Synthesis and upconversion luminescence of N-doped graphene quantum dots

Ming Li, Wenbin Wu, Wencai Ren, Hui-Ming Cheng, Nujiang Tang, Wei Zhong, and Youwei Du

Citation: Appl. Phys. Lett. 101, 103107 (2012); doi: 10.1063/1.4750065

View online: https://doi.org/10.1063/1.4750065
View Table of Contents: http://aip.scitation.org/toc/apl/101/10
Published by the American Institute of Physics

Articles you may be interested in

Synthesis and photoluminescence of fluorinated graphene quantum dots
Applied Physics Letters 102, 013111 (2013); 10.1063/1.4774264

The emission wavelength dependent photoluminescence lifetime of the N-doped graphene quantum dots
Applied Physics Letters 107, 241905 (2015); 10.1063/1.4937923

Chlorine doped graphene quantum dots: Preparation, properties, and photovoltaic detectors
Applied Physics Letters 105, 111116 (2014); 10.1063/1.4896278

Tuning photoluminescence of reduced graphene oxide quantum dots from blue to purple
Journal of Applied Physics 115, 164307 (2014); 10.1063/1.4874180

Potassium doping: Tuning the optical properties of graphene quantum dots

AIP Advances 6, 075116 (2016); 10.1063/1.4959906

Functionalization of graphene quantum dots by fluorine: Preparation, properties, application, and their
mechanisms
Applied Physics Letters 110, 221901 (2017); 10.1063/1.4984238
 APPLIED PHYSICS LETTERS 101, 103107 (2012)

Synthesis and upconversion luminescence of N-doped graphene

quantum dots
Ming Li,1,2 Wenbin Wu,1 Wencai Ren,3 Hui-Ming Cheng,3 Nujiang Tang,1,a) Wei Zhong,1
and Youwei Du1
1
Nanjing National Laboratory of Microstructures and Department of Physics, Nanjing University,
Nanjing 210093, People’s Republic of China
2
College of Science, Guilin University of Technology, Guilin 541004, People’s Republic of China
3
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of
Sciences, Shenyang 110016, People’s Republic of China
(Received 24 May 2012; accepted 21 August 2012; published online 5 September 2012)
A hydrothermal approach was developed for the synthesis of N-doped graphene quantum dots
(N-GQDs) by cutting N-doped graphene. The N-GQDs obtained have a N/C atomic ratio of ca.
5.6% and diameter of 1–7 nm. The photoluminescence (PL) properties of the N-GQDs were
investigated. It was found that the N-GQDs possess bright blue PL and excellent upconversion PL
C 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4750065]
properties. V

