Ultrasonics Sonochemistry 28 (2016) 367–375

Contents lists available at ScienceDirect

Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Facile one-step sonochemical synthesis of ultrafine and stable

fluorescent C-dots
Vijay Bhooshan Kumar a, Ze’ev Porat b,c, Aharon Gedanken a,d,⇑
a
Bar-Ilan Institute for Nanotechnology and Advanced Materials, Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel
b
Division of Chemistry, Nuclear Research Center-Negev, Be’er Sheva 84190, Israel
c
Institute of Applied Research, Ben-Gurion University of the Negev, Be’er Sheva 84105, Israel
d
National Cheng Kung University, Department of Materials Science & Engineering, Tainan 70101, Taiwan

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

Article history: This work describes a one-step synthesis of carbon dots (C-dots), which is carried out by sonication of
Received 2 March 2015 polyethylene glycol (PEG-400) for 0.5–3 h. The effect of the various experimental parameters, such as
Received in revised form 14 July 2015 sonication time, amplitude and temperature on the size and the fluorescence of the C-dots was studied.
Accepted 10 August 2015
It was found that the average diameter of the C-dots is between 2 and 9 nm, depending on the prepara-
Available online 10 August 2015
tion conditions. The highest quantum yield of emission was
16%. These high fluorescence properties of
the C-dots could be used for bioimaging and for solar cell applications.
Keywords:
Ó 2015 Elsevier B.V. All rights reserved.
PEG-400
C-dots
Fluorescence
Sonochemistry
Quantum yield

1. Introduction
Carbon is an extremely versatile material that exists in numer-
ous forms with diverse physical, chemical, electrical, and electro-
chemical properties [1,2]. Carbon dots (C-dots) have attracted
considerable research interest as newly emergent carbon materi-
als. In the last few years C-dots have shown a wide range of poten-
tial applications in different areas of research, due to the superior
optical properties, excellent biocompatibility, small size and low
cost of production [3–5]. The fascinating physical properties of
C-dots are responsible for a wide range of potential applications
[4,5] in bioimaging [6,7], cell imaging [8,9], dye degradation [10],
chemiluminescence [11], solar cells [12,13], photocatalysts [14],
nanoelectronic devices [15], photodynamic therapy [16] and gene
delivery [17].
The C-dots have been synthesized by a variety of methods, such
as laser ablation [18,19], pyrolysis [20], combustion [21], a
hydrothermal process [22,23] and a precipitation method [24].
Sonochemical synthesis of C-dots was also reported: Li et al. pre-
pared monodispersed water-soluble fluorescent carbon nanoparti-
cles from glucose by a one-step alkali or acid assisted ultrasonic
irradiation [25]. Wei et al. demonstrate that a facile sonochemical
⇑ Corresponding author at: Bar-Ilan Institute for Nanotechnology and Advanced
Materials, Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel.
E-mail address: gedanken@mail.biu.ac.il (A. Gedanken).
method for synthesis of C-dots using citric acid as a carbon source
and ethylene diamine as both an N doping source and a surface
passivation agent [26].
The current work introduces additional information that was
not provided in the previous studies [25,26]. While in those
studies an alkaline catalyst was used for the production of
C-dots, our method solely involves sonication of one material,
PEG 400, without any catalyst. In addition, we have studied in
detail the effect of the various sonication parameters on the
physical and chemical properties of the C-dots. Parameters such
as sonication time, sonication amplitude and the reaction
temperature were varied and their effect on the size of the
C-dots and on the fluorescence spectra and yield were moni-
tored. Finally, our paper presents results on the sonochemical
deposition of the C-dots on polyethylene surface. Such deposi-
tion is novel and has not been reported before. The material
uniformly coated by C-dots could be used for antibiofilm and
for other applications.
The physical and chemical effects of ultrasound [27] have led to
several sonochemical preparations of carbon materials including
carbon nanotubes [26–30]. It is well-known that the ultrasonic
cavitation process in liquids induces the formation of gas bubbles
that grow and collapse, thus producing local hot spots of 5500 °C
and pressure of several thousand atmospheres [27]. These local
harsh conditions are responsible for the formation of C-dots in
organic liquids.

