Carbon 175 (2021) 576e584

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Aggregation induced emission transformation of liquid and solid-state

N-doped graphene quantum dots
Derya Ozyurt a, b, *, Sunil Shafqat b, Tuula T. Pakkanen b, Rosalie K. Hocking a,
Adrian Mouritz c, Bronwyn Fox a
a
Faculty of Science, Engineering and Technology, Swinburne University of Technology, Hawthorn, VIC, 3122, Australia
b
Department of Chemistry, University of Eastern Finland, P.O. Box 111, FI-80101, Joensuu, Finland
c
School of Engineering, RMIT University, Melbourne, VIC, 3000, Australia

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

Article history: Aggregation induced photoluminescent quenching of graphene quantum dots (GQDs) is a well-known
Received 13 September 2020 effect, although there are limited reports of multicolour light emissions from such aggregates. In the
Received in revised form present work, we demonstrate a novel aggregation induced bathochromic shift in emission similar to J-
21 December 2020
aggregates observed in dye molecules. Nitrogen-doped graphene quantum dots (N-GQDs) prepared in
Accepted 9 January 2021
Available online 18 January 2021
the presence of diethylenetriamine show blue emission which is attributed to monomers at low con-
centration (58 mg/ml) while cyan (1.75 mg/ml), and greenish yellow (3.5 mg/ml) emissions are observed
at higher concentrations under 365 nm UV lamp. These materials for the first time show yellow and
Keywords:
Graphene quantum dots
orange emission from drop cast film of N-GQDs under 365 nm UV-light while the parent powder gives
Photoluminescence orange emission. The variety of emission colours that could be made simply by controlling the degree of
Aggregation aggregation presents exciting possibilities in a range of applications such as sensing, bioimaging, solar
Bathochromic shift harvesting and forensic science.
Multicolour emission © 2021 Elsevier Ltd. All rights reserved.
Solid state luminescence

1. Introduction dipole moments of individual monomers of J aggregates are aligned

Molecular self-assembly offers a novel approach for materials
design, and is inspired by many examples in nature such as the
nanophotonic structure on a morpho rhetenor butterfly [1,2]. Since
these ordered assemblies are such a universal theme, the physical
principles which govern the interactions in this size realm are not
only limited to nanostructures but also apply to molecules. Supra-
molecular chemistry has enabled the study of intriguing optical and
physical properties, including the ability to control light emission
through self-assembly and delocalization and coherence of excitons
[3]. These structures, which are formed through the aggregation of
monomers, were named after one of its discoverers Jelley and are so-
called ‘J-aggregates’, these are functional in plant pigments for light
harvesting. Fig. 1 illustrates bathrochromically shifted J aggregates on
the left and hypsochromically shifted H aggregates (H for hyp-
sochromic) on the right based on molecular exciton theory [4]. While
monomers of H aggregates stack in parallel (i.e. face-to-face), the
* Corresponding author. Faculty of Science, Engineering and Technology, Swin-
burne University of Technology, Hawthorn, VIC, 3122, Australia.
E-mail address: dozyurt@swin.edu.au (D. Ozyurt).
parallel to the centre of dipole moments (i.e. head-to-tail) and they
act as one being a molecular assembly with increased dipoles [5].
Interestingly, the fluorescence properties of J aggregates did not
attract significant attention as conventional applications did not
require fluorescence. However, photovoltaics, bioimaging, bio-
sensing, optoelectronics and nonlinear optics are growing applica-
tions. Recently, J aggregates have been observed by Chen et al. [6]
and Thiyagarga et al. [7] in graphene quantum dots (GQDs). How-
ever, J aggregates have not been used in the replacement of dyes,
even though they have potential longer distances of exciton coupling
due to their relatively long monomer units (>1 nm). This translates
to aggregates much larger than dye molecule aggregates and
potentially longer distances of exciton diffusion. GQDs are zero-
dimensional graphene derivatives with one or several layers of
graphene sheets with functionalities on the edges [8,9]. They are also
promising in optoelectronics, photovoltaics, bio-imaging, solar cells,
biosensors, electronic devices, photoluminescent materials, light
emitting diodes and other applications.
Colloidal semiconductor quantum dots (QDs) such as CdSe and
ZnS have size dependent electro-optical properties, although there
is concern with their potential toxicity due to the heavy metals (e.g.

https://doi.org/10.1016/j.carbon.2021.01.026
0008-6223/© 2021 Elsevier Ltd. All rights reserved.
D. Ozyurt, S. Shafqat, T.T. Pakkanen et al.
Fig. 1. Schematic representation of ideal red shifted J and blue shifted H aggregates based on molecular exciton theory. (A colour version of this figure can be viewed online.)
