cut product
with oxygen-based chemical groups on the surfaces),
most PL centers of the reported CNDs were proven to
be surface states. Sun and co-workers systematically
investigated the surface passivation of CNDs by
amino-polyethylene glycol (PEG). The CDs were
initially produced via laser ablation of a carbon target
in the presence of water vapor with argon as the
carrier gas [37]. The authors proved that many organic
molecules could provide surface passivation, which
further proved that surface energy traps controlled the
PL mechanism. Although the excitation may induce the
band-gap absorption band, the resulting fluorescence
was also controlled by the surface state emission
Figure 9 Quantum size effect in carbon quantum dots (CQDs). (Fig. 10(a)) [113].
a) Fluorescent microscopy images of CQDs with an excitation From then on, many oxidation-based surface states
wavelength of 360 nm (scale bar: 50 mm). (b)–(g) HRTEM
were directly attached during the process of preparing
images of typical CQDs with different diameters (scale bar:
2 nm). (h) Optical images of typical-size CQDs illuminated under CNDs. In another words, oxygen-based groups on the
white (daylight lamp) and UV light (365 nm). (i) PL spectra of carbon core were the primary surface state of CNDs.
typical-size CQDs: the red, black, green, and blue lines are the Mao and co-workers obtained colorful CNDs derived
PL spectra for blue-, green-, yellow-, and red-emission CQDs, from oxidizing candle soot and further separation
respectively. (j) Relationship between the CQD size and the PL
(top-down route). The PL, which ranged from violet
properties. (k) HOMO–LUMO gap dependence on the size of the
graphene fragments. Reproduced with permission of Wiley-VCH
to red, may have been induced by different surface
from Ref. [23]. oxidation [28]. CNDs with surface-state emission were
also achieved by the bottom-up carbonization method,
opposite those of the quantum size effect, are further and the PL could be tuned from blue to green using
explained by the presence of sp2 clusters with certain different reaction conditions. It is very interesting that
energy gaps and oleylamine ligands, which act as most surface-state emission studies focused on the
auxochromes to reduce the energy gaps. As a result, blue–green range. Pang and co-workers proved that
large CNDs with relative small ratios of ligand/sp2 the surface states were the key factor in tuning the
clusters possess larger band gaps as compared with luminescence of electrochemical CNDs [41]. Red-shifted
small CNDs. emissions were observed for CNDs with a high