http://dx.doi.org/10.1016/j.ultsonch.2015.08.005
1350-4177/Ó 2015 Elsevier B.V. All rights reserved.
368 V.B. Kumar et al. / Ultrasonics Sonochemistry 28 (2016) 367–375
The current work describes a simple sonochemical synthesis of
C-dots in polyethylene glycol (PEG-400) without any catalyst and
studies the effect of the various sonication parameters on the phys-
ical and chemical properties of the C-dots. The mechanism of the
C-dot formation has been investigated. The highest quantum yield
of emission was
16%.
2. Experimental section
2.1. Chemicals
Polyethylene glycol-400 (99.998%) was purchased from Sigma–
Aldrich and used as received.
2.2. Experimental procedure
12 mL of polyethylene glycol (PEG-400) was transferred into a
test tube which was dipped in a water/Si-oil bath at 4–150 °C.
The tip of an ultrasonic transducer was dipped in the solution,
about 1 cm above the bottom of the test tube. The ultrasonic trans-
ducer (Sonics and Materials Inc., USA, model VCX 750, frequency
20 kHz, volt 230V AC) applied ultrasonic irradiation while the
experimental conditions of time (3 min, 30 min, 1 h, 2 h, 2.5 h,
and 3 h), reaction amplitude (40–70%) and temperature of the
water/Si-oil bath (4–150 °C) were varied.
2.3. Analytic equipment
The fluorescence of the C-dots was measured by a fluorescence
spectrophotometer (Varian Cary Eclipse). High resolution trans-
mission electron microscopy (HRTEM) was carried out on a JEOL
2100 microscope, operated at accelerating voltage of 200 kV. The
samples for TEM were prepared by drying a droplet of isopropanol
solution of PEG containing C-dots on a carbon coated copper grid.
Elemental analysis and elemental mapping were performed using
HRTEM Energy Dispersive X-ray Spectroscopy (EDS). X-ray photo-
electron spectroscopy (XPS) analyses of samples were recorded
using an ESCALAB 250 spectrometer with a monochromatic X-ray
source with Al Ka excitation (1486.6 eV). Binding energy calibra-
tion was based on C1s at 285 eV. Zeta potential measurements of
the particles were performed on ZetaSizer Nano-ZS (Malvern
Instruments Ltd., Worcestershire, UK).
3. Results and discussion
3.1. The effect of the sonication amplitude on the C-dot formation and
fluorescence
Formation of C-dots under different sonication amplitudes was
performed at constant conditions of time (2 h) and temperature
(55 °C) which were similar to those in our previous works
[31,32]. The fluorescence emitted from the C-dots in the super-
natant solution was recorded for different excitation wavelengths
(330, 350, 370, 390, 410, 430, 450, 470 and 490 nm). Fig. 1A–D
presents the typical spectra that were obtained from the C-dots
which were produced at different sonication amplitudes (40%,
50%, 60% and 70% respectively). All of the emission spectra man-
ifested broad bands centered between 440 and 480 nm. It can be
observed that the emission intensity and the area under the emis-
sion curves increase as the sonication amplitude increases, up to
70%. This can be explained by a larger amount of C-dots that
formed at higher sonication intensities, due to the more efficient
decomposition of PEG. In all four cases, the maximum emission
intensity was obtained at the excitation wavelength of 370 nm,
while the most intense emission was obtained at 460–480 nm,
where the full-width at half-maximum (FWHM) was relatively
narrow (ca. 115 nm), suggesting a relatively small size distribu-
tion of the particles. This is consistent with the TEM results
(Fig. 2) that show that the particles were rather even in size
and mostly smaller than 10 nm. For excitation at 370 nm, the
emission peaks of the particles formed at 70% amplitude and
above were
30 nm higher than the emission peaks of the parti-
cles formed at 40% amplitude. The reason might be an increase in
the average size of the C-dots, as can be seen in the TEM images
(Fig 2).
The TEM images of the C-dots that were obtained in PEG-400 at
different amplitudes show that the small C-dots are spherical and
their diameters varied with the amplitude of sonication. At an
amplitude of 40% the diameters were
2–5 nm. At an amplitude
of 50% the diameters varied in the range of 3–5 nm range. At 60%
amplitude the diameters were 3–6 nm. For the higher formation
amplitude (70%), it seems that slightly larger particles (
4–9 nm)
were obtained. This can be explained as follows: it is well known
that in the presence of solid materials, further collapse of the
acoustic bubbles results in the formation of microjets moving at
a very high speed in the direction of the solid particles. Although
the target particles are small, the chances for collisions are high,
thus leading to the coalescence of the two colliding particles. Thus,
the collision probability will be enhanced at higher sonication
amplitudes. Moreover, since the dissociated liquid in this case is
of relatively high density, a higher amplitude might lead to simul-
taneous dissociation of neighboring molecules leading to the for-
mation of larger particles.
The stability of the C-dots was examined by occasional fluores-
cence measurements. For several weeks, no changes in the inten-
sity of the fluorescence bands could be observed. However, after
two months, the strong yellow color of the suspension started to
fade and the intensity of the fluorescence bands was slightly
reduced. The photograph in Fig. 3A shows the blue photolumines-
cence of the suspension when illuminated with UV light (365 nm)
while at day light the suspension appears to be yellow (Fig. 3B).
High resolution TEM images reveal that the C-dots are crys-
talline. Fig. 4A shows the image of a cluster of C-dots obtained at
70% amplitude with its selected area electron diffraction (SAED)
that revealed a ring pattern that correspond to the {01.3} {10.6}
{11.0} planes of a hexagonal carbon structure (PDF 26-1083). The
high resolution image of two individual carbon particles shows
their crystal lattice with d-spacing of 0.2 nm which is consistent
with earlier reports [33,34]. The cell parameter are a = 2.522 and
c = 20.59 for hexagonal carbon (PDF 26-1023).
3.2. The effect of the sonication duration on the formation of the C-dots
In order to find the minimal sonication duration of PEG which
is required to form small-size C-dots and yield high florescence
intensity, we performed several experiments at various sonica-
tion durations of 1, 2, 2.5 and 3 h, at 70% amplitude and starting
temperatures of 55 °C. The fluorescence spectra of these products
are presented in Fig. 5A–C for the various excitation wave-
lengths. Fig. 5A shows slight effect of the sonication duration,
in this span of time, on the excitation wavelength and on the
emission wavelength and intensity, as summarized in Table 1.
However, sonication for only 30 min yielded very low fluores-
cence intensity. It can thus be concluded that the decomposition
of PEG to form C-dots is time dependent, with a certain thresh-
old for each set of conditions, below which only a small amount
of C-dots can be formed. Beyond such threshold the changes are
rather moderate. The 50 nm difference in wavelengths between
the excitation and emission for one of these cases is demon-
strated in Fig. 5D.
 V.B. Kumar et al. / Ultrasonics Sonochemistry 28 (2016) 367–375 369