Cd). Moreover, their high market cost limits their use in industry
(thousands of US dollars per gram) [10]. In comparison, GQDs have
a low cytotoxicity, high water solubility, good grafting ability, stable
photoluminescence and low production cost, and are a promising
new class of QDs to replace inorganic QDs in some applications
[11,12]. Unlike dye molecules, GQDs are chemically and thermally
stable, and are resistant to photobleaching. Moreover, GQDs can be
grafted to control their self-assembly and thus the properties of
their aggregates [13] and their aggregation seems to be affected by
outer factors i.e. pH, just like in the case of dye molecules [6].
Herein, Nitrogen-doped graphene quantum dots (N-GQDs) were
synthesized using an one-pot solvothermal method reported by Qu
et al. [14]. Predominantly aggregation induced photoluminescence
quenching of GQDs has been reported [15,16]. Unlike one colour
green emission reported by Qu et al. [14], in the present study
aggregation induced tunable multicolour PL emissions have been
observed by simply changing the concentration of N-GQDs. The
emission of N-GQDs extended from blue (NB-GQDs, 58 mg/ml) to
cyan (NC-GQDs, 1.75 mg/ml) and greenish yellow (NG-GQDs,
3.5 mg/ml) with increasing concentration. Special focus was placed
on the aggregation effect on color emissions which lead us to draw
comparisons between J aggregates in dye molecules and the ag-
gregates of N-GQDs. Different concentrations of N-GQDs were
studied via PL emission, PL excitation, and UVevis spectroscopy to
get insight into the nature of aggregation dependent emission by
altering the concentration of the solutions. In addition, we draw
attention to solid-state luminescence and concentration dependent
emission change in drop cast samples of N-GQDs for their possible
applications. J aggregates with long-distance exciton coupling can
be useful in photonic devices and coupled with absorption in visible
region, they can also be used in energy conversion. Moreover, GQDs
with the longer distance exciton coupling, thermal stability, and
resistance to photobleaching are candidates to replace dyes.
2. Materials and experimental methodology
2.1. Materials
Citric acid monohydrate (Sigma Aldrich), diethylenetriamine
(DETA, Sigma Aldrich), dimethylformamide (DMF AR, Chem-
Supply), petroleum ether (AR Chem-Supply), ethyl acetate (AR
Chem-Supply), were used as received. Deionized water obtained
through a Milli-Q ultra-pure water system was used in all
experiments.
2.2. Synthesis of N-GQDs
N-GQDs were synthesized in an autoclave using the one-pot
solvothermal method following the procedure described by Dan
577
Carbon 175 (2021) 576e584
et al. [14] To summarise, 6 mmol citric acid was mixed with
18 mmol DETA and 30 ml DMF in an autoclave under continuous
stirring at room temperature until the solution became clear. The
sealed autoclave was then placed into an oven at 180
C for ~6 h.
The autoclave was cooled to room temperature, and the solution
was observed to have changed from clear to brown. This solution
was mixed with petroleum ether and ethyl acetate (~60  1/4 pe-
troleum ether/ethyl acetate), and the resulting precipitate sepa-
rated by centrifugation. Precipitates were collected and redispersed
in water, from which solid particles were extracted by drying.
2.3. Characterization of N-GQDs
Transmission electron microscopy (TEM) images were obtained
using a JEOL 1010 operated at a beam voltage of 100 kV. Atomic Force
Microscopy (AFM) measurement was performed using Bruker multi-
mode 8. X-ray diffraction (XRD) was conducted with Bruker
Advanced D8 in the 2q range of 10-80
with a step size 0.01
using Cu
Ka (l ¼ 0.154 nm) radiation. Raman spectra were measured at room
temperature using a Renishaw Invia Raman microscope with 785 nm
laser excitation. X-ray photoelectron spectroscopy (XPS) was per-
formed using a Kratos AXIS NOVA spectrometer (Kratos Analytical,
Inc., Manchester, UK), and the data was analyzed using CASAXPS
processing software. Fourier transform infrared (FTIR) spectra were
recorded using a Thermo Scientific Nicolet iS5 spectrometer. 13C and
1
H nuclear magnetic resonance spectroscopy (NMR) were measured
using a Bruker Avance 400 MHz NMR spectrometer at 25 ± 0.1
C.
The samples were prepared by dissolving the N-GQD in deuterated
D2O within a 5 mm NMR tube. The NMR data was processed using
MestreNova software. The optical properties were determined using
ultravioletevisible (UVevis) spectroscopy with a Shimadzu UV-2450
spectrophotometer in the range of 200  l  800 nm using 2 mm
path length cuvette and photoluminescence (PL) spectroscopy was
performed using a Cary Eclipse Fluorescence Spectrophotometer.