370 Nano Res. 2015, 8(2): 355–381
surface oxidation degree. Zheng and other researchers predominantly showed a single level. A possible
also proved that the emission of CNDs can be explanation for this is that after the initial excitation,
changed from green to blue by surface reduction [56]. the energy is transferred from the higher energy
Furthermore, Richards and co-workers used single- absorbing site to a lower energy emissive site in the
particle fluorescence technology to investigate the PL oxidized CND particles. In contrast, when CNDs are
fluctuations of oxidized/reduced CNDs [114]. They reduced, the low-energy emissive traps are entirely or
suggested that single dots can possess multiple partially removed, blocking energy-transfer pathways.
fluorophore units associated with the CND core and In addition, the authors proved that the CNDs
oxygenated defect-related emissive traps. The majority possessed photo-bleaching at the single- particle level,
of the reduced CND particles showed multiple which is in contrast to the reported steady-state
levels of excited state, whereas the oxidized particles fluorescence characterization (Fig. 10(b)).
Figure 10 Surface state and carbon-core state in CNDs. (a) The CND structure and AFM topography image of CNDs on mica
substrate with the height profile along the line in the image. Reproduced with permission of American Chemical Society from Ref. [53].
(b) Photostability measurements of CNDs with 561 nm excitation under continuous higher intensity (0.3 kW/cm2) confocal excitation
(561 nm). Reproduced with permission of American Chemical Society from Ref. [114]. (c) Dual fluorescence bands observed in CNDs,
which could be attributed to core- and surface-state emission. Reproduced with permission of American Chemical Society from Ref.
[115]. (d) Three types of CDs with green emission chosen to clarify the surface-state PL mechanism. (e)–(f) The electronic state in CDs.
(g) TA spectra for CDs 1–3 at 400 nm excitation. CDs 1: electrochemically synthesized CNDs, CDs 2: solvothermally synthesized GQDs 1,
CDs 3: microwave-synthesized CNDs, GSB: ground-state bleaching, ESA: excited-state absorption, SE: stimulated emission. Reproduced
with permission of American Chemical Society from Ref. [117].
Nano Res. 2015, 8(2): 355–381 371
Tang and co-workers pointed out that the dual PL proved that all the investigated CDs had the same
bands of CNDs were attributed to core and surface- excited-state behaviors. The only difference was the
state emissions [115]. They conducted temperature- proportion of radiative recombination during the
dependent fluorescence measurements and found that whole relaxation process of the photogenerated
the dual emission bands exhibited similar temperature carriers. It is considered that the degree of carbon
dependence (Fig. 10(c)). The strong electron–electron crystallization decreased, whereas the QYs increased
interactions and weak electron–phonon interactions for CDs 1–3. The common photophysics unraveled:
could account for the very broad PL band, even at 77 K. the photogenerated carriers are first stored in the
Wen et al. indicated that the PL of CNDs consisted of carbon backbone. They then leak quickly into any
two overlapping spectral bands, which were ascribed possible emission state (the hybridization structure
to the intrinsic and extrinsic states [116]. Band I of the carbon backbone and chemical groups) and
originated from the localized sp2 nanodomains, in trap (meaningless structures), in which graphitic
which the energy band gap was determined by the size crystallinity acts as a temporary reservoir (Fig. 10(f)).
and shape of the domains with a small bandwidth of In this mechanism, the increased degree of graphitic
175 meV. Band II originated from the surface states crystallinity or carbonization will lead to better
with a much broader bandwidth of 450 meV. A fast photostability but lower the QY because of different
trapping process was observed from the nanodomains non-radiative relaxation channels created by the
into the surface states, with a time constant of 400 fs. carbon structures (for example, the interlamination of
Relaxation with time constants of a few picoseconds, the graphite). Furthermore, because the green PL can
tens of picoseconds, and a few nanoseconds observed be translated to blue by chemical reduction (–COOH
at each wavelength arose from the relaxation by changes to –OH) and the green PL is quenched at
optical phonon scattering, acoustic phonon scattering, high or low pH ranges (protonation/deprotonation of
and e–h recombination, respectively. The wavelength- carboxyl groups), the surface state can be attributed
dependent PL was attributed to the isolated and to the special molecule conformations consisting of
broadly distributed PL in the surface. these oxygen-based groups and several edge carbon
Furthermore, in our recent collaboration, the surface atoms of the carbon backbone. Also, owing to the
states for green emission of several CDs were con- variety of possible edge states, some edge states
firmed. Three types of CDs (denoted as CDs 1–3) with could be non-radiative states (traps). Hence, the
different carbon structures and similar PL emissions competition among different emission centers and
were chosen as the model system (Figs. 10(d)–10(e)) traps dominates the optical properties of carbon
[117]. CD-1 was synthesized by electrochemical ablation nanomaterials. The fact that the CDs used contained
of graphite rod electrodes (top-down method), and both GQDs and CNDs explains how the surface states
they possessed high graphitic crystallinity [23]; CD-2 could be common and similar for both GQDs and
was fabricated by a two-step method combining CNDs [41, 56, 90, 96, 119, 120].
“top-down” cutting of GO and various separation Although the origin of fluorescence in CNDs is not
routes (a kind of GQD) [30]; CD-3 was synthesized yet entirely understood, there is mounting evidence
by microwave-assisted small-molecule carbonization that emission arises from both an intrinsic band gap
(bottom-up method) [118]. Femtosecond TA spectros- resulting from confined sp2 conjugation in the core
copy was used to shed light on the PL mechanism of CNDs and extrinsic fluorescence resulting from a
for these three samples at 400 nm excitation. From surface state that can be either directly excited or
Fig. 10(g), despite the spectral superposition in each excited by energy transfer from an intrinsic band. As
TA spectrum, it is still amazing that the transient a result, the tunable fluorescence emission of CDs
features in the three types of carbon nanomaterials can can be achieved by either controlling the domain size
be attributed to the same model. The main difference of sp2 conjugation or modifying the chemical groups
is the intensity of the stimulated emission. This result formed on the surfaces of CNDs.