500 500
330 nm Ex 330 nm

400
A 350 nm
370 nm 400
B Ex 350 nm
Ex 370 nm
390 nm Ex 390 nm

PL Intensity
PL Intensity
410 nm Ex 410 nm
300 300
430 nm Ex 430 nm
450 nm Ex 450 nm
200 470 nm 200 Ex 470 nm
490 nm Ex 490 nm

100 100

0 0
350 400 450 500 550 600 650 700 350 400 450 500 550 600 650 700
Wavelength (nm) Wavelength (nm)

800 800
Ex 330 nm Ex 330 nm
700 C Ex 350 nm 700 D Ex 350 nm
Ex 370 nm
Ex 370 nm
600 600
Ex 390 nm Ex 390 nm

PL Intensity
PL Intensity

500 Ex 410 nm 500 Ex 410 nm

Ex 430 nm Ex 430 nm
400 Ex 450 nm 400 Ex 450 nm
Ex 470 nm Ex 470 nm
300 300
Ex 490 nm Ex 490 nm
200 200

100 100

0 0
350 400 450 500 550 600 650 700 350 400 450 500 550 600 650 700
Wavelength (nm) Wavelength (nm)

Fig. 1. Fluorescence spectra at different excitation wavelength, for C-dots obtained from PEG-400 after sonication of 2 h at different sonication amplitudes: (A) 40, (B) 50, (C)
60 and, (D) 70%.