The absolute quantum yield (QY) was measured using an integrating
sphere connected to FL900 (Edinburgh instruments Ltd., U.K), with
1 mm path length cuvette. The uncertainty in the QY values is about
±5%, and QY values of around 5% or lower indicates no appreciable
emission. QY values are calculated for emission starting þ15 nm
from lex to avoid including the excitation scatter peak, which may
result in slightly lowering of the QY value at lex ¼ 420 and 460 nm.
3. Results and discussion
3.1. Characterization and optical properties of N-GQDs
Several studies have demonstrated that hydrothermal process-
ing methods usually result in the production of blue luminescent
GQDs [17e19]. However, there are many phenomena that can
D. Ozyurt, S. Shafqat, T.T. Pakkanen et al.
influence the photoluminescence of GQDs; including the solvent
type, conjugation length and nitrogen content [17e19]. Citric acid is
a low cost and readily available starting material for the preparation
of GQDs. In this work, N-GQDs were prepared using citric acid as
carbon source, DETA as carbon and nitrogen source, and DMF as the
solvent using the one-pot solvothermal method described by Qu
et al. [14] and explained in the experimental section. The reaction
yield of N-GQDs was 41% which was calculated based on the mass
of the reactants used i.e. CA and DETA, and the mass of the solid N-
GQDs obtained as a product. The following steps describe the for-
mation mechanism of N-GQDs; (i) amide bond forms between
DETA and CA under solvothermal condition [17,20], (ii) citric acid
amide further self-assembles and polymerises via dehydration and
deamination to grow into graphitic structures [21], (iii) moreover,
pyrrolic N is formed via intramolecular dehydration reaction be-
tween amide and eCOOH groups, which can be further trans-
formed to graphite N [17,20]. Unlike water, DMF as polar aprotic
solvent without having ability to donate proton leads greater
dehydration reaction of citric acid through inter and intramolecular
interactions resulting in less carboxylic acid groups on the surface
of GQDs [14].
It has been reported by Zhu et al. [22] that the quantum yield
(QY) in GQDs depends on the degree and type of surface func-
tionalization; with functionalised amine groups resulting in a
higher quantum yield than oxygen-bearing functional groups. The
formation mechanism of GQDs from citric acid follows polymeri-
zation at low temperature and then carbonization at higher tem-
perature. Photoluminescence at the polymer-like stage is due to the
surface/molecule state and amide containing fluorophores. How-
ever, photoluminescence following high temperature treatment
arises from the carbogenic core and the surface/molecule state due
to the carbonization [22]. Unlike green luminescence reported by
Qu et al. [14], here the synthesized N-GQDs when dispersed in
water are colourless under white light (400e700 nm) and emit
several photoluminescent colours (i.e. blue, cyan and greenish-
yellow) under 365 nm UV-lamp, depending on their concentra-
tion in the solution. Fig. 2a and d present TEM images of the syn-
thesized N-GQDs and their aggregates, respectively. The N-GQDs,
when fully dispersed, ranged in size from ~3.4 to 6.6 nm (Fig. 2a).
Fig. 2b shows the particle size distribution of N-GQDs with the
Gaussian fitting curve which is similar to literature [17,23,24].
Statistical analysis was performed on more than 100 particles using
ImageJ software, and the average diameter of N-GQDs was
measured to be ~4.9 nm. The atomic force microscopy (AFM) image
revealed that the typical topographic height of N-GQDs is in the
range of 0.6e2 nm with the average height of 1.3 nm (Fig. 2c)
indicative of 1e5 graphene layers N-GQDs [17,25,26]. Fig. 2d shows
the aggregation of N-GQDs, which is believed to form by self-
assembly of the monomers through J aggregation.
XRD was conducted to characterise the sp2 crystalline graphitic
structure of the synthesized N-GQDs, and the diffractogram is
shown in Fig. 3a. The peaks at 2q z 27.5
and 2q z 40-50
corre-
spond to the graphite (002) planes, which provides strong evidence
for a graphitic structure, and combined (100) and (101) planes,
respectively. The interlayer distance (d) of N-GQDs was calculated
to be 3.24 Å, which is slightly less than the value for graphite
(3.40 Å) [14,27]. The XRD result of N-GQDs is compared in Fig. 3b to
that of nitrogen doped graphene (NG) and graphene oxide (GO)
measured by Li et al. [28] The diffraction peak at 27.5
for N-GQD is
higher than that of NG at 26
, which is indicative of the formation of
a graphitic network with a more compact interlayer spacing via
carbonization of citric acid compared to NG [29]. In addition, the N-
GQDs do not display a diffraction peak in the region of 10-20
,
which exists with GO. The broader XRD peak of the N-GQDs can be
attributed to the disordered structure due to the presence of
578
Carbon 175 (2021) 576e584
oxygen- and nitrogen-bearing functional groups. In addition, the
weak reflection peak at 2q z 40e50
indicates crystalline disorder
due to defects and oxygen- and nitrogen-functional groups formed
in the basal plane during synthesis of the N-GQDs [27,30e33].