372 Nano Res. 2015, 8(2): 355–381
5.3 Molecule state and carbon-core state in CNDs CNDs, small fluorophore molecules are formed at
low reaction temperatures. As the carbonization
First of all, the difference between the surface and temperature increases, the carbon core is formed by
molecule state should be noted. As mentioned above, dehydration of the initial molecules or consumption
the surface state is the PL center, formed by the of the formed fluorophores. These CNDs exhibit
synergetic hybridization of the chemical groups and strong PL emission with high QYs, whereas the
the carbon core, whereas the molecule state is the PL carbon-core state possesses weak PL behavior with
center formed solely by an organic fluorophore; the high photostability.
fluorophore is connected on the surface or interior of Giannelis and co-workers first investigated the
the carbon backbone and can exhibit PL emission formation mechanism of CNDs with both the molecule
directly. The molecule state is the emerging PL center and carbon-core states (Fig. 11(a)) [121]. Using citric
for a type of CND prepared by small-molecule acid (CA) and ethanolamine (EA) as the model system,
carbonization (bottom-up route). To prepare these pyrolysis at 180 °C resulted in a molecular precursor
Figure 11 Molecule state and carbon-core state in CNDs. (a) Schematic representation of the emission characteristics of three
photoactive species produced from the thermal treatment of a mixture of CA and EA. During pyrolysis, the organic fluorophores (blue
groups) are consumed for the buildup of the carbogenic core (black sphere) so that the PL component that corresponds to the carbogenic
core (black bars) increases at the expenses of the component that arises from the organic fluorophores (blue bars). Reproduced with
permission of American Chemical Society from Ref. [121]. (b) The excitation-dependent PL for CNDs 1–4 (from left to right) prepared
from CA and EDA at different temperature. Reproduced with permission of Wiley-VCH from Ref. [65]. (c) The PL intensity of CNDs
as a function of high-power UV exposure time. (d) The PL lifetime of CNDs as a function of UV exposure time Reproduced with
permission of Royal Society of Chemistry from Ref. [122]. (e) The suggested product of CA and EDA at different temperatures. (f) The
determined molecule structure of the fluorophore.
Nano Res. 2015, 8(2): 355–381 373
with a strongly intense PL and high QY of 50%. At the carbon core, and the PL is due to the synergistic
higher temperatures (230 °C), a carbogenic core started effect of the carbogenic core and the molecule state. In
forming, and the PL was due to the presence of both the latest research, the authors purified and confirmed
molecular fluorophores and the carbogenic core. the structure of a fluorophore molecule prepared at
However, the QY for these CNDs was only 15%. This temperatures lower than 150 °C (Fig. 11(f)).
value is significantly lower than the abovementioned
50%, which suggests that a large number of
6 PL mechanism of PDs: the crosslink-
fluorophores were used as the building blocks of the
carbogenic domains. CNPs that exhibited PL mostly
enhanced emission (CEE) effect
or exclusively arising from carbogenic cores were Non-conjugated PDs, which are a specific type of
obtained at even higher temperatures (300 and 400 °C), CDs, possess aggregated polymer structures and have
and the QY decreased markedly. The quenching of drawn increasing attention over the last three years