N-doped graphene (NG) has received much attention Subsequently, the suspension was transferred into a 50 ml
since doping of graphene with nitrogen can module its elec- Teflon-lined stainless-steel autoclave and heated at 180  C
tronic properties and chemical reactivity.1–3 Due to its unique for 10 h. After cooling to room temperature, the resulting
physical and chemical properties, NG has been widely used in black suspension was further dialyzed in a dialysis bag
various fields such as biosensing,4 lithium battery,5 high- (retained molecular weight: 3500 Da) for several days and
performance ultracapacitors,6 fuel cells,7 and electrocatalysis.8 the N-GQDs were obtained. The morphology of the
However, currently available NG synthesized by chemical N-GQDs was examined by transmission electron microscopy
vapor deposition,2 arc-discharge,3 solvothermal,9 and post (TEM) (Model JEOL-2010, Japan) operated at an accelerat-
treatment of graphene or graphene oxide,10 are generally ing voltage of 120 kV. X-ray photoemission spectroscopy
micrometer-sized sheets, which limits their direct implementa- (XPS) measurements were performed on a Thermo Fisher
tion in nanodevices. Therefore, it is urgent to develop effec- Scientific with Al Ka radiation. The absorption and PL spec-
tive methods for producing nanometer-sized pieces, such as tra were recorded at room temperature on a Shimadzu
nanosized N-doped graphene oxide and N-doped graphene UV-3600 ultraviolet spectrophotometer and a Shimadzu
quantum dots (N-GQDs). RF-5301PC fluorescence spectrophotometer, respectively.
Up to now, by cutting and unzipping of N-doped carbon Figs. 1(a) and 1(b) show the typical TEM image and
nanotubes, nanosized N-doped graphene oxide was prepared diameter distribution of the N-GQDs. It is found that the
by Qian et al.11 Very recently, Li et al. presented an electro- N-GQDs are relatively uniform with diameters of ca.
chemical approach for the preparation of N-GQDs with the 1–7 nm, which are much smaller than those of GQDs synthe-
diameter of ca. 2-5 nm.12 Although the electrical and optical sized hydrothermally (ca. 10 nm)16 but similar to those of
properties of GQDs have aroused continuous and tremen-
dous interests,13–18 the optical properties of N-GQDs are still
lacking.12 In this letter, we report a facile hydrothermal
approach for cutting preoxidized NG into N-GQDs. The
results show that the N-GQDs possess excellent upconver-
sion photoluminescent (PL) properties, besides exhibiting
bright blue PL.
The reduced graphene oxide (RGO) was synthesized by
chemical exfoliation of natural flake graphite powder (500
mesh) followed by thermal reduction, as previously
reported.19 NG was obtained by annealing of RGO in a tube
furnace at 300  C for 1 h in an ammonia atmosphere.20 Then,
some of the NG was oxidized in concentrate H2SO4 and
HNO3 for 30 h under mild ultrasonication. After the mixture
was diluted with deionized water and filtered through a
0.22-lm microporous membrane, the oxidized NG was
obtained. Then, the oxidized NG was re-dispersed in deion-
ized water (40 ml) and the pH was tuned to 8 with NaOH.

a)
Author to whom correspondence should be addressed. Electronic mail: FIG. 1. Microstructure of the N-GQDs: (a) TEM image. (b) Diameter distri-
[email protected]. bution. (c), (d) High-resolution N 1s (c) and C 1s (d) spectra.

0003-6951/2012/101(10)/103107/3/$30.00 101, 103107-1 C 2012 American Institute of Physics

V
103107-2 Li et al. Appl. Phys. Lett. 101, 103107 (2012)

