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Facile synthesis and optical properties of

nitrogen-doped carbon dots†
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Cite this: New J. Chem., 2014,

38, 1522
Jingjing Niu,‡ab Hui Gao,‡*a Litao Wang,c Shuangyu Xin,a GangYi Zhang,a
Qian Wang,a Linna Guo,a Wenjing Liu,a Xiuping Gaoa and Yuhua Wanga

Received (in Montpellier, France)
8th September 2013,
Accepted 10th December 2013
DOI: 10.1039/c3nj01068f
www.rsc.org/njc
Among the chemical doping elements, nitrogen atoms play a critical role in tuning the intrinsic
properties or exploiting new phenomena of carbonaceous materials. Herein, we report a facile strategy
to synthesize nitrogen-doped carbon dots (NCDs) using glutamic acid as the precursor via a one-step
thermal conversion process. The as-produced NCDs exhibit bright blue photoluminescence (the
quantum yield of ca. 23.2%), and the emission wavelength could be slightly tuned through changing the
parameters of the synthesizing process. Interestingly, apart from their superior luminescence characters,
unexpected cathodoluminescence (CL) and frequency upconverted emission properties were both
observed in the NCDs.

1. Introduction properties, including low cytotoxicity, resistance to photo-

Nitrogen-doped carbon nanostructures (carbon nanotubes, gra-
phene, nanodiamonds and nanomaterials etc.) have attracted
increasing attention because of their wide potential applications
in biosensing, electronics, supercapacitors and electrocatalysts.1–4
Nitrogen (N) is considered to be an excellent chemical doping
element for tailoring the electronic properties of carbonaceous
nanomaterials due to its comparable atomic size and strong
valence bonds with carbon atoms. The presence of the additional
lone pairs of electrons and the commonly introducing defects
sites from N doping would also provide possible active sites and
modify the local chemical activities of carbon nanostructures.2,5–8
Recently, fluorescent carbon nanodots (CDs) or graphene
quantum dots (GQDs) have generated considerable excitement
for their favorable properties. GQDs are quantum-sized gra-
phene fragments (below 100 nm), which are primarily derived
from the cutting or exfoliation of graphene sheets.9 In compar-
ison, CDs are zero dimensional (0D) quasi-spherical carbon
nanoparticles with diameters less than 10 nm.9,10 As important
carbonaceous nanomaterials, these dots present extraordinary
a
School of Physical Science and Technology, Key Laboratory for Magnetism and
Magnetic Materials of Ministry of Education, Lanzhou University,
Lanzhou 730000, P. R. China. E-mail: hope@lzu.edu.cn; Fax: +81 931 8913554;
Tel: +81 931 8912772
b
Nano Structure and Low Dimensional Physics Laboratory, Peking University,
Beijing 100871, P. R. China
c
Key Laboratory of chemistry of Northwestern Plant Resources, Lanzhou Institute of
Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c3nj01068f
‡ These authors contribute equally to the article.
bleaching, chemical stability and excellent bioconjugate prop-
erties.11–15 For example, the N-doped GQDs show unique
optoelectronic features (such as the bright blue emission and
excellent upconversion photoluminescence (PL)) as well as
distinctive electrocatalytic activities for the oxygen reduction
reaction (ORR).8,16–18 Though electrochemical,8 hydrothermal16,18
and solution chemistry17 approaches have been reported to
successfully fabricate N-doped GQDs, the current methods
inevitably require special synthesis equipment and precursors
along with complex processes for introducing N into the lattice
of the GQDs. In comparison, CDs or doped CDs are much easier
to synthesize especially by bottom-up methods, such as thermal
decomposition,19,20 combustion10 and chemical oxidation,21
etc. These methods primarily benefit from simple fabricating
routes as well as cheap and abundant raw materials.22,23 Very
recently, the ultrasonic method24 and solvothermal route25
have been reported to successfully prepare N-doped CDs
(NCDs) using mixed materials (glucose + ammonia or CCl4 +
NaNH2) as precursors. Similar to N-doped GQDs, the as-
obtained NCDs show an attractive PL performance and efficient
photocatalytic properties.24 However, efficient ways for devel-
oping strong fluorescent CDs and avoiding the inhomogeneous
N doping derived from the mixed precursors are still highly
desirable.
