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Acta Materialia 56 (2008) 259264

www.elsevier.com/locate/actamat

Synthesis and optical properties of CdS quantum dots embedded

in silica matrix thin lms and their applications as luminescent
solar concentrators
S.M. Reda
Chemistry Department, Faculty of Science, Benha University, Benha, Egypt
Received 10 May 2007; received in revised form 9 September 2007; accepted 9 September 2007
Available online 13 November 2007

Abstract
CdS quantum dot (QD) solar concentrators were prepared by a solgel spin coating method. Thin lms were prepared at dierent
annealing temperatures and characterized by X-ray diraction and spectroscopic techniques. The eect of temperature on the optical
properties of CdS QDs embedded in silica matrix was assessed before and after exposure of the samples to sunlight for up to 4 weeks.
The results show that as the annealing temperature increases, the uorescent intensity and Stokes shift decrease. Therefore lower temperatures are preferable for the preparation of highly ecient QD solar concentrator systems.
2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: CdS; Luminescent solar collector; Solgel; Stokes shift

1. Introduction
An interesting approach for conversion of light to electricity is the luminescent at plate concentrator [1]. The
plate contains luminescent particles that absorb the light
and emit part of the absorbed light diusely at a longer
wavelength. The light emitted by the particles is guided
through the plate by total internal reection to a solar cell
tted at the edge (Fig. 1). A fundamental dierence
between the luminescent concentrator compared to other
concentrators is that it concentrates diuse light as well
as direct light, and tracking of the sun is not necessary.
However, the development of such concentrators has been
limited by the performance of luminescent dyes. Recently,
novel luminescent quantum dots (QDs) have been
exploited in an unconventional solar concentrator in which

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the dyes are replaced by QDs [2]. QDs have the following
advantages over dyes: (i) it is possible to tune the absorption threshold by choice of dot diameter; (ii) they can provide high luminescence quantum eciency; and (iii) they
should be inherently more stable than dyes. Moreover,
(iv) the red-shift between absorption and luminescence is
quantitatively related to the spread of QD sizes, which
can be determined during the growth process and allows
losses due to reabsorption to be minimized [2]. QDs in
transparent media, especially in solgel glasses, have
recently received much attention due to their promising
applications in several elds [3]. The solgel process is
based on hydrolysis and condensation reactions of organometallic compounds in alcoholic solutions. The most
widely investigated system involves silica-based glasses
which are prepared by polymerization of a silica alkoxide,
Si(OR)4. The doped SiO2 matrix proved to an excellent
matrix, providing good mechanical and optical properties
and conferring a high kinetic stability on nanometer-size
semiconductor crystallites [4,5]. Among the QDs, cadmium
sulphide (CdS) is an important member of the luminescent

1359-6454/$30.00 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2007.09.017

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S.M. Reda / Acta Materialia 56 (2008) 259264

2.1. Characterization of nanocrystalline CdS-doped silica gel

Solar radiation

Matrix
material

The nanocrystalline CdS-doped silica gels were characterized using X-ray diraction and UVvisible spectroscopic
methods. Optical absorption spectra were recorded using a
PerkinElmer Lambda 40 spectrophotometer. X-ray diraction (XRD) studies were carried out on a Diano Corporation
USA diractometer using Co radiation (k = 0.179 nm).
3. Results and discussion

Quantum dot
Total internal
reflection

Fig. 1. Principle of operation of a quantum dot solar concentrator

(QDSC).

IIVI family, and is a promising material for applications

in biology, solar cells and gas sensors [6].
In spite of the existence of such a large body of work in
this eld, very few reports are available that demonstrate
the control of optical properties of nanoparticles embedded
in thin lm by using solgel technique and its application as
luminescent solar concentrator quantum dots (LSCQDs).
This study reports the solgel synthesis of very stable,
highly luminescent composite thin lms containing CdS
nanoparticles embedded in SiO2 matrix. The eect of drying
temperatures on the optical properties of the nanocrystalline CdS-doped silica glass made using tetraethyorthosilicate Si(OC2H5)4 (TEOS) as a precursor was studied in
order to verify the potential use of this kind of composite
for LSC applications.
2. Experimental
Silica glasses doped with CdS was prepared by hydrolysis and condensation of TEOS using the acid catalyzed procedure. A silica sol was prepared by mixing 7 ml of TEOS
(Aldrich) with 7 ml of ethanol, 8 ml of H2O and 1 ml of
HCl. Cd(NO3)2 4H2O (Merch) and thiourea (Merch) were
used as the precursors for incorporation of Cd and S,
respectively. These precursors were dissolved in ethanol
and distilled water with stirring. The as-prepared solution
was slowly added to the silica sol with vigorous stirring,
and was stirred for 2 h to obtain the nal sol ready for
depositing the thin lms.
The spin-coating technique was used to fabricate thin
lms using the above sol on cleaned quartz glass substrates
rotating at 900 rpm. All the as-deposited lms were
annealed at temperatures ranging from 373 to 673 K, with
100 K intervals, for xed time of 30 min to study the
nucleation and growth of CdS nanoparticles in silica
matrix.