the carbon-core structure to facilitate the emission [13–15, 104, 123–125]. These types of PDs are different
of the neighboring molecule state might also account from the conjugated PDs, which are obtained from an
to some extent for the suppressed emission of the assembly of fluorescent-conjugated polymers [126].
PL center observed for CNPs prepared at high The PDs under discussion here are always prepared
temperature. from non-conjugated polymers by dehydration, con-
Yang and co-workers also investigated the molecule densation, carbonization, or assembly routes. In these
and carbon-core states using CA and ethylenediamine situations, the PL centers are attributed to the formed
(EDA) as model molecules. They prepared four kinds carbon core or the fluorophores. Owing to convenient
of CNDs at 150, 200, 250, and 300 °C (denoted as surface modification, PDs are very promising as
CNDs 1–4) [65]. CNDs prepared below 250 °C always novel fluorescent materials. To extend the application
have difficulty in TEM imaging, perhaps owing to the of these types of materials, it is highly important to
unshaped nanoparticles, especially at low synthesis confirm a clear PL mechanism. In several pioneering
temperatures. The QYs of CNDs 1–4 decreased, works, PL behaviors were preliminary investigated
whereas the photostability increased, and the excitation- for several types of PDs. Liu et al. synthesized PDs by
dependent PL was increasingly obvious (Fig. 11(b)). a grass hydrothermal route [13]. Dai and co-workers
Furthermore, the PL intensity of CND 2 was quenched prepared PDs by polymerizing carbon tetrachloride
over 90% by high-power UV exposure (the generated and ethylenediamine [14]. Zhu et al. used a general
·OH with ultrahigh oxidation potential can destroy route to transform linear non-conjugated polymers into
the molecule state of CNDs), as shown in Fig. 11(c) fluorescent PDs [15]. With these types of materials,
[122]. However, the PL lifetime decreased and was the formation of polymer aggregations (i.e., PDs)
maintained at ca. 6 ns (Fig. 11(d)), which corresponded promoted the PL behavior [15, 127].
to the carbon-core state with strong photostability and The clear PL mechanism of PDs was clarified to be
weak PL. Based on these results, Fig. 11(e) summarizes the CEE effect by Yang’s group [55]. The PL pro-
the rules for CND formation and the PL mechanism. perties of potential fluorescent centers (fluorophores)
At reaction temperatures less than 150 °C, a type of are amplified by the CEE effect. Using branched PEI as
fluorophore with a high QY was formed. At reaction a model non-conjugated polymer, the CEE effect was
temperatures of 150–250 °C, CA and EDA formed investigated for a series of PEI-based PDs (PDs 1–4).
both the fluorophore molecules and the crosslinked The PEI-based PDs possessed potential fluorophores
polymer backbone. In the meantime, CNDs were (secondary and tertiary amines), and the enhanced PL
formed by the dehydration of CA and EDA. In this originated from the decreased vibration and rotation in
situation, the PL mainly results from the formed such crosslinked PEI-based PDs. Figures 12(a)–12(b)
fluorophores connected on the CNDs. At high tem- show the applied crosslinked PDs and their PL
peratures (over 300 °C), owing to further carbonization, properties. The PDs possessed temperature-dependent
partial fluorophores are consumed to further form PL (Fig. 12(c)); high temperatures quenched the PL to