Raman spectroscopy of N-GQDs revealed two peaks at 1318 and
1593 cm1, which correspond respectively to disordered D and
crystalline G bands, as shown in Fig. 3c. The disordered D band
corresponds to defects originating from sp3 hybridized carbon
atoms in the graphitic network and the crystalline G band origi-
nates from the E2g mode of graphite and sp2 vibrations [34,35]. A
small peak around 1497 cm1 might be attributed to D** band
which has been found in disordered carbons [36] and it can be the
result of phonon density of states in graphitic crystals or CeH vi-
brations [37]. The intensity ratio (ID/IG) provides a measure of
relative proportions of disorder and order in a crystalline structure
[38]. The ID/IG ratio of N-GQDs is 1.82 that indicates amorphous
content created by defects at the edges or on the surface [7,39]. It
should be noted that the PL quantum yield (QY) depends on surface
functionalization, and the presence of nitrogen is known to in-
crease the QY when compared with GQDs that only contain
oxygen-bearing functional groups [22]. Gu et al. reported that ni-
trogen (N) atoms in the lattice results in disappearance of the G
band in Raman spectra due to the high QY [38]. In our research,
Raman spectra only showed the D band when measurements of the
N-GQDs were conducted without a quenching agent. However, D
and G bands were detected when N-GQDs were quenched with
Fe3þ, and this suggests the suppression of G band with high fluo-
rescence background in Raman analysis.
1
H and 13C nuclear magnetic resonance spectroscopy (NMR) was
performed to distinguish sp2 and sp3 hybridized carbon atoms and
possible functionalities in N-GQDs. The 1H NMR spectrum of N-
GQDs is presented in Fig. S1a, and the signals at 1e2 ppm represent
aliphatic hydrogens and the peaks between 2 and 4 ppm may
correspond to chemical groups such as HeO, CHeN, NeH, OeH.
The large resonance at 4.8 ppm is due to the OeH group, which is
most probably from D2O. The signals in the range of 5e6 ppm can
be assigned to OeH groups (Ar-OH) and alkenes and the peaks at
7e8.5 ppm to aromatic ring hydrogens [22,40]. The sp2 and sp3
hybridization of N-GQDs were distinguished in the 1H NMR spec-
trum. The 13C NMR spectrum of N-GQDs in D2O solvent gives
additional information about the sp2 hybridized carbon network, as
seen in Fig. S1b. The peaks from 20 to 85 ppm correspond to
aliphatic sp3 hybridized C atoms, with CeC, CeO, CeN between 25
and 50 ppm. The signals between 100 and 180 ppm can be assigned
to sp2 hybridized carbon atoms and the peaks in the range of
160e180 ppm can be assigned to carboxyl/amide groups [22,41].
FTIR and XPS measurements were conducted to determine the
functionalities, elemental and surface composition of N-GQDs. Fig. S2
shows the FTIR spectra of citric acid and synthesized N-GQDs. The
peak at ~3400 cm1 corresponds to stretching vibration of OeH
while the peak at 3269 cm1 corresponds to NeH stretching vibra-
tion. Hydrophilicity and stability of GQDs in aqueous solutions are
improved via these functionalities [14,42]. The peaks at 3061, 2939,
and >2800 cm1 correspond to stretching vibration of sp2 CeH (C]
CeH) in aromatic rings, stretching vibrations of H-Csp3 (-CH3) and H-
Csp2 (-CH2), respectively [14]. The shoulder peak above 1646 cm1
can be assigned to C]O in the carboxylic acid groups. However,
there is no clear peak over 1646 cm1 which might be evidence of
reaction of eCOOH groups through the formation an amide bond
between eNH2 and eCOOH in the presence of amine in the sol-
vothermal reaction [21]. Peaks at 1646 cm1 and 1534 cm1 can be
assigned to C]O in amide (CONH) vibrational absorption band [42]
and skeletal vibration of aromatic rings C]C bending [43], respec-
tively. As shown in Fig. S2, these peaks show a shift compared to the
peaks of pure citric acid monohydrate which is the evidence of
D. Ozyurt, S. Shafqat, T.T. Pakkanen et al. Carbon 175 (2021) 576e584

Fig. 2. a) TEM image of dispersed N-GQDs in dilute solution b) a particle size distribution histogram of N-GQDs obtained from TEM c) The AFM image of N-GQDs with insets
corresponding to height profile of N-GQDs and d) TEM image of aggregates of N-GQDs in a concentrated solution. (A colour version of this figure can be viewed online.)