3.1. Characterization
XRD measurements of nanocrystalline CdS-doped silica
were taken by varying the annealing temperature from 373
to 673 K. Fig. 2 shows that as the annealing temperature
increases, the intensity of the peaks increases and the width
of the peaks decreases. Peaks were obtained at 2h values of
24, 26.5, 28, 44, 48 and 52, corresponding to the
(1 0 0), (0 0 2), (1 0 1), (1 1 0), (1 0 3) and (1 1 2) planes, respectively. By comparing the peak proles with standard
ASTM data, the crystal structure was found to be hexagonal wurtzite. The CdS crystallite sizes were determined
from the width of the XRD peak at a 2h value of 44 using
Scherrers equation [4] and are listed in Table 1. It was
found that the crystallite size of CdS increased from 3.5
to 6.5 nm as the annealing temperature increased from
373 to 673 K. This can be attributed to the quantum connement eects of the SiO2 network. When the temperature
increases, the connement eects of the SiO2 network are
weakened, and the CdS crystallites continue to grow.
Optical absorption spectra for the lms of CdS embedded in SiO2 glass at dierent annealing temperatures are
shown in Fig. 3; it can be seen that the lms annealed at
373, 473, 573 and 673 K showed peaks at 405, 450, 470
and 490 nm, respectively. This gradual shift towards longer
wavelengths (red-shift) indicates the growth of the particles
at higher temperatures [7].
The optical band gaps (Eg) of the CdS lms prepared at
dierent annealing temperatures were calculated using the
relation:

373 K
473 K
573 K

Intensity (a.u)

Photovoltaic
cell

673 K

20

30

40

50

60

70

80

2
Fig. 2. X-ray patterns of CdS crystalline-doped silica at dierent
annealing temperatures.

S.M. Reda / Acta Materialia 56 (2008) 259264

261

Table 1
Comparison between particle sizes obtained from XRD and blue-shift of optical band gap (Eg) for CdS lms annealed at dierent temperatures for 30 min
Annealing temperature (K)

Eg (eV)

Particle size from blue-shift (nm)

Particle size from XRD (nm)

373
473
573
673

4.6
3.8
3.2
2.6

3.3
4.2
5.4
6.2

3.5
4.0
5.1
6.5

0.5
573 K
473 K

0.4

Absorbance

373 K
673 K

0.3

0.2

0.1

0
350

400

450

500

550

600

650

700

Wavelength, (nm)
Fig. 3. The change in the absorption peak maxima of nanocrystalline
CdS-doped solgel glass lm with annealing temperatures.
2

ahm Ahm  Eg ;

where a is the optical absorption coecient derived from

the absorption data, hm is the photon energy and A is a constant. The optical band (Eg) can be calculated by plotting
(ahm)2 vs. hm, and is given in Fig. 4. From extrapolating
the straight line to zero photon energy the values of the
band gaps energy were calculated and these are listed in
Table 1. Table 1 shows that there is a clear blue-shift in
the values of the optical band gap with increasing temperature. The change in Eg with the temperature is attributed
to quantum connement eects [4].
The average particle sizes of the CdS nanoparticles in
the lms of the silica matrix were determined using the
blue-shift value in the optical band gaps [7]. The values
obtained via this method match well with that from
XRD and the results are shown in Table 1.

Emission spectra of the CdS embedded in silica matrix

lms subjected to dierent annealing temperatures were
recorded with an excitation wavelength of 410 nm at
room temperature and are shown in Fig. 5. It can be
from Fig. 5 that lms annealed at temperatures of 373,
473, 573 and 673 K showed peaks at 513, 522, 534,
551 nm, respectively. This gradual shift towards longer
wavelength (red-shift) with increasing temperatures may
be due to an increase in particle size [7]. In addition, it
should be noted that there is a gradual increase in intensity of the uorescent peak with decreasing particle size.
This may be attributed to quantum connement of nano
CdS particles in the silica matrix. The shape of the uorescent peaks is smooth indicating low defect content in
the lms [8].
3.2. Photodegradation of CdS QDSCs
To examine the degradation of CdS solar concentrators
with time, samples were measured at intervals over a period
of 4 weeks. Fig. 6 shows a blue-shift in absorbance peak
with time. QDSCs are sensitive to oxygen and light, and
therefore the blue-shifts could be caused by oxidation of
CdS QD surface [9].
3.3. Fluorescence measurements
The uorescence measurements of CdS QDSCs after
exposure to sunlight for 4 weeks are presented in Fig. 7.
The samples have signicantly dierent luminescent intensities. CdS-silica thin lm annealed at 373 K exhibits twice
as much luminescence as all the other types measured.