Herein, we design a facile bottom-up approach for the
controllable synthesis of NCDs using glutamic acid (Glu) as
the precursor. By directly pyrolyzing and tuning the carboniza-
tion degree of Glu, the precursor is finally converted to NCDs,
which exhibit a bright blue emission with a high quantum yield
(ca. 23.2%) in a water solution of neutral pH. With a high
atomic percentage of N (ca. 9.9%), the obtained NCDs show

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excitation and reaction temperature dependent PL emission
activities. Most interestingly, the NCDs possess upconversion
PL properties (a red fluorescence was observed under a 980 nm
laser) and cathodoluminescence (CL) properties under electron
beam excitation. The simple method may provide a new strat-
egy for fabricating the NCDs with superior combined optical
properties (PL, upconversion PL and CL) and promote the
applications in addressing various bio-imaging and optoelec-
tronics applications.
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2. Experimental
2.1 The preparation of nitrogen-doped carbon dots
The NCDs were synthesized by directly pyrolyzing Glu (L-Glutamic
acid, A.R. 98%). In detail, 0.50 g Glu was put into a beaker and
then heated using a heating mantle (84-1 Magnetic stirring
temperature controlling electric heating sleeve). Glu was con-
verted to a pale yellow liquid when the temperature reached
150 1C. And the color of the liquid changed from yellow, golden
brown to brown at different temperatures of 165 1C, 180 1C and
200 1C, respectively. The liquid was cooled with violent stirring
and then diluted with deionized water (0.02 g ml 1). By control-
ling the temperature strictly and collecting the multicolor solution
at specifically periods, multicolor NCDs with varying sizes could
be obtained [Fig. S1 in the ESI†].
2.2 Sample characterization
The transmission electron microscopy (TEM) was examined
under an F-30 S-TWIN electron microscope (Tecnai G2, FEI
Company). X-ray photoelectron spectroscopy (XPS, PHI-5702,
Physical Electronics) was performed using a monochromated
Al-Ka irradiation. Raman spectroscopy was recorded using a
Fig. 1 (a) The XPS spectra of the as-produced NCDs, the XPS high-resolution C 1s (b) and N 1s (c) peaks of the NCDs, (d) the FT-IR spectrum and (e) the
Raman spectrum of the as-prepared NCDs.
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Renishaw InVia Raman microscope with 532 nm line of an Ar
ion laser as an excitation source. Fourier transform infra-red
spectra (FTIR) of the samples were recorded between 400 and
4000 cm 1 on a Nicolet NEXUS 670 FTIR spectrometer using
KBr pellets. The upconversion photoluminescence (PL) and PL
spectra of the NCDs in water were measured using a FLS-920T
fluorescence spectrophotometer equipped with a continuous
980 nm laser diode and a 450 W Xenon light source, respec-
tively, and the emissions were collected using a HORIBA JOBIN
YVON Fluorolog-3 Spectrofluorometer system. The diffuse
reflectance ultravioletvisible (UV-vis) absorption spectrum was
measured using a Perkin Elmer 950 spectrometer. The low-
voltage cathodoluminescence (CL) spectra were obtained using
a modified Mp-Micro-S instrument. The decay curve was
recorded on a PR305 phosphorophotometer. The absolute
quantum yield measurement was recorded using FLS920 photo-
luminescence spectrometers from Edinburgh instruments. The
UV light irradiation was a low-pressure Hg lamp with power 12 W.
All the measurements were performed at room temperature.