A B

C D

Fig. 2. TEM image of C-dots formed by sonication of PEG-400 for 2 h at different sonication amplitudes: (A) 40%, (B) 50%, (C) 60%, (D) 70%. Amplitude.
370 V.B. Kumar et al. / Ultrasonics Sonochemistry 28 (2016) 367–375

3.3. Optimization of the reaction temperature

After finding the optimal formation condition which yields the

highest fluorescence intensity (2.5 h sonication at 70% amplitude)
we explored the effect of the initial sonication temperature under
these conditions. C-dots were prepared at 6, 25, 55, 65, and 75 °C
and the fluorescence of each of the products was measured. At
6 °C, no fluorescence could be observed, while at 25 °C fluorescence
bands were observed of considerably lower intensities in compar-
ison to those observed at higher temperatures (Fig. 6). At higher
temperatures of formation higher intensities where measured,
with a considerable rise for the sample prepared at 75 °C (Table 2).
Higher intensity means a larger number of C-dots in that sample,
possibly because of the reduced viscosity of the PEG at elevated
temperatures that enable more efficient cavitation process or more
facile decomposition of PEG to form C-dots. This explanation is
supported by the results of a similar experiment in which the son-
Fig. 3. Photographs of a suspension of the C-dots illuminated by (A) UV light ication of PEG was done in a test tube immersed in an oil bath at
(365 nm) and (B) daylight.

Fig. 4. HRTEM images of the C-dots obtained by sonication of PEG-400 at 70% amplitude for 2.5 h. (A) A cluster of C-dots. Inset: selected-area electron diffraction showing
polycryatalline pattern. (B) A higher resolution image of the C-dots. Inset: The crystal lattice of two single particles.

800 900
Ex 330 nm 330 nm
700 A Ex 350 nm 800 B 350 nm
Ex 370 nm 700 370 nm
600 Ex 390 nm 390 nm
600
PL Intensity

PL Intensity

500 Ex 410 nm 410 nm

Ex 430 nm 500 430 nm
400 Ex 450 nm 450 nm
400
Ex 470 nm 470 nm
300
Ex 490 nm 300 490 nm
200 200
100 100
0 0
350 400 450 500 550 600 650 700 350 400 450 500 550 600 650 700
Wavelength (nm) Wavelength (nm)

900 1000
330 nm
800
C 350 nm
Excitation spectra
Emission spectra D
700 370 nm 800
390 nm
600
PL Intensity
PL Intensity

410 nm
600
500 430 nm
Ext 390 nm
450 nm
400 Emi 480 nm
470 nm 400
300 490 nm
200 200
100
0 0
350 400 450 500 550 600 650 700 300 350 400 450 500 550 600 650 700
Wavelength (nm) Wavelength (nm)

Fig. 5. Fluorescence spectra of the products obtained by ultrasonic irradiation of PEG-400 at 70% amplitude for (A) 2 h (B) 2.5 h (C) 3 h. (D) Excitation and emission spectra of
C-dots which were synthesized at 70% amplitude for 2.5 h.
 V.B. Kumar et al. / Ultrasonics Sonochemistry 28 (2016) 367–375 371