14
373 K

10

473 K
573 K
673 K

8
6
4
2
0
2.2

2.7

373 K

Fluorescent intensity (a.u)

(h)2x103 (eV/cm)2

12

3.2

3.7

4.2

4.7

h, (eV)
Fig. 4. The change in the optical band gap energy of nanocrystalline CdSdoped solgel glass lm with annealing temperatures.

400

473 K
573 K
673 K

450

500

550

600

650

700

Wavelength, nm
Fig. 5. The change in the emission peak maxima of nanocrystalline CdSdoped solgel glass lm with annealing temperature.

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S.M. Reda / Acta Materialia 56 (2008) 259264

0.45
473 K before

373 K before
0.36

373 K after

0.27

0.27

0.18

0.18

Absorbance

0.09

0
300

473 K after

0.36

0.09

400

500

600

700

0.45

0
300

400

600

700

0.45

673 K before

573 K before
573 K after

673 K after

0.36

0.36

0.27

0.27

0.18

0.18

0.09

0.09

0
300

500

400

500

600

700

0
400

500

600

700

Wavelength, nm

Fluorescent intensity (a.u)

Fig. 6. Absorption spectra for nanocrystalline CdS-doped solgel glass before and after exposure to sunlight for 4 weeks.

400

373 K
473 K
573 K
673 K

450

500

550

600

650

Wavelength, nm
Fig. 7. The change in the emission peak maxima of nanocrystalline CdSdoped solgel glass lm with annealing temperature after exposure to
sunlight for 4 weeks.

Fig. 8 shows that there is a clear blue-shift in the overall

emission spectra for all samples with time. The cause of
this shift may be due to QD aggregation, where the
QDs are absorbing but are not emitting eciently, giving

the appearance of a blue-shift [10]. Due to the highest

luminescence intensity of CdS-silica annealed at lower
temperature (373 K), this QD can be used for solar
concentrator elds.
QDs with a large Stokes shift (change in the ratio of
emitted to absorbed photons) are essential for ecient
QDSCs. As the absorption and emission bands of QDs
overlap, luminescent photons propagating through the
plate are reabsorbed and reemitted successively. However,
if the spectra are well separated, the photon will be
absorbed at one wavelength and reemitted at another;
being absorbed only once by a QD results in higher
QDSC system eciency [10]. The values of Stokes shift
(Dk) before and after exposure to sun light for 4 weeks
for all prepared samples were calculated, and are listed
in Table 2. From Table 2 it can be seen that CdS QDs
annealed at lower temperature (373 K) have the highest
Stokes shift (Dk) compared with the other samples.
Hence, this sample can be used to fabricate high-eciency
QD solar concentrators.

S.M. Reda / Acta Materialia 56 (2008) 259264

263

473 K before

Fluorescent intensity (a.u)

373 K before
373 K after

400

400

450

450

500

500

550

550

600

473 K after

650

400

450

500

550

600

650

573 K before

673 K before

573 K after

673 K after

600

650

400

500

600

700

Wavelength, nm
Fig. 8. Emission spectra for nanocrystalline CdS-doped solgel glass before and after exposure to sunlight for 4 weeks.

Table 2
Spectra characteristics of CdS thin lms annealed at dierent temperatures before and after exposure to sunlight.
Annealing temperature (K)

Exposure time (week)

kabs (nm)

kem (nm)

Dk (nm)

373

0
4
0
4
0
4
0
4

408
390
452
438
471
460
493
483

513
500
522
511
534
526
551
543

105
110
70
73
63
66
58
60

473
573
673

4. Conclusions
We have developed a simple and eective way to fabricate stable, highly luminescent QD solar concentrators.
The solgel process has been applied successfully for preparing thin lms containing CdS nanoparticles in silica
glasses. It was found from XRD that the CdS crystallite
structure in a SiO2 matrix is hexagonal and that the size
of the CdS crystallites increases with increasing annealing

temperature. CdS crystallite sizes of 3.56.5 nm were

obtained from XRD and optical measurements. A red-shift
in the absorption and emission spectra was observed in the
nanocrystalline CdS-doped silica by varying the annealing
temperature from 373 to 673 K due to increasing particle
size. The photostability of CdS QD solar concentrators
was examined after 4 weeks of exposure to sunlight. The
results show that the sample prepared at lower temperature
has the highest uorescent intensity and Stokes shift.

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S.M. Reda / Acta Materialia 56 (2008) 259264

Hence, this sample can be considered as a very ecient QD

solar concentrator.
Acknowledgement
The author is very grateful to the Physics Department,
National Research Center for cooperation and support.
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