3. Results and discussion
The as-synthesized NCDs possess excellent solubility and
remain highly transparent in water and also in ethanol and
dimethyl formamide (DMF) (Fig. S2, ESI†). The XPS measure-
ments were performed to confirm the composition of the
resultant NCDs. As shown in Fig. 1a, the XPS survey spectrum
shows the dominant C 1s peak at ca. 284.5 eV, the N 1s peak at
ca. 399.9 eV and the O 1s peak at ca. 531.8 eV, and the atomic
percentage of N in the sample is ca. 9.9%, which is higher than
that of the NCDs prepared by the ultrasonic method (ca. 7.45%).24
The high-resolution spectrum of C 1s (Fig. 1b) can be fitted into
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four peaks at 284.5, 285.4, 286.4 and 288.5 eV, which would
respectively correspond to C–C, CQN (N–sp2 C), C–N (N–sp3 C)
and CQO bonds.24,25 The high-resolution XPS N 1s peak
(Fig. 1c) reveals the presence of pyrrolic-N (B399.9 eV) and
N–H (B401.1 eV) groups within the resultant carbonaceous
structure.25 The NCDs having signals of C 1s and N 1s remain
clearly distinguished from the starting material Glu (Fig. S3,
ESI†). The nitrogen concentration of all the samples has also
been checked, as shown in Fig. S4 (ESI†). The results indicate
that the N concentration becomes higher and then much lower
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with increasing the reaction temperature and the maximum
intensity can be obtained at 165 1C, which shows the highest
doping concentration with the N atomic percentage of ca. 9.9%.
The details of the reaction mechanism are still unclear, but it
seems that multiple reactions occurred simultaneously. For
example, the pyrrolic-like N could be obtained through the
intramolecular cyclization of Glu (as shown in Fig. S5, ESI†),
and the N and C atoms would be incorporated into the lattice of
the carbon dots in the carbonization process, simultaneously.
During the pyrolyzation and carbonization, oxygen-containing
functional groups (including C–O–C (1010 B 1106 cm 1), C–OH
(1240 cm 1) and CQO (1720 cm 1)) were introduced to the edges
and onto the basal plane of the NCDs, which make the NCDs
exhibit a high solubility in most hydrophilic solvents without
further chemical modifications. The characteristic absorption
band of N–H (3410 cm 1) and the aromatic C–N heterocycles
stretching vibrations at 1420 cm 1 can also be observed in Fig. 1d,
which is consistent with the above XPS analysis.25 Moreover, the
signal of the aromatic CQC stretching at 1610 to 1650 cm 1
indicates the presence of an sp2 hybridized honeycomb lattice.
The shape and peak positions of the FTIR spectrum of the NCDs
are quite different from that of Glu (Fig. S6, ESI†), implying the
corresponding change in the coordination environment of various
functional groups in the NCDs after the pyrolyzation. The Raman
spectrum of the NCDs is shown in Fig. 1e. The D and G peak can
be found at 1422 and 1627 cm 1, respectively. The obtained NCDs
have an ID/IG ratio of ca. 0.8, and the high intensity of the D peak
associated with the defects in the sp2 carbon lattice indicated the
high doping concentration of N into the carbon framework.
Fig. 2(a and b) shows a TEM image and the size distribution
of the NCDs. The average diameter of the as-prepared NCDs is
about 4 nm and mainly distributed in the range of 2.5–6 nm,
Fig. 2 (a) A TEM image of the as-prepared NCDs, (b) the diameter distribution of the NCDs, (c) a typical HRTEM image of an individual NCD.
1524 | New J. Chem., 2014, 38, 1522--1527 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014
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which is similar to that of the reported NCDs by the solvo-
thermal route,25 while smaller than that synthesized by the
ultrasonic reaction.24 Most of the NCDs are elliptical, and it is
believed that some dots would connect with each other to form
the larger-sized NCDs. Moreover, as the reaction temperature
rises, a slight increase in the size as well as a broadened and
uneven size distribution of the as-prepared NCDs can be
observed (as shown in Fig. S7, ESI†), which could be attributed
to the inhomogeneous process of the pyrolysis. The HRTEM
(Fig. 2c) image shows the high crystallinity of the NCDs, and the
lattice spacing of 0.303 nm is consistent with the (002) diffrac-
tion planes of graphite.25
The as-prepared NCDs exhibit the distinctive sp2 graphite
structure character, and the observed optical properties are
much similar to that of the reported N-GQDs or N-doped
carbon dots.9 As shown in Fig. 3a, the UV-Vis absorption
spectrum of the NCDs shows an absorption peak at ca. 324 nm,
which is associated with the n - p* transition of CQO.26 Fig. 3b
shows the PL emission spectra of NCDs (lex = 365 nm) obtained at
different temperatures (150, 165, 180 and 200 1C), and the
samples were marked as NC1, NC2, NC3 and NC4, separately.