Table 1 to the (1 0 2) and (0 0 4) facets of sp2 graphitic carbon, implying that

The excitation and emission wavelengths and the maximal fluorescence intensity for the C-dots are structured like crystalline graphite carbon [33,34].
C-dots that were formed at different durations of time. Sonication conditions: 70%
amplitude, initial temperature 55 °C.
3.4. The effect of the PEG molecular weight on the sonochemical
Time Highest fluorescence band
reaction
(h)
Excitation Emission Fluorescence
wavelength (nm) wavelength (nm) intensity (A.U.)
PEG samples of higher molecular weights (2000, 3000 and
2 390 465 660 6000) were also examined as possible media for the sonochemical
2.5 390 470 800
reaction of C-dots formation. However, no sonochemical process
3 390 474 774
could occur in any of these, even at elevated temperature of
100 °C. We assume that the reason is either the high viscosity of
150 °C. Here, C-dots were clearly observed by TEM after
20 min these PEG samples, or the larger size of the polymeric chains that
sonication at 70% amplitude (Fig. 7). Their fluorescence spectrum prevent them from interacting with the collapsing gas bubbles.
(Fig. S2, see the supporting information) reveals that the excitation
and emission are red shifted by
20 nm. It might be due to larger 3.5. Spectroscopy analysis of C-dots
particles sizes (5–11 nm) that were formed at the higher tempera-
ture, as can be estimated from the TEM micrograph. The lattice X-ray Photoelectron spectroscopy (XPS) was utilized to investi-
planes with interplanar spacing of 0.203 and 0.176 nm are close gate the surface composition and the elemental oxidation state in

300 900
330 nm
A 330 nm
350 nm
800 B 350 nm
700 370 nm
370 nm
390 nm
200 390 nm 600
PL Intensity

PL Intensity
410 nm
410 nm
430 nm 500 430 nm
450 nm
450 nm 400
470 nm
470 nm
100 300 490 nm
490 nm
200
100
0 0
350 400 450 500 550 600 650 700 350 400 450 500 550 600 650 700
Wavelength (nm) Wavelength (nm)

1000 1000
330 nm 330 nm

800
C 350 nm
800
D 350 nm
370 nm 370 nm
390 nm 390 nm
PL Intensity
PL Intensity

410 nm 410 nm
600 600
430 nm 430 nm
450 nm 450 nm
400 470 nm 400 470 nm
490 nm 490 nm

200 200

0 0
350 400 450 500 550 600 650 700 350 400 450 500 550 600 650 700
Wavelength (nm) Wavelength (nm)

Fig. 6. Fluorescence spectra of the product obtained from 2.5 h sonication of PEG-400 at (A) 25 °C, (B) 55 °C, (C) 65 °C, (D) 75 °C. (70% amplitude).

Fig. 7. TEM images of C-dots formed by sonicating PEG-400 for
20 min at 70% amplitude in Silicone oil bath heated to 150 °C.
372 V.B. Kumar et al. / Ultrasonics Sonochemistry 28 (2016) 367–375

Fig. 8. X-ray photoelectron spectroscopy (XPS) spectra of (A) C-dots and (B) C 1s (C) O 1s in the C-dots.

the C-dots. The results revealed that the surface consisted of 72 at.
% carbon and 28 at.% oxygen with the corresponding binding ener-
gies of ca. 280 and 530 eV (Fig. 8A). The XPS curve shows complex
oxidation states of the surface carbon atoms (Fig. 8B). The C1s peak
consists a sp2 C@C bond with binding energy of 284.971 eV,
together with C@O (carbonyl, 286.219 eV), and O–C@O (carboxyl,
289.004 eV) groups. The O 1s peak at 532.345 eV (Fig. 8C) is asso-
ciated with oxygen in the states of C–O and C–OO.
It is important to compare between the relative content of car-
bon and oxygen that were obtained by two other techniques: EDS
 V.B. Kumar et al. / Ultrasonics Sonochemistry 28 (2016) 367–375 373