374 Nano Res. 2015, 8(2): 355–381
Figure 12 PL mechanism of PDs: the crosslinking-enhanced emission (CEE) effect. (a) Scheme of the preparation process of
non-conjugated PDs. Reproduced with permission of Royal Society of Chemistry from Ref. [15]. (b) The absorption and fluorescence
spectra of crosslinking PDs. (c) The temperature-dependent PL of PDs. (d) Representation for the PL mechanism (CEE effect) of bare
PEI and PDs 1–4. (1) Electrons excited from the ground state and trapped by the amino-based states; (2) excited electrons return to the
ground state via the radiative route; (3) excited electrons return to the ground state via a vibration and rotation non-radiative route; (4)
excited electrons return to the ground state via a carbon core-based non-radiative route. Reproduced with permission of Royal Society of
Chemistry from Ref. [55].
some degree. This behavior preliminary proved that rotation process. For PDs 1 and 2, owing to the
the crosslinked skeleton decreases the vibration and crosslinked skeleton, the vibration and rotation of the
rotation of the amine-based PL center in the PDs (the amino-based fluorophores were restricted, and the
high temperature aggravates the vibration and rotation, percentage of radiative process increased (CEE effect).
thus increasing the non-radiative process). The electron For PD 3, the PEI chains were immobilized by the
level of PEI and the PEI PDs is shown in Fig. 12(d). amorphous carbon core; both the immobilization of
For bare PEI, the excited electrons mainly dropped to the PEI chains and the antenna effect of the carbon
the ground state through a non-radiative vibration/ core enhanced the PL. For PD 4, although the PEI
Nano Res. 2015, 8(2): 355–381 375
chains were fixed and the amine-based center was respectable PL principles have been elucidated: the
enhanced by the CEE effect, the carbon core with quantum confinement effect or conjugated π-domains,
its multilayer crystal lattice possessed non-radiative which are determined by the carbon core; the surface
structures and traps. As a result, the radiative process state, which is determined by hybridization of the
was neutralized and confined. carbon backbone and connected chemical groups;
Actually, previous work has confirmed the CEE the molecule state, which is determined solely by the
effect, but the authors did not realize such an fluorescent molecules connected on the surface or
important PL enhancement principle. For example, interior of the CDs; and the CEE effect.
Sun and co-workers reported the fabrication of ultra- We would like to share our perspectives on some
bright amphiphilic PDs by the self-assembly of a critical issues regarding the PL mechanism and
segmented copolymer [125]. They demonstrated that possible solutions to potentially address these issues.
the rigid and compact structure of the PDs played a There are three main challenges. First, it is still a great
crucial role in the excitation-dependent and enhanced challenge to develop an efficient method for mass
fluorescence behavior. The pH-dependent fluorescence production of high-quality CDs. Because of their
of PDs further confirms that an acidic environment “uncertain” chemical groups on the surface, the CDs
results in a much more rigid and compact conforma are types of “uncertain” materials. If the chemical
tion and induces the unique fluorescent effect. structure of CDs can be controlled during the
Furthermore, the concept of non-conjugated PDs synthesis process, it will be convenient and possible
was very different with the dendrimers (such as Poly to provide a definite PL mechanism for CDs. Second,
(amido amine)s, PAMAMs). Dendrimers always researchers should apply sufficient characterization
possess a sphere-like shape, and they are typified by to illuminate the PL center or PL mechanism. Owing
an internal molecular architecture consisting of tree- to inadequate investigation, the PL center for many
like branching, with each outward layer or generation reported CDs has been blurred or even mistaken.
containing exponentially more branching points [128, And last, it would be very useful to study different
129]. In general, non-conjugated PDs include these CDs together for systematic comparison. Although
types of materials, and possessed the most extensive the diversity of existing CDs increases the difficulty
concept in all of the PDs. The concept of the CEE of systematic research, the PL mechanism is similar
effect is also different from the reported aggregation- for these types of CDs.
induced emission (AIE), which mainly refers to small Owing to the outstanding properties of fluorescent
organic molecules exhibiting physical or supramolecular carbon materials, such as superior fluorescence,
aggregation [130, 131]. physiological stability, pH sensitivity, fine biocom-
patibility, and low toxicity, they are being exploited
for energy-related devices, composites materials, and
7 Summary and outlook
environmental and biological applications. For example,
In this review, we have briefly introduced the category, the storage and transport of electrons in CDs have
synthesis methods, and properties of three CD materials been exploited for solar cells [42, 132, 133], organic
(GQDs, CNDs, and PDs), and we have described light-emitting diodes (OLEDs) [50, 134], photodetectors
recent advances in elucidating the PL mechanism of [135], photocatalysts [23], and supercapacitors [136].
these materials. A wide range of approaches (top-down The quench-based PL (on-off and off-on) of CDs has
cutting and bottom-up carbonization) already exist been developed in sensors for biomolecules, metal
for producing CDs with controllable characteristics. ions, and toxic/dangerous substances [74, 137–138].
Investigation of the PL properties of CDs includes The stable PL and low toxicity of CDs make them a
the different emission centers, excitation dependence, perfect candidate for bio-imaging [30, 53], biosensors
and pH and solvent sensitivity, all of which are hot [139], drug delivery [140], and medical diagnosis [141].
research topics. Although a variety of CDs with The rich chemical groups on the surfaces and facile
different chemical structures have been developed, four modification of CDs are beneficial for fluorescent