The maximum emission intensity can be obtained for NC2, which
shows the intensive and stable blue PL emission with the PL
quantum yield as high as 23.2%. As a consequence of the best
photoluminescent emission intensity, NC2 was chosen for all the
characterized measurements. Though the shifts of the emission
maxima among NC1, NC2 and NC3 are inconspicuous, the
tunable brightness and the decreasing of the PL intensity can
be clearly observed with increasing the reaction temperature. The
corresponding optical images of the four NCDs under UV light are
shown in the inset of Fig. 3b. According to the recently reported
NCDs,27 the intensities of the resultant multicolor emission were
demonstrated to be N-content-dependent, whereas the position of
the emission-peak was size-dependent. Therefore, as a con-
sequence of the experimental results and the analyses of XPS
and TEM, we believed that the PL shift of the NCDs obtained at
different temperatures would originate from the contribution of
differently sized NCDs during the nanocrystal growth28–30 and the
surface defects derived from the N doping.25,27,31 For further
exploring their PL properties, different excitation wavelengths
were used to investigate the PL emission of the NCDs, as shown
in Fig. 3c. Like most of the CDs,19,32–34 the as-prepared NCDs

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Fig. 3 The PL properties of the NCDs in water. (a) The UV-Vis spectrum of
the NCDs, (b) the PL spectra of the NCDs excited at 365 nm with different
heating temperatures corresponding to the inset of b (Inset of (b): an
optical photograph of the NCDs dispersed in water under 365 nm irradia-
tion, NC1, NC2, NC3 and NC4 correspond to the synthesized reaction
temperature at 150, 165, 180 and 200 1C, respectively.), (c) the PL spectra
of NC2 under different excitation wavelengths, (d) the PL spectra of the
NCDs solution with different PH conditions under 365 nm excitation, (e)
the PLE spectrum with the detection wavelength of 450 nm, (f) the typical
luminescence decay curve for the UV emission measured at room
temperature.
exhibit an excitation dependent PL behavior. The PL emission
peaks shift from 443 nm to 457 nm as they were excited from
340 nm to 380 nm, suggesting a superposition of different types of
fluorescent species.34 The maximum emission intensity could be
obtained when excited at 365 nm, and the full width at a half
maximum is around 95 nm, which is attributed to the broad size
distribution as well as the N-doping of the prepared NCDs.32 In
addition, the NCDs exhibit a bright PL emission in a water
solution of neutral pH, and the intensity of the emission peaks
decrease both in acidic and alkaline conditions (Fig. 3d).
The PL excitation (PLE) spectrum recorded with the stron-
gest luminescence (450 nm) shows two peaks at 297 and
365 nm, respectively (Fig. 3e). The PLE spectrum clearly con-
firms that the luminescence from the NCDs would be corre-
lated with the two transitions at 297 and 365 nm. According to
the PL mechanism for the N-GQDs,16 it is believed that the two
electronic transitions of 297 nm (4.17 eV) and 365 nm (3.39 eV)
observed in the PLE spectra can be regarded as transitions from
the s and p orbitals (the highest occupied molecular orbital
(HOMO)) to the lowest unoccupied molecular orbital (LUMO),
and the energy difference (dE) between the s and p orbital is
thus determined to be 0.78 eV.
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Fig. 4 (a) The upconverted PL spectrum excited at 980 nm laser, (b) the
upconverted PL mechanisms in NCDs.
The luminescence decay profiles of the blue NCDs are
shown in Fig. 3f. The decay was recorded for the NCDs transi-
tions at 450 nm for blue emission and 365 nm excitation
measured at room temperature by a time-correlated single
photon counting technique. The decay curve was best fitted
with a triple-exponential function as I(t) = A + B1exp( t/t1) +
B2exp( t/t2). The observed lifetimes are t1 = 10.7181 ns and
t2 = 1.5419 ns, which are similar to the reported CDs (about
8.00 ns).35 The observed nanosecond lifetime demonstrates the
radiative recombination nature of the excitations.20
Apart from the strong PL feature, the NCDs show distinctive
upconversion PL properties. As shown in Fig. 4a, the NCDs
excited by a 980 nm laser show a red upconverted emission
located at ca. 675 nm, and the shifting between the up con-
verted emission light and excitation light was 0.57 eV (Fig. 4b).