Table 2 PL curve in the wavelength range from 370 to 700 nm. Then, the
The excitation and emission wavelengths and the maximal fluorescence intensity for integrated fluorescence intensity was plotted against the absor-
the C-dots that were formed by sonication of PEG at different initial temperatures.
Sonication conditions: 70% amplitude, 2.5 h.
bance. The values of the quantum yield were calculated according
to the following equation:
Temp Highest fluorescence band
(°C)
Excitation Emission Fluorescence Ax PLst nx
wavelength (nm) wavelength (nm) intensity (A.U.)
QY ¼ QY st    100%
Ast PLx nst
25 330 410 175
55 390 470 800
where the subscripts st and x denote quinine sulfate standard
65 370 460 830 and C-dots, respectively, QY is the fluorescence quantum yield, A
75 390 450 970 is the absorbance, PL is the area of emission peak and n is the
refractive index of the solvent (both are 1.33). In order to minimize
the re-absorption effects, the absorbance at 360 nm in a 10 mm
Table 3
cuvette was kept below 0.1 OD (optical density).
Results of the elemental analysis by different spectroscopy techniques. The quantum yield was measured for the optimized formation
conditions of C-dots (70% amplitude, 2.5 h sonication at 75 °C).
Method Carbon (at.%) Oxygen (at.%) Hydrogen (at.%)
The aqueous dispersion of the C-dots in water was transparent to
XPS 72 28 – day light and remained stable for several weeks. Upon excitation
EDS 76 22 –
CHNSO chromatogram 73 20 3.5
under a 360 nm UV lamp, the C-dots emitted a strong blue lumi-
nescence and the quantum yield was estimated to be
16% using
quinine sulfate as the reference (Fig. 10). Table 4 presents the liter-
ature data for the quantum yields of C-dots that were prepared by
and elemental analysis (CHNSO). EDS analysis of C-dots showed
various methods. The fluorescence behavior of the C-dots is influ-
that the major components were carbon and oxygen (see the Sup-
enced by their surface chemistry, like ‘‘defect sites” located on the
porting information Fig. S3). CHNSO analysis revealed the presence
surface, which are responsible for trapping of excited-state energy
of C, O and H. Fig. S4A presents the chromatogram of carbon and
leading to the highest quantum yield of 16%. Furthermore, the
hydrogen and Fig. S4B shows the chromatogram for oxygen. The
measurement of fluorescence intensity as a function of time con-
atomic percentages, as calculated by the operating algorithm, were
firmed that the C-dots were photostable as no significant photo
73% carbon, 3% hydrogen and 20% oxygen. The results of XPS, EDS
bleaching behavior was observed upon continuous excitation
and CHNSO analysis, summarized in Table 3, show good agree-
(kex = 390 nm) for 10 h.
ments between these three methods for all three elements. How-
ever, it is clear that a higher percentage of oxygen is found on
the surface due to oxidation of the surface carbon atoms. On the 3.8. Mechanism of formation of C-dots
other hand, finding 20% oxygen in the C-dots indicates that the ori-
gin of some of the oxygen is in the decomposing PEG molecule, and The sonochemical degradation and carbonization of PEG is a
that the precursor was not fully carbonized upon sonication. complex chemical process and it is difficult to determine the exact
Raman analysis was also performed: typical Spectra (Fig. S5) chemical reactions by which it occurs. Previous research by Dong
show the graphitic nature of the C-dots. One sharp and intense et al. [35] showed that heating of pure ethylene glycol, diethylene
Raman peak of G-band was observed at 1602 cm1 and one of D- glycol or polyethylene glycol (PEG400) in the temperature range of
band was observed at 1371 cm1. The Raman spectrum indicates 180–230 °C (T/PEG) resulted in instant formation of colloidal stable
the presence of pristine carbon nanomaterials in the form of C- suspensions of fluorescent carbon nanoparticles under microwave
dots. However, it did not reveal the presence of the oxygen. synthesis. In our case we assume that carbonization may arise
from cross-linking, induced by intermolecular dehydration of
3.6. Zeta potential measurement PEG-400 due the extreme condition of pressure (ca. 500 atm.)
and temperatures (ca. 5500 K) which develop for extremely short
The surface charge (Zeta potential) of the C-dots was measured times during the cavitation process [36]. Even if the vapor pressure
in a suspension of a small droplet of PEG 400 containing C-dots in of PEG is low and only a small amount of PEG vapors are found
1 mL of water. Fig. 9 presents three consecutive plots with good inside the collapsing bubble, the temperature in the 200 nm ring
repeatability for C-dots that were formed during 2.5 h sonication around the collapsing bubble is still very high for the carbonization
at 70% amplitude in hot water bath (75 °C). The average value of of the PEG molecules.
the three measurements is 19.4 mV. The reason for the negatively
charged surface may be the formation of carbanions and carboxylic
groups during sonication of PEG-400, which means that the carbon 4. Fabrication of C-dots on polythene surface
has an unshared pair of electrons and thus bears negative charges.
Another possible explanation is the existence of carboxylate ions Finally, we attempted to form a coating layer of C-dots on poly-
on the surface. ethylene (PE) by sonication. Some small pieces of PE were
immersed in a suspension of C-dots in PEG which were produced
3.7. Quantum yield of fluorescence as previously described. The suspension was sonicated at 30%
amplitude and 4 °C for 30 min using the booster. The product of
The quantum yield of the C-dots fluorescence was estimated by this procedure was C-dots embedded in the polythene. This pro-
comparing the integrated PL intensities (excited at 360 nm) and duct was washed with water and ethanol and dried in a vacuum
the absorbance values at the same wavelength with that of the qui- chamber. Fig. 11 presents a SEM image of the C-dots embedded
nine sulfate in 0.2 M H2SO4 (quantum yield = 54%). Specifically, the on the polyethylene surface. The typical size of these features is
absorbance values of C-dots and quinine sulfate were measured at between 12 and 22 nm, which is larger than the size of the individ-
360 nm. PL emission spectra of C-dots and quinine sulfate were ual C-dots that were observed before. It is possible that these fea-
also recorded at an excitation wavelength of 360 nm to obtain tures contain clusters of several C-dots which have been
the integrated fluorescence intensity, which is the area under the coagulated under the ultrasonic irradiation.
374 V.B. Kumar et al. / Ultrasonics Sonochemistry 28 (2016) 367–375