Fig. 3. a) XRD diffractogram of synthesized N-GQDs with graphite (002) planes and combined (100) and (101) diffraction planes due to plane disorder b) XRD-spectra of N-doped
graphene (NG) and graphene oxide (GO) [28] (Copyright 2014, RSC Advances) c) Raman spectrum of N-GQDs showing disordered D and crystalline G bands. (A colour version of this
figure can be viewed online.)

formation of N-GQDs and amide bonding [42]. Aryl C]C stretching
was detected at 1437 cm1[44] and the peak at 1384 cm1 is
attributed to CeH vibration. Peaks at 2939 and >2800 cm1 indicate
incomplete carbonization.
X-ray photoelectron spectroscopy (XPS) was conducted to
further investigate the chemical composition of N-GQDs, with C1s,
N1s, and O1s peaks detected in the full spectra (Fig. 4a). The high
resolution C1s XPS spectra (Fig. 4b) was well fit by four Gaussian
peaks at 284.6, 285.8, 287.5, and 289.1 eV which correspond
respectively to graphitic sp2 C (CeC, C]C), sp3 carbon C (CeC, CeO
and CeN), carbonyl (C]O), and carboxylate C (O)eO functionalities
[14,45]. The nitrogen peak is evidence of successful nitrogen doping
in the synthesis of N-GQDs. The high resolution N1s XPS spectra
(Fig. 4c) were deconvoluted into three peaks at 398.5, 399.7, and
579
401.1 eV which correspond to pyridinic-N, pyrrolic-N, and
graphitic-N, respectively [46]. Pyrrolic N, which dominates the CeN
configuration, is formed by dehydrolysis of neighbouring carboxyl
and amide groups. Next dominating CeN configuration is graphitic-
N, which is bound to three neighbouring C atoms and is stable in
the high temperature synthesis [17,46]. The O1s XPS spectra
(Fig. 4d) were deconvoluted into three peaks at 530.9, 532.0, and
533.2 eV, which correspond to C]O of quinone, C]O of carbonyl,
and CeOH/CeOeC. C]O of quinone is formed via dehydrolysis of
adjacent carboxyl groups.
3.2. Optical properties of N-GQDs
The optical properties of N-GQDs in solution were measured
D. Ozyurt, S. Shafqat, T.T. Pakkanen et al. Carbon 175 (2021) 576e584

Fig. 4. a) Full-scan XPS spectra of N-GQDs b) high resolution C1s spectra of N-GQDs c) high resolution N1s spectra of N-GQDs and d) high resolution O1s spectra of N-GQDs. (A
colour version of this figure can be viewed online.)

using UVevis and PL spectroscopy. The absorption intensity in-

creases linearly with increasing concentration (Fig. 5) [47]. Two
absorption bands at ~240 nm and ~355e360 nm were detected in
the UVevis spectra of N-GQDs (Fig. 5). The absorption band at
~240 nm represents p/p* electron transition in the molecular
orbital of aromatic sp2 hybridized C]C domains of N-GQDs and the
broad band at ~360 nm corresponds to n/p* electron transition in
the molecular orbital of the functional groups, which can be
considered as defects. The 360 nm band is created mainly by oxy-
gen containing functionalities such as C]O, eCOOH and CeOH
[48]. The 360 nm band can also be due to nitrogen doping or
transition of conjugated CeN/C]N [14,49].
GQDs with p conjugation usually have p-p interactions, which
lead to p-p stacking and photoluminescent quenching with the
increasing concentration. However, here an unusual photo-
luminescent colour change due to the aggregation was observed
since functionalities at the edges and introduction of defects might
restrict p-p molecular interactions. This leads to head to tail
arrangement of monomers called J aggregation instead of face to
face stacking in case of H aggregation. J aggregation can be induced
by increasing concentration and it results in color change and red
shift in excitation and emission spectra [47]. Fig. S3 shows con- Fig. 5. UVevis absorption spectra of N-GQDs at various concentrations from 0.029 mg/
centration dependent luminescence of N-GQDs when excited by mL to 3.5 mg/mL. Shown in the inset is LamberteBeer’s plot for the absorption at 359
365 nm UV light. The emission colour changes from blue (NB-GQDs, and 290 nm. (A colour version of this figure can be viewed online.)