N-GQDs prepared electrochemically.12 XPS measurement is found that the PL peak shifts to longer wavelengths and its
was carried out to determine the composition of the N-GQDs. intensity decreases gradually. On excitation at 310 nm, the
The N/C atomic ratio was calculated to be ca. 5.6%, which is PL spectrum shows a strong peak at 425 nm with a Stokes
higher than that of the N-GQDs prepared electrochemically shift of 115 nm (1.08 eV). The full width at half maximum
(ca. 4.3%).12 The high-resolution N 1s spectrum of the N- (FWHM) is ca. 100 nm. The PL excitation (PLE) spectrum
GQDs [Fig. 1(c)] shows the presence of both pyridine-like recorded with the strongest luminescence shows two sharp
(398.3 eV) and pyrrolic-like (399.6 eV) N atoms.7,12 In addi- peaks at 245 and 310 nm [Fig. 2(c)]. The PLE spectrum
tion to the C–N bond (285.2 eV), the high-resolution C 1s clearly confirms that the luminescence from the N-GQDs is
spectrum of the N-GQDs [Fig. 1(d)] also confirms the pres- correlated with the two transitions at 245 and 310 nm. The
ence of O-rich groups, such as C–O (286 eV), C¼O two electronic transitions of 245 nm (5.06 eV) and 310 nm
(288.1 eV), and O–C¼O (289.5 eV),18 which is consistent (4 eV) observed in the PLE spectrum can be regarded as tran-
with the N-GQDs reported previously.12 sitions from the r and p orbitals (the highest occupied mo-
The UV-vis absorption spectrum of the N-GQDs shows lecular orbital (HOMO)) to the lowest unoccupied molecular
an absorption band at ca. 300 nm [Fig. 2(a)], which is blue- orbital (LUMO), as indicated in Fig. 2(d).
shifted by ca. 20 nm with respect to that of GQDs synthe- Moreover, the quantum yield of N-GQDs was assumed
sized hydrothermally.16 Under irradiation by a 365 nm lamp, by using quinine sulfate as a reference (shown in Table I). It
the N-GQDs emit bright blue luminescence [shown in inset was calculated according to
of Fig. 2(a)]. It has been reported that isolated sp2 clusters
with a size of ca. 3 nm within the carbon-oxygen sp3 matrix / ¼ /r ðI=Ir Þðn2 =n2r ÞðAr =AÞ;
could yield band gaps consistent with blue emission due to
the localization of electron-hole pairs.21 Therefore, the size where / is the quantum yield, I is the measured integrated
effect may be responsible for the observed blue emission for emission intensity, n is the refractive index (1.33 for water),
N-GQDs (diameter: 1–7 nm). Note that the previous observa- and A is the optical density. The subscript “r” refers to the
tion revealed the blue PL from nanosized GO, implying that reference of known quantum yield. The PL quantum yield
the O-rich groups make an important contribution to the measured using quinine sulfate as a reference is ca. 8.6%,
observed blue shift in the PL emission from N-GQDs.22 which is higher than that of reported GQDs (ca. 6.9%).16
Moreover, it has been proved the strong electron- Apart from the strong PL feature, the N-GQDs show
withdrawing ability of the N atoms within the conjugated C clear upconversion PL properties. As shown in Fig. 3(a),
plane by previous experimental observations and quantum- when the excitation wavelength changes from 560 to
mechanical calculations, which will attribute to PL blue
shift.12,23,24 It suggests that the PL blue shift may result from TABLE I. Quantum yield of N-GQDs using quinine sulfate as a reference.
the relatively strong electron affinity of N atoms in the
N-GQDs. Integrated Refractive
To further explore the optical properties of the N-GQDs, emission index of Quantum
a detailed PL study was carried out by using different excita- Sample intensity (I) Abs. (A) solvent (n) yield (/)
tion wavelengths. Similar to GQDs,16,25 the N-GQDs also Quinine sulfate 42180.6 0.0789 1.33 0.54 (known)
exhibit an excitation-dependent PL behavior [Fig. 2(b)]. As N-GODs 3158.7 0.0371 1.33 0.086
the excitation wavelength is changed from 300 to 400 nm, it

FIG. 2. (a) UV-vis absorption and (b) PL spectra of the N-GQDs at different FIG. 3. (a) Upconverted PL spectra and (b) PLE spectrum of the N-GQDs at
excitation wavelengths. Inset of (a): Optical photograph of the N-GQDs dis- different excitation wavelengths and the monitoring wavelength of 425 nm.
persed in water under 365 nm irradiation. (c) PLE spectrum with the detec- (c) and (d) A schematic illustration of two typical electronic transitions proc-
tion wavelength of 425 nm. (d) Typical electronic transitions of triple esses of the N-GQDs: (c) normal PL mechanism and (d) upconverted PL
carbenes in the optical spectrum (c). mechanism.
103107-3 Li et al. Appl. Phys. Lett. 101, 103107 (2012)