Fig. 9. Plots of three consecutive measurements of the Zeta potential of C-dots in PEG/water suspension. The C-dots were formed by 2.5 h sonication at 70% amplitude at
75 °C.

1.0
A QS 800 B
0.8 C-dots

PL Intensity (a.u.)
QS
600
Absorbance

0.6 C-dots

400
0.4

0.2 Abs=0.035, Wavelength=360 nm 200

0.0 0
200 250 300 350 400 450 500 400 450 500 550 600 650 700
Wavelength (nm) Wavelength (nm)

Fig. 10. The quantum yield calculations of C-dots with respect to quinine sulfate (A) Absorbance common peak at 360 nm (B) area under the curve of PL of C-dots and quinine
sulfate.

Table 4
5. Summary
Literature data of quantum yield of pure C-dots from different sources and synthetic
methods. A novel, one-step procedure was developed for the preparation
of high fluorescing C-dots using a sonochemical process. During
Preparation Precursors Reaction conditions Quantum References
method yield the sonication, the collapsing gas bubbles in the liquid act as
micro-reactors in which extreme transient conditions of tempera-
Laser ablation Carbon Catalyst PEG1500N, 4–10% [18]
shoot 120 °C, 72 h ture and pressure are suitable for some decomposition of the PEG
Combustion Candle Washing of Carbon 0.8% [21] medium and formation of C-dots. The fluorescence emission from
shoot nanotube these C-dots is dependent on excitation wavelength. Changes in
Ultrasonic Glucose Catalyst HCl, NaOH, 7% [25]
the formation conditions, such as increasing the power of sonica-
synthesis 4h
Ultrasonic Citric acid Ethylenediamine 1.1% [26]
tion, the duration of ultrasonic irradiation or the reaction temper-
synthesis (NH2/COOH) ature dramatically enhances the amount of the formed C-dots. The
Microwave Saccharide 500 W, 2–10 min 6% [35] C-dots were formed as stable colloidal solution in PEG and have an
pyrolysis, PEG average diameter of 2–7 nm, depending on the preparation condi-
tions. The highest quantum yield obtained for the polyol mediated
C-dots was
16%. The synthesized C-dots were deposited on poly-
thene by sonication.

Acknowledgements

The authors are grateful to Dr. Dan Amir for helping with the
fluorescence measurements and to Dr. Ilana Perelshtein for helping
with the TEM measurement.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in

the online version, at http://dx.doi.org/10.1016/j.ultsonch.2015.08.
005.

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