58 mg/ml) to cyan (NC-GQDs, 1.75 mg/ml) and to yellowish green
(NG-GQDs, 3.5 mg/ml) with increasing concentration of N-GQDs
solution that is further investigated using PL spectroscopy. The wavelengths (lex): Fig. 7a shows maximum emission and corre-
schematic of possible J aggregation process of N-GQDs is presented sponding excitation spectra of NB-GQDs. The PL excitation spectra
in Fig. 6. shows two peaks centred at ~244 and 356 nm, and correspond to
PL excitation spectra at maximum emission and PL emission two transitions of p/p* and n/p* at corresponding wavelengths
spectra of NB-GQDs (blue, 58 mg/ml) at different excitation [50]. The lower wavelength excitation peak at ~244 nm corre-
sponds to the carbogenic core (C-band) and the higher peak at

580
D. Ozyurt, S. Shafqat, T.T. Pakkanen et al.
~356 nm is due to surface states or defects (S-band). Both excitation
peaks have similar intensities and influence on the maximum
emission of NB-GQDs (461 nm), which was supported by PL exci-
tation spectroscopy at different emission wavelengths (Fig. S4).
However, the first excitation peak (C-band) with a higher intensity
should be considered as the main excitation wavelength for the
maximum emission, even though both have a role in PL emission of
NB-GQDs. Fig. 7b shows the PL emission spectra of NB-GQDs at
lex ¼ 280e440 nm. The emission peaks were centred at ~461 nm
with no shift at different excitation wavelengths. The emission
wavelength of carbon-based fluorescence materials usually de-
pends on the excitation wavelength, with the PL emission peaks red
shift with the maximum intensity at the increasing excitation
wavelength [51]. However, NB-GQDs displayed excitation inde-
pendent PL emission, and this is an indication of the uniform size
and surface state of sp2 domains [14].
PL excitation spectra at maximum emission and PL emission
spectra of NC-GQDs (cyan, 1.75 mg/ml) at different lex: Fig. 7c
shows the maximum emission and corresponding excitation
spectra of NC-GQDs. In comparison to NB-GQDs, NC-GQDs gave a
lower intensity, red shifted split C-band (from 244 nm to 278 and
316 nm), and red shifted S-band (424 nm), which are assigned to
the core and surface states, respectively [52]. The dominant PL
excitation peak at 424 nm (S-band), which is due to the activation
of surface states through the formation of aggregates at higher
concentration, can be considered as the excitation wavelength for
the maximum PL emission. The red shift can be attributed to the
increased interactions between monomers in larger aggregates that
occur at higher concentration. The primary synthesized monomers
range in size from ~3.4 to 6.6 nm. Larger monomers aggregate more
with increasing concentration in comparison to the smaller
monomers partitioning the population into two different size dis-
tributions; one mainly contains small monomers and the second
mainly contains large aggregates causing a split in the C-band and
red shift due to aggregation (Fig. 7c and S4c). This is further
confirmed in the comparison of the total emission intensity of the
N-GQDs, where two emission domains at lex ¼ 280e400 nm and
lex ¼ 400e520 nm of the NC-GQDs can be assigned to monomers
and aggregates respectively (Fig. S5).
The PL emission spectra show both excitation independent
Fig. 6. The schematic of N-GQDs at low, medium, and high concentration. Left: monomers at low concentration; middle: J aggregates together with monomers at medium
concentration; right: Higher degree of J aggregates at high concentration. Magnified areas show the head to tail arrangement of monomers in the aggregates. (A colour version of
this figure can be viewed online.)
581
Carbon 175 (2021) 576e584
emission at lex ¼ 280e400 nm from monomers, and excitation
dependent emission with red shift at lex  400 nm from aggregates
(Fig. 7d) [6]. The maximum emission red shifted from 461 to
481 nm compared to NB-GQDs that is indication of J aggregation.
The integration of the emission peaks show that the total emission
intensity of NC-GQDs is lower than that of NB-GQDs due to the
aggregation induced quenching from monomers (AIQ) and low
intensity emission from aggregates (Fig. S5). The intensity of the
emission at lex ¼ 280e400 nm, attributed to monomers, decreased
compared to the NB-GQDs, that is indicative of aggregation induced
quenching (AIQ) common to conventional CDs [53]. However, the
emergence of new peaks with red shift at lex ¼ 400e520 nm can be
attributed to aggregation induced emission (AIE) (Fig. S5). Thus,
aggregation induced quenching (AIQ) together with aggregation
induced emission (AIE) were observed in NC-GQDs and these ob-
servations show the adjustable PL with increasing concentration
[54].