900 nm, the upconverted emission peak shifts from 415 to bandgap around the Dirac point is induced in the system.
516 nm. In addition, it is found that (i) the fluorescent emis- Thus, the dE of p and r orbitals of N-GQDs is lower than
sion peaks are generally broad and dependent on excitation that of GQDs. Similarly, the N-GQDs show a red-shifted in
wavelength and (ii) the peaks shift to longer wavelengths as the positions of the upconversion PL peaks with respect to
the excitation wavelength is increased from 560 to 900 nm. those of GQDs.
Interestingly, the intensity of the peaks increases first and In summary, N-GQDs with a diameter of ca. 1–7 nm
then decreases with increasing excitation wavelength. The and N/C atomic ratio of ca. 5.6% were synthesized by a sim-
intensity of the peaks at the 600–750 nm regions is higher ple hydrothermal approach. The N-GQDs exhibit bright fluo-
than that at other regions. The maximum PL intensity rescence performance and excellent upconversion properties.
(FWHM ca. 100 nm) appears at 425 nm when the excitation The discovery of the upconverted PL properties from
wavelength is 640 nm. The PLE spectrum in Fig. 3(b) shows N-GQDs may expand the applications of graphene in envi-
a strong broad peak centered at ca. 640 nm as the monitoring ronmental and energy technology.
wavelength is 425 nm. Moreover, one can find that the posi-
tions of the peaks show a clear red-shift with respect to those This work was financially supported by the State Key
of GQDs.25 All these results are different from the GQDs Program for Basic Research (Grant Nos. 2012CB932304 and
reported previously.25 It indicates that N-GQDs may be used 2010CB923402), NSFC (Grant No. 51072079), and the Sci-
as a powerful energy-transfer component in photocatalyst entific Research Foundation of Graduate School of Nanjing
design for environmental and energy. University (Grant No. 2012cl05) of China.
To explain the above interesting phenomena observed in
1
N-GQDs, an energy level structural model of the N-GQDs X. Wang, X. Li, L. Zhang, Y. Yoon, P. K. Weber, H. Wang, J. Guo, and
H. Dai, Science 324, 768 (2009).
was established to study the normal fluorescence perform- 2
D. Wei, Y. Liu, Y. Wang, H. Zhang, L. Huang, and G. Yu, Nano Lett. 9,
ance and the upconverted PL properties. Figs. 3(c) and 3(d) 1752 (2009).
3
show the schematic illustrations of two typical electronic L. S. Panchakarla, K. S. Subrahmanyam, S. K. Saha, A. Govindaraj, H. R.
transitions processes of N-GQDs. As illustrated in Fig. 3(c), Krishnamurthy, U. V. Waghmare, and C. N. R. Rao, Adv. Mater. 21, 4726
(2009).
the normal PL spectrum can be regarded as a transition from 4
Y. Wang, Y. Shao, D. W. Matson, J. Li, and Y. Lin, ACS Nano 4, 1790
LUMO to HOMO. Namely, when the electrons of the r or- (2010).
5
bital were excited by a bunch of low-energy photons, they A. L. M. Reddy, A. Srivastava, S. R. Gowda, H. Gullapalli, M. Dubey, and
would transition to a high-energy state such as the LUMO. P. M. Ajayan, ACS Nano 4, 6337 (2010).
6
H. M. Jeong, J. W. Lee, W. H. Shin, Y. J. Choi, H. J. Shin, J. K. Kang, and
Subsequently, the electrons transition back to a low-energy J. W. Choi, Nano Lett. 11, 2472 (2011).
state. Thus, a normal PL can be emitted when the electrons 7
L. Qu, Y. Liu, J. B. Baek, and L. Dai, ACS Nano 4, 1321 (2010).
8