376 Nano Res. 2015, 8(2): 355–381
nanocomposites [127], functional hybrids [142], and [6] Zhu, S. J.; Tang, S. J.; Zhang, J. H.; Yang, B. Control the size
high-refractive-index materials [143]. In the future, we and surface chemistry of graphene for the rising fluorescent
expect the advent of more facile and robust synthetic materials. Chem. Commun. 2012, 48, 4527–4539.
methods and novel applications to better realize [7] Shen, J. H.; Zhu, Y. H.; Yang, X. L.; Li, C. Z. Graphene
the increasing potential of CD materials. Moreover, quantum dots: emergent nanolights for bioimaging, sensors,
catalysis and photovoltaic devices. Chem. Commun. 2012,
the synthesis process, the CDs themselves, and their
48, 3686–3699.
application is thought to be safe and environmentally
[8] Zhang, Z. P.; Zhang, J.; Chen, N.; Qu, L. T. Graphene
benign, which shows the powerful potential of these
quantum dots: An emerging material for energy-related
materials for the abovementioned applications. For
applications and beyond. Energy Environ. Sci. 2012, 5,
all these reasons, it is extremely important to promote 8869–8890.
the development of CDs, which could be a promising [9] Li, L. L.; Wu, G. H.; Yang, G. H.; Peng, J.; Zhao, J. W.;
candidate to replace organic dyes or inorganic Zhu, J.-J. Focusing on luminescent graphene quantum dots:
quantum dots in related fields. Rapid developments Current status and future perspectives. Nanoscale 2013, 5,
in synthesizing CDs with controllable sizes, tailorable 4015–4039.
chemical structures, and a clear PL mechanism will [10] Bacon, M.; Bradley, S. J.; Nann, T. Graphene quantum dots.
promote their application. Part. Part. Syst. Charact. 2014, 31, 415–428.
[11] Zhou, X. J.; Guo, S. W.; Zhang, J. Y. Solution-processable
graphene quantum dots. ChemPhysChem 2013, 14, 2627–
Acknowledgements 2640.
[12] Lin, L. P.; Rong, M. C.; Luo, F.; Chen, D. M.; Wang, Y. R.;
This work was supported by the National Science
Chen, X. Luminescent graphene quantum dots as new
Foundation of China (Grand Nos. 51373065, 21221063,
fluorescent materials for environmental and biological
81320108011, 91123031), the National Basic Research
applications. TrAC Trends Anal. Chem. 2014, 54, 83–102.
Program of China (973 Program, Grant No. [13] Liu, S.; Tian, J. Q.; Wang, L.; Zhang, Y. W.; Qin, X. Y.;
2012CB933800), and the Specialized Research Fund Luo, Y. L.; Asiri, A. M.; Al-Youbi, A. O.; Sun, X. P.
for the Doctoral Program of Higher Education Hydrothermal treatment of grass: A low-cost, green route
(No. 20130061130010). to nitrogen-doped, carbon-rich, photoluminescent polymer
nanodots as an effective fluorescent sensing platform for
label-free detection of Cu(II) ions. Adv. Mater. 2012, 24,
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The Photoluminescence Mechanism in Carbon Dots (Graphene Quantum Dots, Carbon Nanodots, and Polymer Dots) : Current State and Future Perspective

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Nano Research 2015, 8(2): 355–381

The photoluminescence mechanism in carbon dots

Received: 9 September 2014 ABSTRACT

1 Introduction fluorescent carbon-based nanomaterials have been

Address correspondence to [email protected]

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scattering dominates over electron–phonon scattering. 5 PL mechanism of CNDs

5.2 Surface state in CNDs

Functional groups have various energy levels, which

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[19] Song, Y. B.; Zhu, S. J.; Yang, B. Bioimaging based on 2717–2720.

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