PL excitation spectra at maximum emission and PL emission
spectra of NG-GQDs (greenish yellow, 3.5 mg/ml) at different lex:
Fig. 7e shows the maximum emission and corresponding excitation
spectra of NG-GQDs. The intensity of the C-band showed a further
decrease compared to the NC-GQDs, and the dominant S-band at
lex ¼ 471 nm can be considered as excitation for maximum emis-
sion at 514 nm. The PL emission spectra of NG-GQDs at different lex
are presented in Fig. 7f.
The total emission intensity at lex ¼ 280e400 nm from mono-
mers further decreased while the total emission intensity at
lex ¼ 420e540 nm from aggregates were higher compared to those
of NC-GQDs (Fig. S5b). The PL emission peaks showed no red shift at
lex ¼ 280e400 nm, while there was a red shift at >400 nm exci-
tation wavelengths. However, inner filter effect (IFE) is due to the
absorption of the emitted light by other particles in solution and
may also contribute to the red shift in emission and excitation
spectra [55]. The asymmetric excitation-emission matrix of NG-
GQDs implies the existence of IFE, while there is no substantial IFE
in NB-GQDs and NC-GQDs (Fig. S6) [56]. This is further confirmed by
analyzing individual emission spectra as described in SI for
lex ¼ 420 nm (Fig. S7). These results clearly show that both ag-
gregation and IFE have influence on the red shift in emission at
lex ¼ 420e540 nm in NG-GQDs. The lower intensity of the emission
D. Ozyurt, S. Shafqat, T.T. Pakkanen et al.
Fig. 7. a, c, e) Maximum PL emission and corresponding excitation spectra of NB-GQDs, NC-GQDs, and NG-GQDs with increasing concentration, respectively. b, d, f) PL emission
spectra of NB-GQDs, NC-GQDs, and NG-GQDs at different excitation wavelengths with increasing concentration, respectively. (A colour version of this figure can be viewed online.)
peaks at lex ¼ 280e400 nm and higher intensity of the emission
peaks at lex ¼ 420e540 nm compared to NC-GQDs support the
higher degree of AIQ and AIE together with IFE, respectively [54].
The absolute PL quantum yield (QY) of NB-GQDs, NC-GQDs, and
NG-GQDs was measured at 360, 420, and 460 nm excitation
wavelengths (Table S1) to give decreasing QY with increasing
excitation wavelength. NB-GQDs have 39% QY at lex ¼ 360 nm with
negligible QY at lex ¼ 420 and 460 nm and the QY at lex ¼ 360 nm
decreases from 39% to 24% with increasing concentration. NC-GQDs
show higher QY of 17% than that of NB-GQDs and NG-GQDs at
lex ¼ 420 nm, while NG-GQDs exhibit higher QY of 10% at
lex ¼ 460 nm compared to that of NB-GQDs and NC-GQDs. The
reduction in QY at lex ¼ 360 nm with increasing concentration can
be attributed to AIQ at lower emission wavelengths. However, the
17% QY at lex ¼ 420 nm for NC-GQDs, and 10% QY at lex ¼ 460 nm for
NG-GQDs can be considered as AIE and emission red shift with
increasing concentration.
PL excitation spectra at different emission wavelengths (lem):
PL excitation spectra of N-GQDs with different lem were measured
to identify the origin of the excitation dependent emission. Fig. S4
shows PL excitation and normalized PL excitation spectra corre-
sponding to NB-GQDs, NC-GQDs and NG-GQDs. No shifts in S- and C-
bands were observed for NB-GQDs, in the PL excitation (Fig. S4a) or
normalized PL excitation spectra (Fig. S4b). However, while there
was no shift to the C-band, a slight shift was detected in the S-band
in NC-GQDs (Fig. S4c, d). This indicates the effect of different surface
states on the excitation dependent emission in NC-GQDs [7]. Also,
the decrease of C-band intensity compared to the S-band in the PL
excitation spectra with increasing concentration from 58 mg/ml
(NB-GQDs) to 1.75 mg/ml (NC-GQDs) is the indication of quenching
of emission due to the carbogenic core, which is the result of the
activation of different surface states via interactions between
monomers or particles. Further decrease in intensity of the C-band
compared to the S-band and higher red shift at the S-band with
further increase of concentration from 1.75 mg/ml (NC-GQDs) to
582
Carbon 175 (2021) 576e584
3.5 mg/ml (NG-GQDs) can be attributed to the coexistence of higher
degree of aggregation and IFE as explained in detail above (Fig. S4e,
f).