transition back to the r orbital. By contrast, the upconverted Z. Luo, S. Lim, Z. Tian, J. Shang, L. Lai, B. MacDonald, C. Fu, Z. Shen,
T. Yu, and J. Lin, J. Mater. Chem. 21, 8038 (2011).
PL spectrum can be considered as an anti-Stokes transition 9
D. Deng, X. Pan, L. Yu, Y. Cui, Y. Jiang, J. Qi, W. X. Li, Q. Fu, X. Ma,
(as indicated in Fig. 3(d)).25 That is, when the electrons of Q. Xue, G. Sun, and X. Bao, Chem. Mater. 23, 1188 (2011).
10
the p orbital are excited, the p electrons would transition to X. Li, H. Wang, J. T. Robinson, H. Sanchez, G. Diankov, and H. Dai,
the LUMO, and then the electrons transition back to a low- J. Am. Chem. Soc. 131, 15939 (2009).
11
Z. Qian, J. Zhou, J. Chen, C. Wang, C. Chen, and H. Feng, J. Mater.
energy state. As a result, an upconverted PL is emitted when Chem. 21, 17635 (2011).
the electrons transition back to the r orbital. It is well known 12
Y. Li, Y. Zhao, H. Cheng, Y. Hu, G. Shi, L. Dai, and L. Qu, J. Am. Chem.
that the energy levels of r and p orbitals are provided by the Soc. 134, 15 (2012).
13
carbene ground-state multiplicity, which is related to the K. A. Ritter and J. W. Lyding, Nat. Mater. 8, 235 (2009).
14
L. A. Ponomarenko, F. Schedin, M. I. Katsnelson, R. Yang, E. W. Hill, K.
energy difference (dE) between the r and p orbitals.16 As S. Novoselov, and A. K. Geim, Science 320, 356 (2008).
proposed by Hoffmann, the dE should be below 1.5 eV.26 It 15
V. Gupta, N. Chaudhary, R. Srivastava, G. D. Sharma, R. Bhardwaj, and
is worth noting that the dE in the upconversion process in 16
S. Chand, J. Am. Chem. Soc. 133, 9960 (2011).
the case of N-GQDs is ca. 0.98 eV, lower than that of GQDs D. Pan, J. Zhang, Z. Li, and M. Wu, Adv. Mater. 22, 734 (2010).
17
S. Zhuo, M. Shao, and S. T. Lee, ACS Nano 6, 1059 (2012).
(1.1 eV).25 18
Y. Li, Y. Hu, Y. Zhao, G. Shi, L. Deng, Y. Hou, and L. Qu, Adv. Mater.
Clearly, compared to the GQDs, the N-GQDs show a 23, 776 (2011).
19
clear red-shifted in the positions of the upconversion PL Z. S. Wu, W. Ren, L. Gao, B. Liu, C. Jiang, and H. M. Cheng, Carbon 47,
peaks and exhibit a lower dE. The exact mechanism remains 493 (2009).
20
M. Li, N. Tang, W. Ren, H. Cheng, W. Wu, W. Zhong, and Y. Du, Appl.
unknown and need to be addressed. We proposed that this Phys. Lett. 100, 233112 (2012).
may be due to the shift of Fermi level and the increasing of 21
G. Eda, Y. Y. Lin, C. Mattevi, H. Yamaguchi, H. A. Chen, I. S. Chen, C.
bandgap because of N-doping.1–3 Theoretical calculations 22
W. Chen, and M. Chhowalla, Adv. Mater. 22, 505 (2010).
Z. Luo, P. M. Vora, E. J. Mele, A. T. C. Johnson, and J. M. Kikkawa,
indicated that the carbon pr orbitals hybridizes with the
Appl. Phys. Lett. 94, 111909 (2009).
nitrogen pr orbitals below approximately EF3.5 eV, 23
K. P. Gong, F. Du, Z. H. Xia, M. Durstock, and L. M. Dai, Science 323,
while the graphene p orbitals hybridizes with the nitrogen 760 (2009).
24
pz orbitals over a wide range and dominates the states near S. Y. Wang, D. S. Yu, and L. M. Dai, J. Am. Chem. Soc. 133, 5182 (2011).
25
J. Shen, Y. Zhu, C. Chen, X. Yang, and C. Li, Chem. Commun. 47, 2580
the Fermi level.27 The consequences are that (i) the Fermi (2011).
level is shifted above the Dirac point and (ii) because of the 26
R. Hoffmann, J. Am. Chem. Soc. 90, 1475 (1968).
27
shift of the p orbitals arising from N-doping, an extra M. Wu, C. Cao, and J. Z. Jiang, Nanotechnology 21, 505202 (2010).