Compared to that of the reported NCDs via the solvothermal
route (dE is around 1.1 eV),25 the band gap between the
upconverted emission and the excitation light in our sample
is narrower, which may be related to the different doping type
of N. For our samples, the predominant doping type is pyrrolic-N,
while the pyridinic-like N and pyrrolic-like N were both dominant
in the reported NCDs. Moreover, the upconverted emission is
relatively higher than in the previous reported NCDs,24 and the
emission spectra under 980 nm and under 365 nm have been
compared in Fig. S8 (ESI†). The up-conversion PL property of
NCDs indicates their potential application in catalysis and energy
conversion.25 In summary, the effects of the size distribution,
different emissive trap sites and the defects induced by N doping
in the carbene-like structure could account for the luminescence
phenomena.36–40
Fig. 5a shows typical CL spectrum of the NCDs, it is of very
considerable interesting to study the CL behavior of NCDs, since
Fig. 5 (a) The CL emission spectrum of the NCDs under electron beam
excitation (excitation voltage = 5.0 kV, filament current = 50 mA), (b) a
simple scheme showing the cathodoluminescence processes in the NCDs.
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no CL research, to the best of our knowledge, has been carried
out on NCDs. Under a 5 kV electron beam excitation, three
distinctive emissions were observed at the wavelength center
of ca. 328 nm, 464 nm and 616 nm. The first two emissions
have also been observed in PL, and it is reasonable to believe
that the two emissions should share the same luminescence
origins both in PL and CL. Apart from the blue emission
(ca. 464 nm), the emission in the ultraviolet region (300–
370 nm) is ascribed to the transition from the LUMO to the
p orbital in the NCDs. However, the PL of the NCDs did not
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show any emission around 616 nm which is observed in the
CL spectrum, which can be attributed to the different lumi-
nescence mechanisms between PL and CL. It is well known
that the excitation energy is much larger in CL (1–5 keV) than
in PL (B3 eV). The ultraviolet light could usually excite the
photons from the LUMO to the p orbital or the localization of
the electron–hole pairs, similar to the activator in phos-
phors.41,42 While for CL excitation, after penetrating into the
lattice of the NCDs, the fast primary electrons will cause
ionization and create many secondary electrons, which would
further create more electrons. Due to the large density of the
electrons as well as the large excitation energy, the host lattice
of the NCDs would be excited and result in the corresponding
emission. Several researches have reported that the graphene
oxide (GO) derived from the oxidation products of graphite
could exhibit the emission from the red to near-infrared (NIR)
regions and the lateral size of the sheets is not the main factor
controlling the emission energy.43,44 Therefore, the observed
red CL in our results is reasonably related to the emission
from the host lattice of the NCDs. When the filament current
is fixed at 50 mA, the CL intensity decreases with the decreas-
ing accelerating voltage from 5.0 to 1.0 kV (Fig. S9, ESI†). The
larger electron beam energy (5 keV) would provide more
energy to excite the electrons of the NCDs and then generate
a higher CL emission intensity.
4. Conclusion
In summary, we have presented a simple and effective bottom-
up strategy for fabricating NCDs with oxygen-rich functional
groups. The as-synthesized NCDs exhibit excellent optical
features including a strong blue fluorescence performance,
upconversion properties and cathodoluminescence properties.
The NCDs possess unique PL properties, demonstrating their
potential usage in bioimaging and light-emitting diodes.
Acknowledgements
This work was financially supported by the Fundamental
Research Funds for the Central Universities (lzujbky-2013-
186), the Natural Science Foundation of Gansu Province, China
(Grant No. 1208RJYA005 and 1208RJYA047) and the Specialized
Research Fund for the Doctoral Program of Higher Education
(No. 20120211120007).
1526 | New J. Chem., 2014, 38, 1522--1527 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014
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