Aggregation effect on luminescence of N-GQDs was further
investigated by solid state fluorescence spectroscopy. Aggregation-
caused quenching (ACQ) is a well-known phenomenon in solid
state through direct p-p stacking interactions similar to organic
molecules and it is generally prevented by dispersing particles into
polymer matrices blocking the direct contact between monomers
[57,58]. Nevertheless, synthesized N-GQDs in solid state appear
brown under day light and emit orange luminescence under
365 nm UV-light without incorporation into a matrix as shown in
Fig. 8 a, b. Drop-cast N-GQDs were also examined under 365 nm
UV-light, and they showed colour change from yellow to orange
with the increasing concentration due to aggregation. Even though
solid-state luminescence has been previously reported, to our
knowledge Fig. 8 shows the first reported results of aggregation
induced solid-state colour change in N-GQDs [35]. Emission spectra
of drop cast N-GQDs (orange) was measured at lex ¼ 490 nm and
emission was centred at ~ 600 nm (Fig. S8).The continuity of the red
shift in emission spectra with increasing concentration in solution
up to solid state suggests higher degree of aggregation.
4. Conclusions
N-GQDs were synthesized using the one-pot solvothermal
method [14], which in solution exhibit bright blue PL. At higher
concentrations, the N-GQDs show extensive aggregation-induced
multicolour PL emission that is tuneable by simply varying the
concentration. The red shift in the maximum PL excitation band
from 356 nm to 424 nm and further to 471 nm with increasing
concentration (NB-GQDs to NC-GQDs and NG-GQDs) is an indication
of activation of different surface states and higher degree of ag-
gregation. This was also supported by the corresponding suppres-
sion of the C band and the red shift in maximum PL emission band
D. Ozyurt, S. Shafqat, T.T. Pakkanen et al.
Fig. 8. N-GQDs particles a) under day light and b) under 365 nm UV light. Low concentration drop cast N-GQDs c) under day light and d) under 365 nm UV-light. Higher con-
centration drop cast N-GQDs together with low concentration drop cast N-GQDs e) under day light and f) under 365 nm UV light. (A colour version of this figure can be viewed
online.)
from 461 to 481 and then to 514 nm at progressively higher
concentrations.
The aggregation resulted in two PL process; AIQ of the monomers
in the blue region, and AIE due to aggregates at higher wavelengths.
This has resulted in 53% and 51% reduction of the total emission
intensity in NC-GQDs and NG-GQDs, while the emission from
monomers in the blue region reduced to 8% and 6% of the NB-GQDs
(NB-GQDs produces only well dispersed monomers). The IFE was
also observed at high concentration in NG-GQDs that resulted in
asymmetry in the emission spectra. The red shift in emission and
excitation spectra is attributed to aggregation in NC-GQDs while
aggregation together with IFE is responsible for the red shift in NG-
GQDs. This has been further confirmed by the QY values measured at
lex ¼ 360, 420 and 480 nm. NB-GQDs gave QY of 39% at lex ¼ 360 nm
while NC-GQDs and NG-GQDs gave QY of 17% at lex ¼ 420 nm and
10% at lex ¼ 460 nm, respectively.
In addition, N-GQDs in the powder form emits orange lumi-
nescence and emission of drop cast samples shift from yellow to
orange under 365 nm UV light with increasing concentration.
Therefore, tailoring the emission colours as a function of concen-
tration could be useful in many applications such as sensors, solar
harvesting and bioimaging. Solid-state and drop-cast luminescence
have potential applications in multiple fields, including forensic
science, tracing analysis and diodes.
CRediT authorship contribution statement
Derya Ozyurt: Conceptualization, Methodology, Investigation,
Data curation, Writing - original draft. Sunil Shafqat: Writing -
review & editing. Tuula T. Pakkanen: Writing - review & editing.
Rosalie K. Hocking: Supervision, (Co-Supervisor), Spectroscopy
advice and, Writing - review & editing. Adrian Mouritz: Writing -
review & editing. Bronwyn Fox: Supervision, (Principal Supervi-
sor), Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
The authors gratefully acknowledge the RMIT Microscopy and
Microanalysis Facility (RMMF) for TEM access. The authors would
like to express appreciation to Dr Andrew Scully of CSIRO for QY
measurements and expert advice. The authors also acknowledge Dr
Jonathan Tollerud for solid state PL spectroscopy measurement. We
are thankful to Dr Karyn Jarvis for help with the XPS data analysis
using CASAXPS processing software. Lastly, we thank to Nishar
Hameed for his contributions to the very early stages of this research.
583
Carbon 175 (2021) 576e584
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2021.01.026.
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